WO2009033833A2 - Coloring agent having natural dyes and 1,3-dihydroxyacetone - Google Patents

Coloring agent having natural dyes and 1,3-dihydroxyacetone Download PDF

Info

Publication number
WO2009033833A2
WO2009033833A2 PCT/EP2008/057592 EP2008057592W WO2009033833A2 WO 2009033833 A2 WO2009033833 A2 WO 2009033833A2 EP 2008057592 W EP2008057592 W EP 2008057592W WO 2009033833 A2 WO2009033833 A2 WO 2009033833A2
Authority
WO
WIPO (PCT)
Prior art keywords
group
amino
acid
dyes
alkyl
Prior art date
Application number
PCT/EP2008/057592
Other languages
German (de)
French (fr)
Other versions
WO2009033833A3 (en
Inventor
Thomas Döring
Armin Wadle
Original Assignee
Henkel Ag & Co. Kgaa
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel Ag & Co. Kgaa filed Critical Henkel Ag & Co. Kgaa
Priority to EP08761090A priority Critical patent/EP2182915A2/en
Publication of WO2009033833A2 publication Critical patent/WO2009033833A2/en
Publication of WO2009033833A3 publication Critical patent/WO2009033833A3/en

Links

Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/10—Preparations for permanently dyeing the hair
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/35—Ketones, e.g. benzophenone
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/96—Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution
    • A61K8/97—Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution from algae, fungi, lichens or plants; from derivatives thereof
    • A61K8/9783—Angiosperms [Magnoliophyta]
    • A61K8/9789—Magnoliopsida [dicotyledons]
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/96—Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution
    • A61K8/97—Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution from algae, fungi, lichens or plants; from derivatives thereof
    • A61K8/9783—Angiosperms [Magnoliophyta]
    • A61K8/9794—Liliopsida [monocotyledons]

Definitions

  • the invention relates to agents for coloring keratin fibers, in particular human hair, containing natural dyes and 1, 3-dihydroxyacetone, and its use for coloring keratin fibers and a dyeing process in which these agents are used.
  • oxidation colorants For permanent, intensive colorations with corresponding fastness properties, so-called oxidation colorants are used. Such colorants usually contain oxidation dye precursors, so-called developer components and coupler components. The developer components form under the influence of oxidizing agents or of atmospheric oxygen with one another or with coupling with one or more coupler components, the actual dyes.
  • the oxidation dyes are characterized by excellent, long-lasting dyeing results. For naturally acting dyeings, however, usually a mixture of a larger number of oxidation dye precursors must be used; In many cases, direct dyes are still used for shading.
  • the developer components used are usually primary aromatic amines having a further, in the para or ortho position, free or substituted hydroxy or amino group, heterocyclic hydrazones, diaminopyrazole derivatives and 2,4,5,6-tetraaminopyrimidine and its derivatives.
  • coupler components m-phenylenediamine derivatives, naphthols, pyridine derivatives, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenols are generally used.
  • Particularly suitable as coupler substances are 1-naphthol, 1,5-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinomonomethyl ether, m-phenylenediamine, 1-phenyl 3-methyl-pyrazol-5-one, 2,4-dichloro-3-aminophenol, 1, 3-bis- (2,4-diaminophenoxy) -propane, 2-amino-3-hydroxypyridine, A- Chlororesorcinol, 2-chloro-6-methyl-3-aminophenol, 2-methylresorcinol, 5-methylre
  • dyeing or tinting agents which contain so-called direct drawers as a coloring component. These are dye molecules that attach directly to the substrate and do not require an oxidative process to form the paint. These dyes include, for example, the henna already known from antiquity for coloring body and hair. These dyeings are generally much more sensitive to shampooing than the oxidative dyeings, so that a much more undesirable change in shade or even a visible, homogeneous color loss occurs much more quickly.
  • precursors of the natural hair dye melanin are applied to the substrate, e.g. Hair, applied; These then form naturally-analogous dyes in the course of oxidative processes in the hair.
  • multiple use of agents with 5,6-dihydroxyindoline it is possible to reproduce natural hair color to people with graying hair.
  • the coloration can be done with atmospheric oxygen as the sole oxidant, so that no further oxidizing agents must be used.
  • the indoline can be used as the sole dye precursor.
  • satisfactory results can often only be achieved for use in persons with originally red and, in particular, dark to black hair color, by using other dye components, in particular special oxidation dye precursors.
  • a first class of oxo dye precursors are compounds having at least one reactive carbonyl group. This first class is called a component (Oxo1).
  • a second class of oxo dye precursors form CH-acidic compounds and compounds having primary or secondary amino groups or hydroxy groups, which in turn are selected from compounds of the group formed from primary or secondary aromatic amines, nitrogen-containing heterocyclic compounds and aromatic hydroxy compounds. This second class is called a component (Oxo2).
  • the aforementioned components (oxo1) and (oxo2) are generally not themselves dyes, and therefore are not in themselves suitable for coloring keratin-containing fibers.
  • oxo dyeing In combination, they form dyes in a non-oxidative process of so-called oxo dyeing.
  • the resulting dyeings have partially color fastness on the keratin-containing fiber, which are comparable to those of the oxidation dyeing.
  • the Nuancenspektrum achievable with the gentle oxo staining is very broad and the color obtained often has an acceptable brilliance and color depth.
  • the method of oxo staining can be readily combined with the oxidative staining system.
  • the dyes coloring the substrate are usually decolorized oxidatively using appropriate oxidizing agents, for example hydrogen peroxide.
  • Colorants for coloring keratin-containing fibers, in particular human hair, in which the use of synthetic dyes or dye precursors is dispensed with are based essentially on henna as a natural dye.
  • henna the specialist is only able to achieve a limited spectrum of color nuances, predominantly in the area of red shades.
  • the range of natural hair shades is very difficult to access when using naturally occurring dyes.
  • the dyeings obtained should have a high degree of color fastness, e.g. against sweat, washing, light or friction and must be compatible with other hair treatment products, especially in the context of hair care.
  • Colorants for human hair are already known to the person skilled in the art, in which a combination of dihydroxyacetone with various synthetic oxidation dye precursors is used, as described, for example, in EP1250908 B1 to EP1250912 B1 and in EP1293192 A2.
  • the use of dihydroxyacetone with various synthetic oxidation dye precursors in combination with other ingredients is known in particular from US20050210606 A1 and EP1237817 A2 and EP1237818 A2.
  • vat dyes together with dihydroxyacetone for dyeing hair has been described in WO2005094762 A1 and WO2005094763 A1.
  • all these colorants contain synthetic dyes or dye precursors.
  • a first subject of the invention is therefore an agent for dyeing keratin-containing fibers, in particular human hair, characterized in that it contains 1, 3-dihydroxyacetone and at least one natural dye.
  • inventive agent 1 3-dihydroxyacetone in an amount of 0.1 to 10.0 wt .-%, in particular in an amount of 1, 0 to 5.0 wt .-%, each based on the weight of the agent contains.
  • the agent according to the invention at least one natural dye in an amount of 0.001 to 20.0 wt .-%, in particular in an amount of 0.01 to 15.0 wt .-%, each based on the weight of the composition , contains.
  • natural dyes are harvestable compounds from plant parts which on the one hand represent dyes (i.e., are inherently colored) or compounds recoverable from plant parts which are dye precursors which form the actual dye by subsequent chemical reaction. Mentioned here in particular the oxidation with atmospheric oxygen to form the chromophore.
  • the natural dyes are preferably different parts of plants, depending on the desired dye. It is understood, however, that a dye can be obtained from more than one plant part.
  • the preferred plant parts for obtaining natural dyes are included in the group formed from root, stem, bark, heartwood, resin, flower, leaf, fruit and / or sap.
  • the natural dyes or natural dye precursors are each one of the same compounds. Due to different, non-uniform extraction methods such as different extraction or fermentation conditions or by using different, regional subspecies and different parts of plants or partly from culture-historical tradition, some natural dyes mentioned deliberately contain no uniform compounds, but mixtures of dyes, dye precursors and other components , in particular tannins.
  • a natural dye is understood to mean, of course, a discrete dye isolated from such a mixture, or optionally also a plurality of discrete, coloring compounds isolated from such a mixture.
  • Diaryloylmethane dyes such as, for example, contained in the root of turmeric (Turmeric, Cl.Natural Yellow 3) - Curcuma domestica with the coloring ingredients curcumin (Cl.75300), demethoxycurcumin and bisdemethoxycurcumin.
  • Naphthoquinone dyes such as contained in henna, red (Cl. Natural Orange 6) from the leaves of henna - Lawsonia inermis L with the coloring ingredient Lawson (Cl.75480):
  • alkana root or shikonin root (Cl.Natural Red 20) - Alkanna tinctoria or Lithospermum erythrorhizon with the coloring ingredients alkannane (Cl.75520) and alkannine (Cl.75530) or shikonin (Cl.75535):
  • anthraquinone dyes such as, for example, madder roots (Cl., Natural Red 8), Rubia peregrina and Rubia tinctorum with the coloring constituents purpurin (Cl.75410), pseudopurpurine (Cl.75420, Cl.
  • Indigoid dyes such as, for example, in the leaves and partial stems of Indian Indigo Indigo Farmera (Indigofera argentea), Fawnwort lsatis tinctoria, Dyeing Colanders - Wrightia tinctoria and Wild Indigo - Baptisia tinctoria (CI Natural Blue 1) with the dye precursors lsatan B and Indican, which are oxidatively converted by a fermentation process into the actual dye indigo (Cl.75780, Cl.73000) and subordinated indirubin (Cl.75790, Cl.73200) and isatin:
  • Indirine isatin inter alia, under the name Indigofera folium or Henna, black as a commercial product, mostly in combination with extracts of Lawsonia Inermis, available,
  • flavonoid dyes such as, for example, in the flower heads of Roman chamomile - Chamaemelum nobile (Cl., Natural Yellow 1) and German chamomile - Chamomilla recutica with the coloring constituents apigenin (Cl.75580, CI Natural Yellow 1, 2), rutin (Cl 75530, Natural Yellow 10) and camphor oil (Cl.75460, Cl.Natural Yellow 13, 10) and quercetin (Cl.75670, CI Natural Yellow 10, 13; Cl. Natural Red 1) and glucosides derived therefrom:
  • neoflavanoid dyes such as, for example, in bluewood (Cl.Natural Black 1), heartwood of Haematoxylum campechianum L with the coloring flavonoid quercetin and the dye precursor hematoxylin, which oxidatively binds to hematin dye (CI 75290, CI Natural Black 1 and 2) is converted:
  • insoluble redwood dyes as for example in red sandalwood, heartwood of Pterocarpus santalinus L, Narrawood - Pterocarpus indicus L, Barwood - Pterocarpus soyauxii L, Camwood - Bahia nitida (Cl. Natural Red 22) with the coloring ingredients Santalin A, Santalin B, Tetra-O-methyl - santarubin, hompterocarpine, pterocarpine, maackiain, the isoflavionides formononetin and santal, and the chalcone isoliquiritigenin and the flavone liquiritigenin:
  • Betaine dyes such as beetroot roots - Beta vulgaris containing the main coloring constituents betanidine and prebetanine and subordinate further betacyanines, betaxanthines, vulgaxanthines, anthocyanins and iron and copper complexes:
  • Gallotannin dyes for example in the bark of stalk or summer areas - Quercus robur L. with the main coloring constituents from the group of gallotannins and ellagannins (glycosides of gallic acid or ellagic acid, Cl.75270):
  • condensed tannin dyes as for example in Catechu (CI Natural Brown 3), a mixture of extracts of staining plants, preferably Acacia catechu, Areca catechu and Uncaria gambier, with a high proportion of condensed tannins ('proanthocyanidins') of catechin type:
  • the cosmetic compositions according to the invention contain at least one natural dye from the group comprising diaryloylmethane dyes, naphthoquinone dyes, flavonoid dyes, anthraquinone dyes, betalain dyes, gallotannin dyes and indigoid dyes.
  • Natural dyes preferred according to the present invention are those obtained from a plant selected from the group consisting of Indigofera tinctoria, Curcuma longa, Lawsonia inermis, Chamomilla recutita, Quercus robur, Rosmarinus officinalis, Rheum undulatum and Beta vulgaris.
  • the natural dyes are each preferably used in an amount of from 0.01 to 20% by weight, based on the total application preparation.
  • the total amount of natural dyes is preferably at most 20% by weight.
  • n 1 or 2
  • R is a hydrogen atom or a hydroxymethyl group
  • the compounds of the formula (I) are preferably selected from one or more compounds of the formulas (1-1) to (1-12):
  • Compounds of the formula (I) which are selected from at least one compound from the group formed from D-erythrulose, L-erythrulose, DL-erythrulose, D-ribulose and 2,3,4-trihydroxybutanal, in particular from the group D-erythrulose, L-erythrulose, DL-erythrulose are particularly preferred. It is preferred according to the invention if the agent according to the invention contains the additional carbohydrate according to formula (I) in an amount of 0.1 to 10.0% by weight, in particular in an amount of 2.0 to 6.0% by weight, each based on the weight of the agent contains.
  • agents according to the invention are preferred for the purposes of the invention which do not dispense with further dyes of non-natural origin, in a further embodiment the agents according to the invention may contain at least one color-changing component which is different from the natural dyes according to the invention.
  • the additional color-changing components in the sense of the present invention are preferably selected
  • At least one oxidation dye precursor of the type of developer components and optionally additionally at least one coupler component and / or
  • p-phenylenediamine derivatives of the formula (E1) it may be preferred according to the invention to use as the developer component a p-phenylenediamine derivative or one of its physiologically acceptable salts. Particular preference is given to p-phenylenediamine derivatives of the formula (E1)
  • G 1 represents a hydrogen atom, a (C 1 to C 4 ) -alkyl radical, a (C 1 to C 4 ) monohydroxyalkyl radical, a (C 2 to C 4 ) -polyhydroxyalkyl radical, a (C 1 to C 4 ) -alkoxy - (C 1 -C 4 ) -alkyl radical, a 4'-aminophenyl radical or a (C 1 to C 4 ) -alkyl radical which is substituted by a nitrogen-containing group, a phenyl or a 4'-aminophenyl radical;
  • G 2 represents a hydrogen atom, a (C 1 to C 4 ) -alkyl radical, a (C 1 to C 4 ) monohydroxyalkyl radical, a (C 2 to C 4 ) -polyhydroxyalkyl radical, a (C 1 to C 4 ) -alkoxy - (C 1 -C 4 ) -alkyl radical
  • G 3 represents a hydrogen atom, a halogen atom such as a chlorine, bromine, iodine or fluorine atom, a (C 1 to C 4 ) alkyl radical, a (C 1 to C 4 ) monohydroxyalkyl radical, a (C 2 to C 4 ) -polyhydroxyalkyl radical, a (C 1 to C 4 ) -hydroxyalkoxy radical, a (C 1 to C 4 ) - Acetylaminoalkoxy, a Mesylamino- (Ci to C 4 ) alkoxy or a (Ci to C 4 ) -
  • G 4 represents a hydrogen atom, a halogen atom or a (C 1 to C 4 ) -alkyl radical or, when G 3 and G 4 are ortho to each other, they may together form a bridging ⁇ , ⁇ -alkylenedioxo group, such as, for example, an ethylenedioxy group ,
  • Particularly preferred p-phenylenediamines of formula (E1) are selected from one or more compounds of the group formed from p-phenylenediamine, p-toluenediamine, 2-chloro-p-phenylenediamine, 2,3-dimethyl-p-phenylenediamine , 2,6-dimethyl-p-phenylenediamine, 2,6-diethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, N, N-dimethyl-p-phenylenediamine, N, N-diethyl-p-phenylenediamine , N, N-dipropyl-p-phenylenediamine, 4-amino-3-methyl- (N, N-diethyl) -aniline, N, N-bis ( ⁇ -hydroxyethyl) -p-phenylenediamine, 4-N, N Bis ( ⁇ -hydroxyethyl) amino-2-methylaniline,
  • p-phenylenediamine derivatives of the formula (E1) are selected from at least one compound of the group p-phenylenediamine, p-toluenediamine, 2- (ß-hydroxyethyl) -p-phenylenediamine, 2- ( ⁇ , ß-dihydroxyethyl) - p-phenylenediamine, N, N-bis- ( ⁇ -hydroxyethyl) -p-phenylenediamine, N- (4-amino-3-methylphenyl) -N- [3- (1H-imidazol-1-yl) propyl] amine , as well as the physiologically acceptable salts of these compounds.
  • developer component compounds which contain at least two aromatic nuclei which are substituted by amino and / or hydroxyl groups.
  • binuclear developer components which can be used in the dyeing compositions according to the invention, mention may be made in particular of the compounds corresponding to the following formula (E2) and their physiologically tolerated salts:
  • Z 1 and Z 2 independently of one another represent a hydroxyl or NH 2 radical optionally substituted by a (C 1 to C 4 ) -alkyl radical, by a (C 1 to C 4 ) -hydroxyalkyl radical and / or by a bridge Y
  • the bridging Y is an alkylene group having 1 to 14 carbon atoms, such as a linear or branched alkylene chain or an alkylene ring, which of one or more nitrogen-containing groups and / or one or more heteroatoms such as Oxygen, sulfur or nitrogen atoms may be interrupted or terminated and may be substituted by one or more hydroxyl or (C 1 to C 8 ) alkoxy, or a direct bond,
  • G 5 and G 6 independently of one another represent a hydrogen or halogen atom, a (C 1 to C 4 ) -alkyl radical, a (C 1 to C 4 ) -monohydroxyalkyl radical, a (C 2 to C 4 ) -hydroxyalkyl radical, a ( C 1 to C 4 ) -aminoalkyl radical or a direct compound for bridging Y,
  • G 7 , G 8 , G 9 , G 10 , G 11 and G 12 independently represent a hydrogen atom, a direct bond to the bridge Y or a (C 1 to C 4 ) alkyl radical, with the proviso that the compounds of the Formula (E2) contain only one bridge Y per molecule.
  • Preferred binuclear developer components of the formula (E2) are in particular selected from at least one of the following compounds: N, N'-bis- ( ⁇ -hydroxyethyl) -N, N'-bis- (4'-aminophenyl) -1,3-diamino -propan-2-ol, N, N'-bis ( ⁇ -hydroxyethyl) -N, N'-bis (4'-aminophenyl) ethylenediamine, N, N'-bis (4'-aminophenyl) - tetramethylenediamine, N, N'-bis ( ⁇ -hydroxyethyl) -N, N'-bis (4'-aminophenyl) tetramethylenediamine, N, N'-bis (4- (methylamino) phenyl) tetramethylenediamine, N , N'-diethyl-N, N'-bis (4'-amino-3'-methylphenyl) ethylenediamine,
  • Very particularly preferred binuclear developer components of the formula (E2) are selected from N, N'-bis ( ⁇ -hydroxyethyl) -N, N'-bis (4-aminophenyl) -1,3-diamino-propan-2-ol , Bis (2-hydroxy-5-aminophenyl) -methane, 1, 3-bis (2,5-diaminophenoxy) -propan-2-ol, N, N'-bis (4-aminophenyl) -1, 4-diazacycloheptane, 1, 10-bis (2,5-diaminophenyl) -1, 4,7,10-tetraoxadecane or one of the physiologically acceptable salts of these compounds.
  • p-aminophenol derivatives of the formula (E3) in which:
  • G 13 represents a hydrogen atom, a halogen atom, a (C 1 to C 4 ) -alkyl radical, a (C 1 to C 4 ) -monohydroxyalkyl radical, a (C 2 to C 4 ) -polyhydroxyalkyl radical, a (C 1 to C 4 ) Alkoxy (C 1 to C 4 ) -alkyl radical, a (C 1 to C 4 ) -aminoalkyl radical, a hydroxy (C 1 -C 4 ) -alkylamino radical, a (C 1 to C 4 ) -hydroxyalkoxy radical, a (C 1 to C 4 ) -hydroxyalkyl- (C 1 -C 4 ) -aminoalkyl radical or a (DK (C 1 to C 4 ) -alkyl] amino) - (C 1 -C 4 ) -alkyl radical
  • G 14 represents a hydrogen or halogen atom, a (
  • Preferred p-aminophenols of the formula (E3) are, in particular, p-aminophenol, N-methyl-p-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 2-hydroxymethylamino-4-aminophenol, 4 -Amino-3-hydroxymethylphenol, 4-amino-2- ( ⁇ -hydroxyethoxy) -phenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethyl-phenol, 4-amino -2-aminomethylphenol, 4-amino-2- ( ⁇ -hydroxyethyl-aminomethyl) phenol, 4-amino-2- ( ⁇ , ⁇ -dihydroxyethyl) phenol, 4-amino-2-fluorophenol, 4-amino-2 -chlorophenol, 4-amino-2,6-dichlorophenol, 4-amino-2- (diethyl-aminomethyl) -phenol and their physiological
  • Very particularly preferred compounds of the formula (E3) are p-aminophenol, 4-amino-3-methylphenol, 4-amino-2-aminomethylphenol, 4-amino-2- ( ⁇ , ⁇ -dihydroxyethyl) -phenol and A-amino- 2- (diethylaminomethyl) -phenol.
  • the developer component may be selected from o-aminophenol and its derivatives such as 2-amino-4-methylphenol, 2-amino-5-methylphenol or 2-amino-4-chlorophenol.
  • the developer component may be selected from heterocyclic developer components, such as pyrimidine derivatives, pyrazole derivatives, pyrazolopyrimidine derivatives or their physiologically acceptable salts.
  • heterocyclic developer components such as pyrimidine derivatives, pyrazole derivatives, pyrazolopyrimidine derivatives or their physiologically acceptable salts.
  • Preferred pyrimidine derivatives are selected according to the invention from compounds of the formula (E4) or their physiologically tolerated salts,
  • G 17 , G 18 and G 19 independently represent a hydrogen atom, a hydroxy group, a
  • G 20 represents a hydroxy group or a group -NG 21 G 22 , in which G 21 and G 22 independently of one another represent a hydrogen atom, a (C 1 to C 4 ) -alkyl group, a (C 1 to C 4 ) -
  • Particularly preferred pyrimidine derivatives are in particular the compounds 2,4,5,6-tetra-aminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2-dimethylamino-4 , 5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine and 2,5,6-triaminopyrimidine.
  • Preferred pyrazole derivatives are selected according to the invention from compounds of the formula (E5),
  • G 23, G 24, G 25 are each independently a hydrogen atom, a (C 1 to C 4) - alkyl group, a (C 1 to C 4) monohydroxyalkyl, a (C 2 to C 4) alkyl group -Polyhydroxy-, an optionally substituted aryl group or an optionally substituted AlyI- (C 1 to C 4 ) -alkyl group, with the proviso that when G 25 is a hydrogen atom, G 26 may additionally be a group - NH 2 in addition to the abovementioned groups,
  • G 26 represents a hydrogen atom, a (C 1 to C 4 ) alkyl group, a (C 1 to C 4 ) monohydroxyalkyl group or a (C 2 to C 4 ) polyhydroxyalkyl group and G 27 represents a hydrogen atom, an optionally substituted aryl group, a (Ci to C 4) alkyl group or a (C 1 to C 4) -monohydroxyalkyl, especially for a hydrogen atom or a methyl group.
  • the radical -NG 25 G 26 binds to the 5 position and the radical G 27 to the 3 position of the pyrazole cycle.
  • Particularly preferred pyrazole derivatives are in particular the compounds which are selected from 4,5-diamino-1-methylpyrazole, 4,5-diamino-1- ( ⁇ -hydroxyethyl) pyrazole, 3,4-diaminopyrazole, 4,5- Diamino-1- (4'-chlorobenzyl) -pyrazole, 4,5-diamino-1,3-dimethylpyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole, 4,5-diamino-1-methyl-3 phenylpyrazole, 4-amino-1,3-dimethyl-5-hydrazinopyrazole, 1-benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3-tert-butyl-1-methylpyrazole, 4 5-diamino-1-tert-butyl-3-methylpyrazole, 4,5-diamino-1- ( ⁇ -hydroxyethy
  • Preferred pyrazolopyrimidine derivatives are, in particular, the derivatives of the pyrazolo [1,5-a] pyrimidine of the following formula (E6) and their tautomeric forms, if a tautomeric equilibrium exists:
  • G 28 , G 29 and G 30 , G 31 independently of one another represent a hydrogen atom, a (C 1 to C 4 ) -alkyl radical, an aryl radical, a (C 1 to C 4 ) -monohydroxyalkyl radical, a (C 2 to C 4 ) - Polyhydroxyalkylrest a (Ci to C 4 ) -Alkoxy- (Ci to C 4 ) -alkylrest, a (Ci to C 4 ) - Aminoalkylrest, which can be protected if necessary by a Acetyl Ureid or a Sulfonyl remainder, one (C 1 to C 4) alkylamino (C- ⁇ -C 4) alkyl, a di - [(C- ⁇ -C 4) - alkyl] - (C- ⁇ -C 4) aminoalkyl radical, wherein the Dialkyl radicals optionally form a carbon cycle or a heterocycle having 5 or 6 chain members
  • Sulfonic acid group i has the value 0, 1, 2 or 3
  • p has the value 0 or 1
  • q has the value 0 or 1
  • n has the value 0 or 1, with the proviso that the sum of p + q unequal 0 is - if p + q is 2, n is 0, and the groups NG 28 G 29 and NG 30 G 31 occupy the
  • Group OH occupy the positions (2,3); (5,6); (6,7); (3,5) or (3,7).
  • pyrazolo [1, 5-a] pyrimidines of the above formula (E6) can be prepared as described in the literature by cyclization from an aminopyrazole or from hydrazine.
  • Very particularly preferred developer components are selected from at least one compound from the group formed from p-phenylenediamine, p-toluenediamine, 2- ( ⁇ -hydroxyethyl) -p-phenylenediamine, 2- ( ⁇ , ⁇ -dihydroxyethyl) -p phenylenediamine, N, N-bis ( ⁇ -hydroxyethyl) -p-phenylenediamine, N- (4-amino-3-methylphenyl) -N- [3- (1 H -imidazol-1-yl) propyl] amine, N, N'-bis ( ⁇ -hydroxyethyl) -N, N'-bis (4-aminophenyl) -1, 3-diamino-propan-2-ol, bis (2-hydroxy-5-aminophenyl) - methane, 1,3-bis- (2,5-diaminophenoxy) -propan-2-ol, N, N'-bis (4-amin
  • Examples of (C 1 to C 4 ) -alkoxy radicals according to the invention are -OCH 3 , -OCH 2 CH 3 ,
  • a particularly preferred example of a (C 2 to C 4 ) polyhydroxyalkyl group is 1, 2
  • halogen atoms are F, Cl or Br atoms, Cl atoms are very particularly preferred examples.
  • nitrogen-containing groups are in particular -NH 2 , (C 1 to C 4 ) -
  • Trialkylammonium groups (C 1 to C 4 ) monohydroxyalkylamino groups, imidazolinium and
  • Examples of (C 1 to C 4 ) -monoalkylamino groups are -NHCH 3 , -NHCH 2 CH 3 , -NHCH 2 CH 2 CH 3 ,
  • (C 1 to C 4 ) -dialkylamino groups are -N (CH 3 ) 2 , -N (CH 2 CH 3 ) 2 .
  • Examples of (C 1 to C 4 ) trialkylammonium groups are -N + (CH 3 ) 3 , -N + (CH 3 ) 2 (CH 2 Cl-I 3 ), -N + (CH 3 ) (CH 2 CH 3 2 .
  • Examples of (C 1 to C 4 ) -hydroxyalkylamino radicals are -NH-CH 2 CH 2 OH, -NH-CH 2 CH 2 OH, -NH-CH 2 CH 2 CH 2 OH 1 -NH-CH 2 CH 2 CH 2 OH.
  • Examples of (C 1 to C 4 ) -alkoxy- (C 1 -C 4 ) -alkyl groups are the groups -CH 2 CH 2 -O-CH 3 , -CH 2 CH 2 CH 2 -O-CH 3 , - CH 2 CH 2 -O-CH 2 CH 3 , -CH 2 CH 2 CH 2 -O-CH 2 CH 3 , -CH 2 CH 2 -O-CH (CH 3 ), -CH 2 CH 2 CH 2 -O -CH (CH 3 ).
  • hydroxy (C 1 -C 4 ) -alkoxy radicals are -O-CH 2 OH, -O-CH 2 CH 2 OH, -O-CH 2 CH 2 CH 2 OH, -O-CHCH (OH) CH 3 , -O-CH 2 CH 2 CH 2 CH 2 OH.
  • Examples of (C 1 to C 4 ) -acetylaminoalkoxy radicals are -O-CH 2 NHC (O) CH 3 , -O-CH 2 CH 2 NHC (O) CH 3 ,
  • (C 1 to C 4 ) carbamoylaminoalkoxy radicals are -O-CH 2 CH 2 -NH-C (O) -NH 2 , -O-CH 2 CH 2 CH 2 -NH-C (O) -NH 21 - O-CH 2 CH 2 CH 2 CH 2 -NH-C (O) -NH 2 .
  • Examples of (C 1 to C 4 ) -aminoalkyl radicals are -CH 2 NH 2 , -CH 2 CH 2 NH 2 , -CH 2 CH 2 CH 2 NH 2 , -CH 2 CH (NH 2 ) CH 31 -CH 2 CH 2 CH 2 CH 2 NH 2 .
  • Examples of (C 1 to C 4 ) -cyanoalkyl radicals are -CH 2 CN 1 -CH 2 CH 2 CN 1 -CH 2 CH 2 CH 2 CN.
  • Examples of (C 1 to C 4) -Hydroxyalkylamino- (Ci to C 4) alkyl groups are -CH 2 CH 2 NH-CH 2 CH 2 OH 1 -CH 2 CH 2 CH 2 NH-CH 2 CH 2 OH 1 - CH 2 CH 2 NH-CH 2 CH 2 CH 2 OH 1 -CH 2 CH 2 CH 2 NH-CH 2 CH 2 CH 2 OH.
  • Examples of di [(d to C 4 ) -hydroxyalkyl] amino- (C 1 -C 4 ) -alkyl radicals are CH 2 CH 2 N (CH 2 CH 2 OH) 21
  • aryl groups is the phenyl group.
  • aryl (C 1 -C 4 ) -alkyl groups are the benzyl group and the 2-phenylethyl group.
  • compositions according to the invention which comprise precursors of naturally-analogous dyes are preferably used as air-oxidative colorants. Consequently, in this embodiment said compositions are not added with an additional oxidizing agent.
  • Particularly suitable precursors of naturally-analogous hair dyes are derivatives of 5,6-dihydroxyindoline of the formula (E7), in the independently of each other
  • R 1 is hydrogen, a C 1 -C 4 -alkyl group or a C 1 -C 4 -hydroxy-alkyl group
  • R 2 is hydrogen or a -COOH group, where the -COOH group may also be present as a salt with a physiologically compatible cation
  • R 3 is hydrogen or a C 1 -C 4 -alkyl group
  • R 4 is hydrogen, a dC 4 alkyl group or a group -CO-R 6 , in which R 6 is a C-
  • indoline Particularly preferred derivatives of indoline are 5,6-dihydroxyindoline, N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6 - Dihydroxyindolin and 5,6-dihydroxyindoline-2-carboxylic acid.
  • N-methyl-5,6-dihydroxyindoline N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline and especially 5, 6-Dihydroxyindolin.
  • R 1 is hydrogen, a C 1 -C 4 -alkyl group or a C 1 -C 4 -hydroxyalkyl group
  • R 2 is hydrogen or a -COOH group, wherein the -COOH group may also be present as a salt with a physiologically compatible cation,
  • R 3 is hydrogen or a C 1 -C 4 -alkyl group
  • R 4 is hydrogen, a dC 4 alkyl group or a group -CO-R 6 , in which R 6 is a C-
  • R 5 represents one of the groups mentioned for R 4, and physiologically compatible salts of these compounds with an organic or inorganic acid.
  • Particularly preferred derivatives of indole are 5,6-dihydroxyindole, N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6- dihydroxyindole, 5,6-dihydroxyindole-2-carboxylic acid.
  • N-methyl-5,6-dihydroxyindole N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole, and especially the 5,6 -Dihydroxyindol.
  • the indoline or the indole derivatives can be used both as free bases and in the form of their physiologically acceptable salts with inorganic or organic acids, eg. As the hydrochlorides, sulfates and hydrobromides are used.
  • Coupler components do not form a significant color within the framework of the oxidative dyeing alone, but always require the presence of developer components. Therefore, it is preferred according to the invention that at least one coupler component is additionally used when using at least one developer component.
  • Coupler components according to the invention allow at least one substitution of a chemical residue of the coupler by the oxidized form of the developer component. This forms a covalent bond between the coupler and the developer component.
  • Couplers are preferably cyclic compounds which carry on cycle at least two groups selected from (i) optionally substituted amino groups and / or (ii) hydroxy groups. When the cyclic compound is a six-membered ring (preferably aromatic), said groups are preferably in ortho position or meta position to each other.
  • Coupler components according to the invention are preferably selected as at least one compound from one of the following classes:
  • o-aminophenol derivatives such as o-aminophenol
  • Naphthalene derivatives having at least one hydroxy group having at least one hydroxy group
  • Pyrazolone derivatives such as 1-phenyl-3-methylpyrazol-5-one,
  • Morpholine derivatives such as, for example, 6-hydroxybenzomorpholine or 6-aminobenzomorpholine,
  • m-aminophenols or derivatives thereof which can be used according to the invention are preferably selected from at least one compound of the formula (K1) and / or from at least one physiologically tolerated salt of a compound of the formula (K1),
  • G 1 and G 2 independently represent a hydrogen atom, a (Ci to C 4) - alkyl group, a (C 3 -C 6) cycloalkyl group, a (C 2 to C 4) alkenyl group, a (C 1 to C 4) monohydroxyalkyl, a (C 2 to C 4) -polyhydroxyalkyl group, a (C 2 to C 4) -Perfluoracyl distr, an aryl (C- ⁇ -C 6) alkyl group, a AmJnO- (C 1 to C 6 ) alkyl group, a (C 1 to C 6) dialkylamino (C- ⁇ alkyl to C 6) or a (C 1 to C 6) alkoxy (C- ⁇ -C 6) alkyl group, wherein G 1 and G 2 together with the nitrogen atom can form a five-membered, six-membered or seven-membered ring,
  • G 3 and G 4 independently represent a hydrogen atom, a halogen atom, a (C 1 to C 4 ) alkyl group, a (C 1 to C 4 ) alkoxy group, a hydroxy group, a (C 1 to C 4 ) monohydroxyalkyl group , a (C 2 to C 4 ) polyhydroxyalkyl group, a hydroxy (C 1 to C 4 ) alkoxy group, a (C 1 to C 6 ) -alkoxy (C 2 to C 6 ) alkoxy group, an aryl group or a heteroaryl.
  • Particularly preferred m-aminophenol coupler components are selected from at least one compound selected from the group consisting of m-aminophenol, 5-amino-2-methylphenol, N-cyclopentyl-3-aminophenol, 3-amino-2-chloro-6 -methylphenol, 2-hydroxy-4-aminophenoxyethanol, 2,6-dimethyl-3-aminophenol, 3-trifluoroacetylamino-2-chloro-6-methylphenol, 5-amino-4-chloro-2-methylphenol, 5-amino-4 -methoxy-2-methylphenol, 5- (2'-hydroxyethyl) amino-2-methylphenol, 3- (diethylamino) -phenol, N-cyclopentyl-3-aminophenol, 1, 3-dihydroxy-5- (methylamino) - benzene, 3-ethylamino-4-methylphenol, 2,4-dichloro-3-aminophenol and the physiologically acceptable salts of all the abovementioned compounds.
  • m-diaminobenzenes or derivatives thereof which can be used according to the invention are preferably selected from at least one compound of the formula (K2) and / or from at least one physiologically tolerated salt of a compound of the formula (K2), wherein
  • G 5, G 6, G 7 and G 8 are independently a hydrogen atom, a (Ci to C 4) - alkyl group, a (C 3 -C 6) cycloalkyl group, a (C 2 to C 4) - alkenyl group, a (Ci to C 4) monohydroxyalkyl, a (C 2 to C 4) - polyhydroxyalkyl group, a (C 1 to C 4) alkoxy alkyl (C- ⁇ -C 4), aryl (C- ⁇ to C 4 ) alkyl group, a heteroaryl (C 1 -C 4 ) -alkyl group, a (C 2 to C 4 ) perfluoroacyl group, or together with the nitrogen atom form a five-membered or six-membered heterocycle
  • G 9 and G 10 independently of one another represent a hydrogen atom, a halogen atom, a (C 1 to C 4 ) -alkyl group, an ⁇ - (2,4-diaminophenyl) - (C 1 -C 4 ) -alkyl group, an ⁇ - (2,4-Diaminophenyloxy) - (C- 1 to C 4 ) alkoxy, a (C 1 to C 4 ) alkoxy, a hydroxy group, a (C 1 to C 4 ) alkoxy (C 2 to C 4) alkoxy group, an aryl group, a heteroaryl group, a (C 1 to C 4) monohydroxyalkyl, a (C 2 to C 4) -polyhydroxyalkyl group, a hydroxy (C- ⁇ -C 4) alkoxy.
  • Particularly preferred m-diaminobenzene coupler components are selected from at least one compound from the group formed from m-phenylenediamine, 2- (2,4-diaminophenoxy) ethanol, 1, 3-bis (2,4-diaminophenoxy) propane, 1-Methoxy-2-amino-4- (2'-hydroxyethylamino) benzene, 1, 3-bis (2,4-diaminophenyl) propane, 2,6-bis (2'-hydroxyethylamino) -1-methylbenzene, 2- ( ⁇ 3 - [(2-hydroxyethyl) amino] -4-methoxy-5-methylphenyl ⁇ amino) ethanol, 2 - ( ⁇ 3 - [(2-hydroxyethyl) amino] -2-methoxy-5-methylphenyl ⁇ amino) ethanol, 2 - ( ⁇ 3 - [(2-hydroxyethyl) amino] -4,5-dimethylphenyl ⁇ amino) ethanol, 2- [3-morpholin-4
  • o-diaminobenzenes or their derivatives which can be used according to the invention are preferably selected from at least one compound of the formula (K3) and / or from at least one physiologically tolerated salt of a compound of the formula (K3), wherein
  • G 11, G 12, G 13 and G 14 are independently a hydrogen atom, a (Ci to C 4) - alkyl group, a (C 3 -C 6) cycloalkyl group, a (C 2 to C 4) - alkenyl group, a (C 1 to C 4) monohydroxyalkyl, a (C 2 to C 4) - polyhydroxyalkyl group, a (C 1 to C 4) alkoxy alkyl (C- ⁇ -C 4), aryl (d to C 4 ) alkyl group, a heteroaryl (C-1 to C 4 ) alkyl group, a (C 2 to C 4 ) perfluoroacyl group, or together with the nitrogen atom form a five-membered or six-membered heterocycle
  • G 15 and G 16 independently represent a hydrogen atom, a
  • Halogen atom a carboxyl group, a (C 1 to C 4 ) alkyl group, a (C 1 to C 4 ) alkoxy group, a hydroxy group, a (C 1 to C 4 ) monohydroxyalkyl group, a (C 2 to C 4 ) - Polyhydroxyalkyl group, a hydroxy (C- ⁇ to C 4 ) alkoxy group.
  • Particularly preferred o-diaminobenzene coupler components are selected from at least one compound selected from the group consisting of 3,4-diaminobenzoic acid and 2,3-diamino-1-methylbenzene and the physiologically acceptable salts of all of the aforementioned compounds.
  • Preferred di- or trihydroxybenzenes and their derivatives are selected from at least one compound of the group formed from resorcinol, resorcinol monomethyl ether, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 2-chlororesorcinol, 4-chlororesorcinol, pyrogallol and 1 , 2,4-trihydroxybenzene.
  • the pyridine derivatives which can be used according to the invention are preferably selected from at least one compound of the formula (K4) and / or from at least one physiologically tolerable salt of a compound of the formula (K4),
  • G 17 and G 18 independently of one another represent a hydroxyl group or a group - NG 21 G 22 , wherein G 21 and G 22 are independently a hydrogen atom, a (C 1 to C 4 ) alkyl group, a (C 3 to C 6 ) cycloalkyl group, a (C 2 to C 4 ) alkenyl group, an aryl group, a (C 1 to C 4) monohydroxyalkyl, a (C 2 to C 4) -polyhydroxyalkyl group, a (C 1 to C 4) alkoxy (C- ⁇ -C 4) - alkyl group, an aryl (d-C 4 ) -alkyl group, a heteroaryl (C 1 -C 4 ) -alkyl group,
  • G 19 and G 20 independently of one another represent a hydrogen atom, a halogen atom, a (C 1 to C 4 ) -alkyl group or a (C 1 to C 4 ) -alkoxy group.
  • radicals G 17 and G 18 are in the ortho position or in the meta position relative to one another.
  • Particularly preferred pyridine derivatives are selected from at least one compound of the group formed from 2,6-dihydroxypyridine, 2-amino-3-hydroxypyridine, 2-amino-5-chloro-3-hydroxypyridine, 3-amino-2-methylamino 6-methoxypyridine, 2,6-dihydroxy-3,4-dimethylpyridine, 2,6-dihydroxy-4-methylpyridine, 2,6-diaminopyridine, 2,3-diamino-6-methoxypyridine, 3,5-diamino-2, 6-dimethoxypyridine, 3,4-diaminopyridine, 2- (2-methoxyethyl) amino-3-amino-6-methoxypyridine, 2- (4'-methoxyphenyl) amino-3-aminopyridine, and the physiologically acceptable salts of the aforementioned compounds.
  • Preferred naphthalene derivatives having at least one hydroxy group are selected from at least one compound of the group formed from 1-naphthol, 2-methyl-1-naphthol, 2-hydroxymethyl-1-naphthol, 2-hydroxyethyl-1-naphthol, 1, 3 Dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,7-dihydroxynaphthalene and 2,3-dihydroxynaphthalene.
  • the indole derivatives which can be used according to the invention are preferably selected from at least one compound of the formula (K5) and / or from at least one physiologically tolerated salt of a compound of the formula (K5),
  • G 23 is a hydrogen atom, a (C 1 to C 4 ) -alkyl group, a (C 3 to C 6 ) -
  • Cycloalkyl group a (C 2 to C 4 ) alkenyl group, a (C 1 to C 4 ) -
  • Monohydroxyalkyl group a (C 2 to C 4 ) polyhydroxyalkyl group, an aryl (d to C 4 ) alkyl group
  • G 24 represents a hydroxy group or a group -NG 26 G 27 , wherein G 26 and G 27 are independently a hydrogen atom, a (C 1 to C 4 ) alkyl group, a (C 3 to C 6 ) - Cycloalkyl group, a (C 2 to C 4 ) alkenyl group, a (Ci to C 4 ) -
  • Monohydroxyalkyl group a (C 2 to C 4 ) polyhydroxyalkyl group, G 25 hydrogen atom, a halogen atom or a (C 1 to C 4 ) alkyl group, with the proviso that G 24 is in the meta position or ortho position to the structural fragment NG 23 the formula binds.
  • Particularly preferred indole derivatives are selected from at least one compound of the group which is formed from 4-hydroxyindole, 6-hydroxyindole and 7-hydroxyindole and the physiologically acceptable salts of the abovementioned compounds.
  • the indoline derivatives which can be used according to the invention are preferably selected from at least one compound of the formula (K6) and / or from at least one physiologically tolerable salt of a compound of the formula (K6),
  • G 28 represents a hydrogen atom, a (C 1 to C 4 ) alkyl group, a (C 3 to C 6 ) cycloalkyl group, a (C 2 to C 4 ) alkenyl group, a (C 1 to C 4 ) monohydroxyalkyl group , a (C 2 to C 4 ) -polyhydroxyalkyl group, an aryl- (C 1 -C 4 ) -alkyl group,
  • G 29 represents a hydroxy group or a group -NG 31 G 32 , in which G 31 and G 32 independently of one another represent a hydrogen atom, a (C 1 to C 4 ) -alkyl group, a (C 3 to C 6 ) -cycloalkyl group, a (C 2 to C 4 ) alkenyl group, a (C 1 to C 4 ) monohydroxyalkyl group, a (C 2 to C 4 ) polyhydroxyalkyl group,
  • G 30 is a hydrogen atom, a halogen atom or a (C 1 to C 4 ) alkyl group, with the proviso that G 29 in the meta position or ortho position to the structural fragment NG 28 of
  • Particularly preferred indoline derivatives are selected from at least one compound of the group formed from 4-hydroxyindoline, 6-hydroxyindoline and 7-hydroxyindoline and the physiologically acceptable salts of the aforementioned compounds.
  • Preferred pyrimidine derivatives are selected from at least one compound of the group formed from 4,6-diaminopyrimidine, 4-amino-2,6-dihydroxypyrimidine, 2,4-diamino-6-hydroxypyrimidine, 2,4,6-trihydroxypyrimidine, 2 -Amino-4-methylpyrimidine, 2-amino-4-hydroxy-6-methylpyrimidine and 4,6-dihydroxy-2-methylpyrimidine and the physiologically acceptable salts of the aforementioned compounds.
  • coupler components according to the invention are selected from m-aminophenol, 5-amino-2-methylphenol, 3-amino-2-chloro-6-methylphenol, 2-hydroxy-4-aminophenoxyethanol, 5-amino-4-chloro-2-methylphenol , 5- (2'-hydroxyethyl) amino-2-methylphenol, 2,4-dichloro-3-aminophenol, o-aminophenol, m-phenylenediamine, 2- (2,4-diaminophenoxy) ethanol, 1,3-bis (2,4-diaminophenoxy) propane, 1-methoxy-2-amino-4- (2'-hydroxyethylamino) benzene, 1, 3-bis (2,4-diaminophenyl) propane, 2,6-bis (2'-bis) hydroxyethylamino) -1-methylbenzene, 2 - ( ⁇ 3 - [(2-hydroxyethyl) amino] -4-methoxy-5-methylphenyl ⁇
  • the coupler components are preferably used in an amount of 0.005 to 20 wt .-%, preferably 0.1 to 5 wt .-%, each based on the ready oxidation dye.
  • developer components and coupler components are generally used in approximately molar amounts to each other.
  • a certain excess of individual oxidation dye precursors is not disadvantageous, so that developer components and coupler components in a molar ratio of 1: 0.5 to 1: 3, in particular 1: 1 to 1: 2 , can stand.
  • Inventive examples of (C 3 to C 6 ) -cycloalkyl groups are the cyclopropyl, the
  • Examples of (C 1 to C 4 ) -alkoxy radicals according to the invention are -OCH 3 , -OCH 2 CH 3 ,
  • Group -CH 2 CH 2 OH is preferred.
  • a particularly preferred example of a (C 2 to C 4 ) polyhydroxyalkyl group is the 1, 2-Dihyd roxyethylg ru ppe.
  • halogen atoms are F, Cl or Br atoms, Cl atoms are very particularly preferred examples.
  • nitrogen-containing groups are especially -NH 2, (C 1 to C 4) - monoalkylamino, (C 1 -C 4) -dialkylamino, (C 1 to C 4) - trialkylammonium groups, (C 1 to C 4) -Monohydroxyalkylamino phenomenon, Imidazolinium and - NH 3 + .
  • Examples of (C 1 to C 4 ) monoalkylamino groups are -NHCH 3 , -NHCH 2 CH 3 , -NHCH 2 CH 2 CH 3 , -NHCH (CH 3 ) 2 .
  • Examples of (C 1 to C 4 ) -dialkylamino group are -N (CH 3 ) 2 , -N (CH 2 CH 3 ) 2 .
  • Examples of (C 1 to C 4) alkoxy (C- ⁇ -C 4) -alkyl groups are the groups -CH 2 CH 2 -O-CH 3, - (- / H 2 (_ / H 2 (- / H 2 -O - (- / H 3 , - (H 2 / H 2 (- / H 2 -O - (- / H 2 (- / H 3 , - (_ / H 2 (_ / H 2 (- / H 2 -O - (- / H 2 (- / H 3 , - (H 2 / H 2 - / H 2 -O - (- / H ((- / H 3 ) 2 , -CH 2 CH 2 CH 2 -O-CH (CH 3 ) 2 .
  • Examples of (C 1 to C 4 ) -alkoxy- (C 1 -C 4 ) -alkoxy groups are the groups -O-CH 2 CH 2 -O-CH 3 , -O-CH 2 CH 2 CH 2 -O- CH 3, -0-CH 2 CH 2 -O-CH 2 CH 3, -0-CH 2 CH 2 CH 2 -O-CH 2 CH 3, -0-CH 2 CH 2 -O- CH (CH 3) 2 ,
  • hydroxy- (C- ⁇ -C 4) alkoxy groups are -0-CH 2 OH, -0-CH 2 CH 2 OH, -0-CH 2 CH 2 CH 2 OH, -O-CH 2 CH (OH ) CH 3 , -O-CH 2 CH 2 CH 2 CH 2 OH.
  • Examples of (C 1 to C 4 ) -aminoalkyl radicals are -CH 2 NH 2 , -CH 2 CH 2 NH 2 , -CH 2 CH 2 CH 2 NH 2 , -CH 2 CH (NH 2 ) CH 31 -CH 2 CH 2 CH 2 CH 2 NH 2 .
  • aryl groups is the phenyl group, which may also be substituted.
  • aryl (C 1 to C 4 ) alkyl groups are the benzyl group and the 2-phenylethyl group.
  • Preferred oxo dye precursors are a combination of at least one compound containing at least one reactive carbonyl group (component (oxo 1)) with at least one compound (component oxo2) compounds selected from (oxo2a) CH-acidic compounds and / or
  • Reactive carbonyl compounds as component (oxo1) have in the context of the invention at least one carbonyl group as a reactive group which reacts with the component (oxo2) to form a covalent bond.
  • Preferred reactive carbonyl compounds are selected from compounds which carry at least one formyl group and / or at least one keto group, in particular at least one formyl group.
  • those compounds according to the invention are also suitable as component (Oxo1) in which the reactive carbonyl group is derivatized or masked such that the reactivity of the carbon atom of the derivatized carbonyl group with respect to the component (Oxo2) is always present.
  • These derivatives are preferably addition compounds a) of amines and their derivatives to form imines or oximes as addition compound b) of alcohols to form acetals or ketals as addition compound c) of water to form hydrates as addition compound (component (Oxo1) is derived in in this case c) from an aldehyde) to the carbon atom of the carbonyl group of the reactive carbonyl compound.
  • Preferred reactive carbonyl compounds of the component (oxo1) are selected from the group consisting of benzaldehyde and its derivatives, naphthaldehyde and its derivatives, cinnamaldehyde and its derivatives, 2-formylmethylene-1,3,3-trimethylindoline (Fischer's aldehyde or tribasic aldehyde), 2-indolaldehyde, 3-indolaldehyde, 1-methylindole-3-aldehyde, 2-methylindole-3-aldehyde, 2- (1 ', 3', 3'-trimethyl-2-indolinylidene) -acetaldehyde, 1-methylpyrrole-2 aldehyde, pyridoxal, antipyrin-4-aldehyde, furfural, 5-nitrofurfural, chromone-3-aldehyde, 3- (5'-nitro-2'-furyl) -acrolein, 3- (2'
  • Benzaldehyde and / or cinnamaldehyde and / or naphthaldehyde and / or at least one derivative of these abovementioned aldehydes, which in particular carry one or more hydroxyl, alkoxy or amino substituents, are very particularly preferably used as the reactive carbonyl component in the oxo dyeing.
  • the reactive carbonyl compound of the component (oxo1) selected from at least one compound of the formula (AC-1),
  • R 1 , R 2 and R 3 independently of one another represent a hydrogen atom, a halogen atom, a (C 1 to C 6 ) -alkyl group, a (C 2 to C 6 ) -alkenyl group, a formyl group, a hydroxy group, a C 1 to C 6
  • Z ' is a direct bond or a vinylene group
  • R 4 and R 5 represent a hydrogen atom or together form, together with the remainder of the molecule, a 5- or 6-membered aromatic or aliphatic ring.
  • the derivatives of benzaldehydes, naphthaldehydes or cinnamaldehydes of the reactive carbonyl compound according to component (Oxo1) are preferably selected from at least one compound of the group consisting of 4-hydroxy-3-methoxybenzaldehyde, 3,5-dimethoxy-4-hydroxybenzaldehyde, 4-hydroxy 1-naphthaldehyde, 4-hydroxy-2-methoxybenzaldehyde, 3,4-dihydroxy-5-methoxybenzaldehyde, 3,4,5-trihydroxybenzaldehyde, 3,5-dibromo-4-hydroxybenzaldehyde, 4-hydroxy-3-nitrobenzaldehyde, 3 Bromo-4-hydroxybenzaldehyde, 4-hydroxy-3-methylbenzaldehyde, 3,5-dimethyl-4-hydroxybenzaldehyde, 5-bromo-4-hydroxy-3-methoxybenzaldehyde, 4-diethylamino-2-hydroxybenzaldehyde, 4-di
  • CH-acidic compounds are generally considered those compounds which carry a bound to an aliphatic carbon atom hydrogen atom, wherein due to electron-withdrawing substituents, activation of the corresponding carbon-hydrogen bond is effected.
  • these are preferably those CH-acidic compounds which contain an aromatic and / or a heterocyclic radical.
  • the heterocyclic residue may again be aliphatic or aromatic.
  • the CH-acidic compounds are particularly preferably selected from heterocyclic compounds, in particular cationic, heterocyclic compounds.
  • component (oxo2a) at least one CH-acidic compound having an aromatic or aliphatic, heterocyclic basic body which is selected from cyclic onium compounds having the structural unit of the formula (CH-1) and / or compounds of the formula (CH-) 2)
  • R 6 represents a linear or cyclic (C 1 to C 6 ) alkyl group, a (C 2 to C 6 ) alkenyl group, an optionally substituted aryl group, an optionally substituted heteroaryl group, an aryl (d to C 6 ) alkyl group, a (C 1 -C 6) - hydroxyalkyl group, a (C 2 -C 6) -polyhydroxyalkyl group, a (C 1 to C 6) alkoxy alkyl (C- ⁇ to C 6), a group R ' R "N- (CH 2 ) m -, in which R 1 and R 11 independently of one another represent a hydrogen atom, a (C 1 to C 4 ) -alkyl group, a (C 1 to C 4 ) -hydroxyalkyl group or an aryl- ( C 1 -C 6 ) -alkyl group, where R 1 and R "together with the nitrogen atom can form a 5-, 6- or 7-member
  • R 7 is a (C 1 to C 6 ) -alkyl group, in particular a methyl group,
  • X ' is a physiologically acceptable anion
  • the cycle of the formula (CH-1) represents all ring structures which may additionally contain other heteroatoms such as nitrogen, oxygen or sulfur and may further carry fused ring structures, all of these ring structures being able to carry additional substituents,
  • Het is an optionally substituted heteroaromatic
  • X 1 represents a direct bond or a carbonyl group.
  • Preferred ring structures which carry the structural unit of the formula (CH-1) are preferably selected according to the invention from 3H-indolium, benzothiazolium, benzoxazolium, 1, 2-dihydro-2-oxopyrimidinium, quinolinium, quinoxalinium or pyridinium.
  • compounds of the formula (CH-2) are particularly suitable for those in which the radical Het according to formula (CH-2) is derived from one of the heteroaromatic compounds furan, thiophene, pyrrole, isoxazole, isothiazole, imidazole, oxazole, thiazole, pyridine , Pyridazine, pyrimidine, pyrazine, 1, 2,3-triazine, 1, 2,4-triazine, 1, 3,5-triazine, benzopyrrole, benzofuran, benzothiophene, benzimidazole, benzothiazole, benzoxazole, indazole, benzoisoxazole, benzoisothiazole, indole .
  • the compounds of formula (CH-2) are selected from at least one compound of the group consisting of 2- (2-furoyl) -acetonitrile, 2- (5-bromo-2-furoyl) -acetonitrile, 3- (2.5 -Dimethyl-3-furyl) -3-oxopropanitrile, 2- (2-thenoyl) -acetonitrile, 2- (3-thenoyl) -acetonitrile, 2- (5-fluoro-2-thenoyl) -acetonitrile, 2- (5 -Chloro-2-thenoyl) -acetonitrile, 2- (5-bromo-2-thenoyl) -acetonitrile, 2- (5-methyl-2-thenoyl) -acetonitrile, 2- (2,5-dimethylpyrrol-3-oyl ) -acetonitrile, 2- (1, 2,5-trimethylpyrrol-3-oyl) -acetonitrile, 2-
  • the CH-acidic compounds of the oxo dye precursors of the component (oxo2a) are preferably selected from at least one compound of the formula (CH-3),
  • R 8 and R 9 are each independently a linear or cyclic (C 1 to C 6 ) alkyl group, a (C 2 to C 6 ) alkenyl group, an optionally substituted aryl group, an optionally substituted heteroaryl group, an aryl (d to C 6 ) alkyl group, a (C 1 to C 6 ) hydroxyalkyl group, a (C 2 to C 6 ) polyhydroxyalkyl group, a (C 1 to C 6 ) alkoxy (C 1 to C 6 ) alkyl group, a R 'R M is N- (CH 2 ) m -, wherein R 1 and R "are each independently hydrogen, (C 1 to C 4 ) alkyl, (C 1 to C 4 ) hydroxyalkyl or a Aryl- (C 1 -C 4 ) -alkyl group, wherein R 1 and R 11 together with the nitrogen atom can form a 5-, 6- or 7-membered ring and m is a number
  • R 11 represents a hydrogen atom, a (C 1 to C 6) alkyl group, a (C 1 -C 6) - hydroxyalkyl group, a (C 2 -C 6) -polyhydroxyalkyl group, a (C 1 to C 6) - Alkoxy group, a (C 1 to C 6 ) -hydroxyalkoxy, a group R "'R lv N- (CH 2 ) q -, wherein R 1 " and R IV independently represent a hydrogen atom, a (C 1 to C 6 ) Alkyl group, a (C 1 to C 6 ) hydroxyalkyl group or an AIyI (C 1 to C 6 ) alkyl group and q is a number 1, 2, 3, 4, 5 or 6, wherein the radical R 11 together with one of the radicals R 10 or R 12 may form a 5- or 6-membered aromatic ring optionally substituted by a halogen atom, a (C 1 to C 6 ) -alkyl
  • Y represents an oxygen atom, a sulfur atom or a group NR V ", wherein R v" stands for a hydrogen atom, an aryl group, a heteroaryl group, a (C 1 to C 6) alkyl group or an aryl (d-C 6 ) alkyl,
  • At least one group R 10 or R 12 according to formula (CH-3) necessarily stands for a (C 1 to C 6 ) -alkyl group.
  • This alkyl group preferably carries at least two hydrogen atoms on its ⁇ -carbon atom.
  • Particularly preferred alkyl groups are the methyl, ethyl, propyl, n-butyl, iso-butyl, n-pentyl, neo-pentyl, n-hexyl group.
  • R 10 and R 12 are each independently hydrogen or a methyl group, wherein at least one group R 10 or R 12 is a methyl group.
  • Y of the formula (CH-3) is an oxygen or a sulfur atom, more preferably an oxygen atom.
  • the radical R 8 of the formula (CH-3) is preferably selected from a (C 1 to C 6 ) -alkyl group (particularly preferably a methyl group), a (C 2 to C 6 ) -alkenyl group (in particular an allyl group), a ( C 2 to C 6 ) hydroxyalkyl group (especially a 2-hydroxyethyl group) or an optionally substituted benzyl group.
  • R 11 of the formula (CH-3) is preferably a hydrogen atom.
  • radicals R 9 , R 10 and R 12 is a methyl group
  • the radical R 11 is a hydrogen atom
  • Y is an oxygen or sulfur atom
  • the radical R 8 is selected from a ( C 1 to C 6 ) -alkyl group (particularly preferably a methyl group), a (C 2 to C 6 ) alkenyl group (especially an allyl group), a (C 2 to C 6 ) hydroxyalkyl group (especially a 2-hydroxyethyl group) or an optionally substituted benzyl group.
  • the compounds of formula (CH-3) are selected from one or more
  • Very particularly preferred compounds according to formula (CH-3) are selected from one or more compounds of the group of salts with physiologically acceptable counterion X "
  • X ' in the formulas (CH-1) and (CH-3) and in the above lists is preferably halide, benzenesulfonate, p-toluenesulfonate, (C 1 to C 4 ) -alkanesulfonate, trifluoromethanesulfonate, perchlorate, 0.5 sulfate, hydrogensulfate, Tetrafluoroborate, hexafluorophosphate or tetrachlorozincate.
  • the anions chloride, bromide, iodide, hydrogen sulfate or p-toluenesulfonate are used as X ' .
  • the CH-acidic compounds of the oxo dye precursors of the component (oxo2a) are most preferably selected from at least one compound of the group consisting of 2- (2-furoyl) -acetonitrile, 2- (5-bromo-2-furoyl) -acetonitrile, 3- (2,5-dimethyl-3-furyl) -3-oxopropanitrile, 2- (2-thenoyl) -acetonitrile, 2- (3-thenoyl) -acetonitrile, 2- (5-fluoro-2-thenoyl) - acetonitrile, 2- (5-chloro-2-thenoyl) -acetonitrile, 2- (5-bromo-2-thenoyl) -acetonitrile, 2- (5-methyl-2-thenoyl) -acetonitrile, 2- (2.5 Dimethylpyrrol-3-oyl) -acetonitrile, 2- (1, 2,5-trimethylpyr
  • component (Oxo2b) at least one oxidation dye precursor having at least one primary or secondary amino group and / or at least one hydroxyl group can be used. Preferred suitable representatives are found under the execution of the oxidation dye precursors. However, it is preferred according to the invention if the compounds of the component (oxo2) are selected only among CH-acidic compounds.
  • the above-mentioned compounds of the component (Oxo1) and the component (Oxo2) are, when used, each preferably in an amount of 0.03 to 65 mmol, in particular from 1 to 40 mmol, based on 100 g of the total composition , used.
  • the agents according to the invention may contain at least one substantive dye. These are dyes that raise directly on the hair and do not require an oxidative process to form the color. Direct dyes are usually nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols.
  • the substantive dyes are each preferably used in an amount of 0.001 to 20% by weight, based on the total application preparation.
  • the total amount of substantive dyes is preferably at most 20% by weight.
  • Direct dyes can be subdivided into anionic, cationic and nonionic substantive dyes.
  • Particularly suitable anionic direct dyes are 6-hydroxy-5 - [(4-sulfophenyl) azo] -2-naphthalenesulfonic acid disodium salt (CI 15.985, Food Yellow No. 3, FD & C Yellow No. 6), 2,4-dinitro-1 -naphthol-7-sulfonic acid disodium salt (Cl.10.316; Acid Yellow 1, Food Yellow No. 1), 2- (indan-1, 3-dion-2-yl) quinoline-x, x-sulfonic acid (mixture of mono and disulfonic acid) (CI 47,005, D & C Yellow No. 10, Food Yellow No.
  • Acid Red 51 N- [6- (diethylamino) -9- (2,4-disulfophenyl) -3H-xanthen-3-ylidene] -N-ethylethanammonium hydroxide, inner salt, sodium salt (CI 45, 100; Acid Red 52), 8 - [(4- (phenylazo) phenyl) azo] -7-naphthol-1,3-disulphonic acid disodium salt (CI 27,290, Acid Red 73), 2 ', 4', 5 ', 7'- Tetrabromo-3 ', 6'-dihydroxyspiro [isobenzofuran-1 (3H), 9'- [9H] xanthene] -3-one disodium salt (Cl.45, 380; Acid Red 87), 2', 4 ', 5', 7'-tetrabromo-4,5,6,7-tetrachloro-3 ', 6'-dihydroxys
  • Preferred anionic substantive dyes are those under the international designations or trade names Acid Yellow 1, Yellow 10, Acid Yellow 23, Acid Yellow 36, Acid Orange 7, Acid Red 33, Acid Red 52, Pigment Red 57: 1, Acid Blue 7, Acid Green 50, Acid Violet 43, Acid Black 1 and Acid Black 52 known compounds.
  • Particularly suitable cationic direct dyes are 9- (dimethylamino) benzo [a] phenoxazine-7-ium chloride (Cl 51, 175, Basic Blue 6), di [4- (diethylamino) phenyl] [4- (ethylamino ) naphthyl] carbenium chloride (Cl 42,595, Basic Blue 7), di- (4- (dimethylamino) phenyl) - (4- (methylphenylamino) naphthalen-1-yl) carbenium chloride (CI 42,563; Basic Blue 8), 3,7-di (dimethylamino) -phenothiazine-5-ium chloride (CI 52.015 Basic Blue 9), di [4- (dimethylamino) phenyl] [4- (phenylamino) naphthyl] carbenium chloride ( Cl.44,045; Basic Blue 26), 2 - [(4- (ethyl (2-hydroxy
  • aromatic systems substituted with a quaternary nitrogen group such as Basic Yellow 57, Basic Red 76, Basic Blue 99, Basic Brown 16 and Basic Brown 17, as well as
  • Preferred cationic substantive dyes of group (c) are in particular the following compounds:
  • the cationic direct dyes which are sold under the trademark Arianor ®, according to the invention are also very particularly preferred cationic direct dyes.
  • Nonionic substantive dyes are:
  • nonionic substantive dyes are in particular nonionic nitro and
  • Suitable blue nitro dyes are in particular:
  • Suitable red nitro dyes are in particular:
  • Suitable yellow nitro dyes are in particular:
  • 1,2-diamino-4-nitrobenzene (CI 76,020), 1 - [(2-hydroxyethyl) amino] -2-nitrobenzene (HC Yellow 2), 1- (2-hydroxyethoxy) -2 - [(2-hydroxyethyl ) amino] -5-nitrobenzene (HC Yellow 4), 1-amino-2 - [(2-hydroxyethyl) amino] -5-nitrobenzene (HC Yellow 5), 4 - [(2,3-dihydroxypropyl) amino] 3-nitro-1-trifluoromethylbenzene (HC Yellow 6), 2- [di (2-hydroxyethyl) amino] -5-nitrophenol, 2 - [(2-hydroxyethyl) amino] -1-methoxy-5-nitrobenzene , 2-amino-3-nitrophenol, 2-amino-4-nitrophenol, 1-amino-2-methyl-6-nitrobenzene, 1- (2-hydroxyethoxy) -3-methylamino-4-nitrobenzene, 2,3- ( Di
  • Suitable quinone dyes are in particular:
  • Suitable neutral azo dyes are in particular:
  • Preferred nonionic substantive dyes are those under the international designations or trade names HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, HC Orange 1, Disperse Orange 3, HC Red 1, HC Red 3, HC HC Red 11, HC Red 11, HC Red 11, HC Blue 11, HC Blue 2, HC Blue 11, HC Blue 12, Disperse Blue 3, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Disperse Black 9 well-known compounds, as well 1, 4-diamino-2-nitrobenzene, 2-amino-4-nitrophenol, 1,4-bis (2-hydroxyethyl) amino-2-nitrobenzene, 3-nitro-4- (2-hydroxyethyl) aminophenol, 2- (2-hydroxyethyl) amino-4,6-dinitrophenol, 4 - [(2-hydroxyethyl) amino] -3-nitro-1-methylbenzene, 1-amino-4- (2-hydroxyethyl) amino-5- chloro-2-nitrobenzene, 4-amino-3-nitrophenol, 1-
  • the substantive dyes each represent uniform compounds. Rather, due to the production process for the individual dyes, minor amounts of other components may be included, as far as these do not adversely affect the dyeing result or for other reasons, e.g. toxicological, must be excluded.
  • the teaching according to the invention can be carried out in the presence of at least one additional oxidizing agent, although it is preferred according to the invention that the agents according to the invention are free of additional oxidizing agents.
  • the additional oxidizing agents are different from atmospheric oxygen and have such an oxidation potential which makes it possible to bond disulfide bridges within or between the proteins of the hair keratin and / or oxidatively lighten the natural color pigment melanin and / or to oxidize a developer-type oxidation dye precursor.
  • Such oxidizing agents are, for example, hydrogen peroxide and its addition products, organic percarboxylic acids or organic peroxides.
  • Suitable organic percarboxylic acids according to the invention are in particular monoperphthalic acid, peracetic acid or 6- (phthalimidoperoxy) hexanoic acid (CAS No .: 128275-31-0).
  • the oxidizing agent is preferably hydrogen peroxide and / or at least one addition product thereof, in particular to inorganic or organic compounds in question.
  • the appropriate addition products of hydrogen peroxide are again preferred selected from at least one compound of the group consisting of sodium perborate,
  • the oxidizing agents can also be used together with a catalyst.
  • the catalyst activates the oxidation of the substrate, such as oxidation of the oxidation dye precursors or melanin.
  • Such catalysts are e.g. Metal ions, iodides, quinones or certain enzymes.
  • Suitable metal ions are, for example, Zn 2+ , Cu 2+ , Fe 2+ , Fe 3+ , Mn 2+ , Mn 4+ , Li + , Mg 2+ , Ca 2+ and Al 3+ . Particularly suitable are Zn 2+ , Cu 2+ and Mn 2+ .
  • the metal ions can in principle be used in the form of any physiologically acceptable salt or in the form of a complex compound.
  • Preferred salts are the acetates, sulfates, halides, lactates and tartrates.
  • Suitable enzymes are e.g. Peroxidases that can significantly increase the effect of small amounts of hydrogen peroxide. Furthermore, such enzymes are suitable according to the invention, which generate with the aid of atmospheric oxygen in situ small amounts of hydrogen peroxide and biocatalytically activate the oxidation of the dye precursors in this way.
  • Particularly suitable catalysts for the oxidation of dye precursors are the so-called 2-electron oxidoreductases in combination with the specific substrates, e.g.
  • Lactate oxidase and lactic acid and their salts Lactate oxidase and lactic acid and their salts
  • the oxidizing agent is preferably contained in an amount of from 1.0 to 10% by weight, in particular from 3.0 to 10.0% by weight, in each case based on the weight of the ready-to-use agent, in an agent which can be used according to the invention.
  • the agents used according to the invention may contain at least one surfactant.
  • surfactant in principle, both further anionic and zwitterionic, ampholytic, nonionic and cationic surfactants are suitable. In many cases, however, it has proved to be proven advantageous to select the surfactants from anionic, zwitterionic or nonionic surfactants.
  • anionic surfactants suitable in preparations according to the invention are all anionic surfactants suitable for use on the human body. These are characterized by a water-solubilizing, anionic group such. Example, a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group having about 10 to 22 carbon atoms. In addition, glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups may be present in the molecule.
  • anionic surfactants are, in each case in the form of the sodium, potassium and ammonium and the mono-, di- and Trialkanolammoniumsalze with 2 or 3 C atoms in the alkanol group, linear fatty acids having 10 to 22 carbon atoms (soaps )
  • G glycoside unit which is derived from a sugar containing 5 or 6 carbon atoms, p number from 1 to 10, in particular the Laurylglucosidcarboxylat, such as is available as Plantapon ® LGC from Cognis Germany,
  • esters of tartaric acid and citric acid with alcohols which are adducts of about 2-15 molecules of ethylene oxide and / or propylene oxide with fatty alcohols having 8 to 22 carbon atoms.
  • Preferred additional anionic surfactants are selected from the abovementioned anionic alkyl oligoglycoside or anionic alkenyl oligoglycoside derivatives, ether carboxylic acids having 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule, and in particular salts of saturated and in particular unsaturated C 8 -C 22 Carboxylic acids such as oleic acid, stearic acid, isostearic acid and palmitic acid.
  • Nonionic surfactants contain as hydrophilic group z.
  • Such compounds are, for example
  • Alkylphenols having 8 to 15 C atoms in the alkyl group having 8 to 15 C atoms in the alkyl group
  • Preferred nonionic surfactants are alkyl polyglycosides of the general formula R 1 O- (Z) x . These connections are identified by the following parameters.
  • the alkyl radical R 1 contains 6 to 22 carbon atoms and may be both linear and branched. Preference is given to primary linear and methyl-branched in the 2-position aliphatic radicals.
  • Such alkyl radicals are, for example, 1-octyl, 1-decyl, 1-lauryl, 1-myristyl, 1-cetyl and 1-stearyl. Particularly preferred are 1-octyl, 1-decyl, 1-lauryl, 1-myristyl.
  • oxo-alcohols compounds with an odd number of carbon atoms in the alkyl chain predominate.
  • the alkyl polyglycosides which can be used according to the invention can contain, for example, only one particular alkyl radical R 1 .
  • these compounds are prepared starting from natural fats and oils or mineral oils.
  • the alkyl radicals R are mixtures corresponding to the starting compounds or corresponding to the particular work-up of these compounds.
  • R 1 consists essentially of C 8 and C 10 alkyl groups, essentially of C 12 and C 14 alkyl groups, essentially of C 8 to C 16 alkyl groups or essentially from Ci 2 - to C-
  • sugar building block Z it is possible to use any desired mono- or oligosaccharides.
  • sugars with 5 or 6 carbon atoms and the corresponding oligosaccharides are used.
  • Such sugars are, for example, glucose, fructose, galactose, arabinose, ribose, xylose, lyxose, allose, altrose, mannose, gulose, idose, talose and sucrose.
  • Preferred sugar building blocks are glucose, fructose, galactose, arabinose and sucrose; Glucose is particularly preferred.
  • alkyl polyglycosides which can be used according to the invention contain on average from 1.1 to 5 sugar units. Alkyl polyglycosides having x values of 1.1 to 1.6 are preferred. Very particular preference is given to alkyl glycosides in which x is 1: 1 to 1, 4.
  • the alkyl glycosides can also serve to improve the fixation of fragrance components on the hair.
  • the person skilled in the art will therefore prefer to use this class of substance as further constituent of the preparations in the event that an effect of the perfume oil on the hair which exceeds the duration of the hair treatment is desired.
  • alkoxylated homologs of said alkyl polyglycosides can also be used according to the invention. These homologs may contain on average up to 10 ethylene oxide and / or propylene oxide units per alkyl glycoside unit.
  • zwitterionic surfactants can be used, in particular as cosurfactants.
  • Zwitterionic surfactants are those surface-active compounds which carry at least one quaternary ammonium group and at least one -COO () or -SO 3 () group in the molecule.
  • Particularly suitable zwitterionic surfactants are the so-called betaines such as N-alkyl-N, N-dimethylammonium glycinates, for example cocoalkyldimethylammonium glycinate, N-acylaminopropyl-N, N-dimethylammonium glycinates, for example cocoacylaminopropyl-dimethylammonium glycinate, and 2-alkyl-3-carboxylmethyl-3-hydroxyethyl imidazolines having in each case 8 to 18 C atoms in the alkyl or acyl group and the coco acylaminoethylhydroxyethylcarboxymethylglycinate.
  • a preferred zwitterionic surfactant is the fatty acid amide derivative known by the INCI name Cocamidopropyl Betaine.
  • the cationic surfactants used are, in particular, those of the quaternary ammonium compound type, the esterquats and the amidoamines.
  • Preferred quaternary ammonium compounds are ammonium halides, in particular chlorides and bromides, such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, e.g.
  • alkyltrimethylammonium chlorides dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, e.g.
  • cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride as well as the imidazolium compounds known under the INCI names Quaternium-27 and Quaternium-83.
  • the long alkyl chains of the above-mentioned surfactants preferably have 10 to 18 carbon atoms.
  • Esterquats are known substances which contain both at least one ester function and at least one quaternary ammonium group as a structural element.
  • Preferred ester quats are quaternized ester salts of fatty acids with triethanolamine, quaternized ester salts of fatty acids with diethanolalkylamines and quaternized ester salts of fatty acids with 1,2-dihydroxypropyldialkylamines.
  • Such products are marketed under the trade names Stepantex® ®, ® and Dehyquart® Armocare® ®.
  • the alkylamidoamines are usually prepared by amidation of natural or synthetic fatty acids and fatty acid cuts with dialkylaminoamines.
  • An inventively particularly suitable compound from this group of substances under the name Tegoamid ® S 18 commercial stearamidopropyl dimethylamine is.
  • cationic surfactants which can be used according to the invention are the quaternized protein hydrolysates.
  • Glucquat ® 100 is, according to INCI nomenclature a "lauryl methyl Gluceth-10 Hydroxypropyl Dimonium Chloride”.
  • the compounds used as surfactant with alkyl groups may each be uniform substances. However, it is generally preferred to use native vegetable or animal raw materials in the production of these substances, so that substance mixtures having different alkyl chain lengths depending on the respective raw material are obtained.
  • both products with a "normal” homolog distribution and those with a narrow homolog distribution can be used.
  • "normal” homolog distribution are meant mixtures of homologs obtained in the reaction of fatty alcohol and alkylene oxide using alkali metals, alkali metal hydroxides or alkali metal alcoholates as catalysts. Narrowed homolog distributions are obtained when, for example Hydrotalcites, alkaline earth metal salts of ether carboxylic acids, alkaline earth metal oxides, hydroxides or - alkoxides can be used as catalysts.
  • the use of products with narrow homolog distribution may be preferred.
  • agents used according to the invention may contain further active ingredients, auxiliaries and additives, such as, for example, nonionic, zwitterionic and amphoteric, anioic or cationic polymers
  • Structural agents such as maleic acid and lactic acid, hair conditioning compounds such as phospholipids, for example soya lecithin, egg lecithin and cephalins,
  • Protein hydrolysates in particular elastin, collagen, keratin, milk protein, soy protein and
  • Solvents and mediators such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol and diethylene glycol, fiber-structure-improving agents, especially mono-, di- and oligosaccharides such as glucose, galactose, fructose, fructose and lactose, quaternized amines such as methyl-1-alkylamidoethyl -2-alkylimidazolinium methosulfate
  • Anti-dandruff agents such as Piroctone Olamine, Zinc Omadine and Climbazole,
  • Light stabilizers in particular derivatized benzophenones, cinnamic acid derivatives and
  • Active ingredients such as allantoin, pyrrolidonecarboxylic acids and their salts, and bisabolol,
  • Vitamins, provitamins and vitamin precursors in particular those of groups A, B 3 , B 5 , B 6 ,
  • Plant extracts such as extracts of green tea, oak bark, stinging nettle, witch hazel,
  • Spruce needle horse chestnut, sandalwood, juniper, coconut, mango, apricot, lime,
  • Bodying agents such as sugar esters, polyol esters or polyol alkyl ethers,
  • Fats and waxes such as spermaceti, beeswax, montan wax and paraffins,
  • Swelling and penetration substances such as glycerol, propylene glycol monoethyl ether, carbonates,
  • Opacifiers such as latex, styrene / PVP and styrene / acrylamide copolymers
  • Pearlescing agents such as ethylene glycol mono- and distearate and PEG-3-distearate, pigments
  • Stabilizers for hydrogen peroxide and other oxidizing agents propellants such as propane-butane mixtures, N 2 O, dimethyl ether, CO 2 and air, antioxidants.
  • the effect can be further increased with polymers.
  • polymers are meant both natural and synthetic polymers which may be anionic, cationic, amphoteric or nonionic.
  • Cationic polymers are polymers which have groups in the main and / or side chain which may be “temporary” or “permanent” cationic.
  • “permanently cationic” refers to those polymers which have a cationic group independently of the pH of the agent These are generally polymers which contain a quaternary nitrogen atom, for example in the form of an ammonium group
  • Preferred cationic groups are quaternary ammonium groups .
  • those polymers in which the quaternary ammonium group 4 hydrocarbon group bound to a synthesized from acrylic acid, methacrylic acid or derivatives thereof, polymer main chain via a CI_ have been found to be particularly suitable.
  • R 18 -H or -CH 3
  • R 19, R 20 and R 21 are independently selected from C- ⁇ - 4 -alkyl, -alkenyl or -hydroxyalkyl groups
  • m 1, 2, 3 or 4
  • n is a natural number
  • X ' is a physiologically acceptable organic or inorganic anion
  • copolymers consisting essentially of the monomer units listed in formula (III) and nonionic monomer units are particularly preferred cationic polymers.
  • R 18 is a methyl group
  • R 19 , R 20 and R 21 are methyl groups m has the value 2.
  • Suitable physiologically tolerated counterions X " are, for example, halide ions, sulfate ions, phosphate ions, methosulfate ions and organic ions such as lactate, citrate, tartrate and acetate ions, preference being given to halide ions, in particular chloride.
  • a particularly suitable homopolymer is, if desired cross-linked, Po ⁇ methacryloyloxyethyltrimethylammoniumchlorid) with the INCI name Polyquaternium- 37.
  • the crosslinking can, if desired, using poly olefinically unsaturated compounds, for example divinylbenzene, tetraallyloxyethane, methylenebisacrylamide, diallyl ether, polyallylpolyglycerylether, or allyl ethers of sugars or Sugar derivatives such as erythritol, pentaerythritol, arabitol, mannitol, sorbitol, sucrose or glucose.
  • Methylenebisacrylamide is a preferred crosslinking agent.
  • the homopolymer is preferably used in the form of a nonaqueous polymer dispersion which should not have a polymer content of less than 30% by weight.
  • Such polymer dispersions are (under the names Salcare ® SC 95 about 50% polymer content, additional components: mineral oil (INCI name: Mineral Oil) and tridecyl-polyoxypropylene-polyoxyethylene-ether (INCI name: PPG-1 trideceth-6) ) and Salcare ® SC 96 (about 50% polymer content, additional components: mixture of diesters of propylene glycol with a mixture of caprylic and capric acid (INCI name: propylene glycol Dicaprylate / Dicaprate) and tridecyl polyoxypropylene-polyoxyethylene-ether (INCI Designation: PPG-1-trideceth-6)) are commercially available.
  • Copolymers with monomer units of the formula (III) contain, as nonionic monomer units, preferably acrylamide, methacrylamide, acrylic acid C 1 -4 -alkyl esters and methacrylic acid C 1. 4- alkyl esters. Among these nonionic monomers, the acrylamide is particularly preferred. These copolymers can also be crosslinked, as described above in the case of the homopolymers. A copolymer preferred according to the invention is the crosslinked acrylamide-methacryloyloxyethyltrimethylammonium chloride copolymer. Such copolymers in which the monomers are present in a weight ratio of about 20:80, are commercially available as approximately 50% non-aqueous polymer dispersion 92 under the name Salcare ® SC.
  • quaternized cellulose derivatives such as are available under the names of Celquat ® and Polymer JR ® commercially.
  • the compounds Celquat ® H 100, Celquat ® L 200 and Polymer JR ® 400 are preferred quaternized cellulose derivatives, cationic alkyl polyglycosides according to DE-PS 44 13 686, cationized honey, for example the commercial product Honeyquat ® 50, cationic guar derivatives, such as in particular the products sold under the trade names Cosmedia® ® guar and Jaguar ® products,
  • Quaternary group polysiloxanes such as the commercially available products Q2-7224 (manufactured by Dow Corning, a stabilized trimethylsilylamodimethicone), Dow Corning® 929 emulsion (containing a hydroxylamino-modified silicone, also referred to as amodimethicones), SM-2059 (manufacturer: General Electric), SLM-55067 (Manufacturer: Wacker) and Abil ® -Quat 3270 and 3272 (manufacturer: Th Goldschmidt; di- quaternary polydimethylsiloxanes, quaternium-80).
  • Q2-7224 manufactured by Dow Corning, a stabilized trimethylsilylamodimethicone
  • Dow Corning® 929 emulsion containing a hydroxylamino-modified silicone, also referred to as amodimethicones
  • SM-2059 manufactured by General Electric
  • SLM-55067 Manufacturer: Wacker
  • Such compounds are sold under the names Gafquat ® 734 and Gafquat ® 755 commercially,
  • Vinylpyrrolidone-Vinylimidazoliummethochlorid copolymers such as those available under the names Luviquat ® FC 370, FC 550, FC 905 and HM 552, quaternized polyvinyl alcohol, as well as those under the names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and
  • Polyquaternium 27 known polymers with quaternary nitrogen atoms in the polymer main chain.
  • Can be used as cationic polymers are sold under the names Polyquaternium-24 (commercial product z. B. Quatrisoft ® LM 200), known polymers.
  • Gaffix ® VC 713 manufactured by ISP:
  • the copolymers of vinylpyrrolidone such as the commercial products Copolymer 845 (ISP manufacturer) are Gafquat ® ASCP 1011, Gafquat ® HS 110, Luviquat ® 8155 and Luviquat ® MS 370 available are.
  • cationic polymers of the present invention are usually contain an amino group present at certain pH values as a quaternary ammonium group and hence cationic.
  • chitosan and its derivatives are preferred, such as for example, under the trade designations Hydagen ® CMF, Hydagen® ® HCMF, Kytamer ® PC and Chitolam ® NB / 101 are freely available commercially.
  • chitosans are deacetylated, in different degrees of deacetylation and varying degrees of degradation (molecular weights) are commercially available. Their preparation is, for example, in DE 44 40 625 A1 and described in DE 1 95 03 465 A1.
  • Particularly useful chitosans have a degree of deacetylation of at least 80% and a molecular weight of 5 '10 5 to 5' 10 6 (g / mol).
  • the chitosan must be converted into the salt form. This can be done by dissolving in dilute aqueous acids. Suitable acids are both mineral acids such as hydrochloric acid, sulfuric acid and phosphoric acid and organic acids, for example low molecular weight carboxylic acids, polycarboxylic acids and hydroxycarboxylic acids. Furthermore, higher molecular weight alkyl sulfonic acids or alkyl sulfuric acids or organophosphoric acids can be used, provided that they have the required physiological compatibility.
  • Suitable acids for converting the chitosan into the salt form are, for example, acetic acid, glycolic acid, tartaric acid, malic acid, citric acid, lactic acid, 2-pyrrolidinone-5-carboxylic acid, benzoic acid or salicylic acid. Preference is given to using low molecular weight hydroxycarboxylic acids, for example glycolic acid or lactic acid.
  • anionic polymers which can support the action of the active ingredient according to the invention are anionic polymers which have carboxylate and / or sulfonate groups.
  • anionic monomers from which such polymers may consist are acrylic acid, methacrylic acid, crotonic acid, maleic anhydride and 2-acrylamido-2-methylpropanesulfonic acid.
  • the acidic groups may be wholly or partly present as sodium, potassium, ammonium, mono- or triethanolammonium salt.
  • Preferred monomers are 2-acrylamido-2-methylpropanesulfonic acid and acrylic acid.
  • anionic polymers to support the action of the agent according to the invention preferably polysaccharides which substantiate their anionic character either by the incorporation of carboxylic acid-bearing furanoses or pyranoses or by the anionic functionalization of hydroxyl groups of individual sugar building blocks.
  • carboxylic acid groups bearing pyranoses and furanoses are in particular uronic acids, such as guluronic acid, glucuronic acid, mannuronic acid, iduronic acid or galacturonic acid.
  • uronic acids such as guluronic acid, glucuronic acid, mannuronic acid, iduronic acid or galacturonic acid.
  • anionic polymers can either be isolated directly from vegetable raw materials or obtained by biochemical reaction.
  • plant extracts are the glycosaminoglycans hyaluronic acid, chondroitin sulfate and keratan sulfate, and the gums gum arabic, karaya gum, ghatti gum and gum tragacantha.
  • algin which is marketed for example under the tradename Kelgin ® or Texamid ®, and xanthan (gum), which is available for example under the trademarks Kelzan ® or Keltrol ® commercially, and gellan (gum) which obtained by fermentation will and available under the trademark Gelrite ® and Kelcogel ® is commercially.
  • anionically functionalized sugar units contain mostly sulfated, phosphated or carboxymethylated hydroxy groups.
  • Naturally occurring sulfates are the red algae extracts carrageenan (Genuvisco ®) and agar.
  • Particularly suitable anionic polymers are in particular the carboxymethyl ether derivatives of polysaccharides.
  • Polysaccharides by used include, inter alia cellulose (Cellogen ®, Denvercel ®), Potato starch, corn starch, carob gum, guar gum, tamarind seed gum, chitin (Chitin Liquid ® 111 140), beta-glucan (glucan CM ®), inulin and amylose.
  • Anionic polymers have also proved to be effective which comprise 2-acrylamido-2-methylpropanesulfonic acid as sole or co-monomer, it being possible for the sulfonic acid group to be wholly or partly present as sodium, potassium, ammonium, mono- or triethanolammonium salt.
  • copolymers of at least one anionic monomer and at least one nonionic monomer are preferable to use copolymers of at least one anionic monomer and at least one nonionic monomer.
  • anionic monomers reference is made to the substances listed above.
  • Preferred nonionic monomers are acrylamide, methacrylamide, acrylic esters, methacrylic esters, vinylpyrrolidone, vinyl ethers and vinyl esters.
  • Preferred anionic copolymers are acrylic acid-acrylamide copolymers and in particular polyacrylamide copolymers with sulfonic acid-containing monomers.
  • a particularly preferred anionic copolymer consists of 70 to 55 mol% of acrylamide and 30 to 45 mol% of 2-acrylamido-2-methylpropanesulfonic acid, wherein the sulfonic acid group is wholly or partly in the form of sodium, potassium, ammonium, mono- or triethanolammonium Salt is present.
  • This copolymer may also be crosslinked, with crosslinking agents preferably polyolefinically unsaturated compounds such as tetraallyloxyethane, allylsucrose, allylpentaerythritol and methylenebisacrylamide are used.
  • crosslinking agents preferably polyolefinically unsaturated compounds such as tetraallyloxyethane, allylsucrose, allylpentaerythritol and methylenebisacrylamide are used.
  • crosslinking agents preferably polyolefinically unsaturated compounds such as tetraallyloxyethane, allylsucrose, allylpentaerythritol and methylenebisacrylamide are used.
  • Such a polymer is contained in the commercial product Sepigel ® 305 from SEPPIC.
  • Simulgel ® 600 as a compound with isohexadecane and polysorbate 80 Natriumacryloyldimethyltaurat copolymers have proven to be particularly effective according to the invention.
  • anionic homopolymers are uncrosslinked and crosslinked polyacrylic acids. Allyl ethers of pentaerythritol, sucrose and propylene may be preferred crosslinking agents. Such compounds are for example available under the trademark Carbopol ® commercially.
  • Copolymers of maleic anhydride and methyl vinyl ether, especially those with crosslinks, are also color-retaining polymers.
  • amphoteric polymers can be used as constituents as polymers for increasing the action of the active ingredient according to the invention.
  • amphoteric polymers includes both those polymers which contain in the molecule both free amino groups and free -COOH or SO 3 H groups and are capable of forming internal salts, as well as zwitterionic polymers which in the molecule have quaternary ammonium groups and -COO ' or -SO 3 ' groups, and those polymers comprising -COOH or SO 3 H groups and quaternary ammonium groups.
  • amphopolymer suitable is the acrylic resin commercially available as Amphomer ®, which is a copolymer of tert-butylaminoethyl methacrylate, N- (1, 1, 3,3-tetramethylbutyl) -acrylamide and two or more monomers from the group of acrylic acid, Represents methacrylic acid and its simple esters.
  • Amphomer ® is a copolymer of tert-butylaminoethyl methacrylate, N- (1, 1, 3,3-tetramethylbutyl) -acrylamide and two or more monomers from the group of acrylic acid, Represents methacrylic acid and its simple esters.
  • amphoteric polymers are those polymers which are composed essentially
  • R 22 -CH CR 23 -CO-Z- (C n H 2n ) -N (+) R 24 R 25 R 26 A () (IV)
  • R 22 and R 23 independently of one another are hydrogen or a methyl group and R 24 , R 25 and R 26 independently of one another are alkyl groups having 1 to 4 carbon atoms, Z is an NH group or an oxygen atom, n is an integer from 2 to 5 and A () is the anion of an organic or inorganic acid
  • R 27 and R 28 are independently hydrogen or methyl groups.
  • These compounds can be used both directly and in salt form, which is obtained by neutralization of the polymers, for example with an alkali metal hydroxide, according to the invention.
  • alkali metal hydroxide an alkali metal hydroxide
  • R 27 and R 28 are independently hydrogen or methyl groups.
  • These compounds can be used both directly and in salt form, which is obtained by neutralization of the polymers, for example with an alkali metal hydroxide, according to the invention.
  • monomers of the type (a) are used in which R 24 , R 25 and R 26 are methyl groups, Z is an NH group and A () is a halide, methoxysulfate or ethoxysulfate ion is; Acrylamidopropyl trimethyl ammonium chloride is a particularly preferred monomer (a).
  • Acrylic acid is preferably used as monomer (b) for the stated polymers.
  • the agents according to the invention may furthermore contain nonionogenic polymers.
  • Suitable nonionic polymers are, for example:
  • Vinylpyrrolidone / vinyl ester copolymers as sold, for example, under the trademark Luviskol ® (BASF).
  • Luviskol ® VA 64 and Luviskol ® VA 73, each vinylpyrrolidone / vinyl acetate copolymers are also preferred nonionic polymers.
  • Cellulose ethers such as hydroxypropyl cellulose, hydroxyethyl cellulose and
  • Methylhydroxypropylcellulose as for example sold under the trademarks Culminal ® and Benecel ® (AQUALON). shellac
  • Siloxanes These siloxanes can be both water-soluble and water-insoluble. Both volatile and nonvolatile siloxanes are suitable, nonvolatile siloxanes being understood as meaning those compounds whose boiling point is above 200 ° C. under normal pressure.
  • Preferred siloxanes are polydialkylsiloxanes, such as, for example, polydimethylsiloxane, polyalkylarylsiloxanes, such as, for example, polyphenylmethylsiloxane, ethoxylated polydialkylsiloxanes and polydialkylsiloxanes which contain amine and / or hydroxyl groups. Glycosidically substituted silicones according to EP 0612759 B1.
  • the preparations used contain a plurality of, in particular two different polymers of the same charge and / or in each case an ionic and an amphoteric and / or nonionic polymer.
  • the term polymer also means special preparations of polymers, such as spherical polymer powders.
  • Various methods are known for producing such microspheres from different monomers, for example by special polymerization processes or by dissolving the polymer in a solvent and spraying it into a medium in which the solvent evaporates or from the particles can diffuse out.
  • Suitable polymers are, for example, polycarbonates, polyurethanes, polyacrylates, polyolefins, polyesters or polyamides. Particularly suitable are those spherical polymer powders whose primary particle diameter is less than 1 micron.
  • Such products based on a polymethacrylate copolymer are, for example, under the trademark Polytrap ® Q5-6603 (Dow Corning) in the trade.
  • Other polymer powders for example based on polyamides (nylon 6, nylon 12) having a particle size of 2 - (10 microns (90%) and a specific surface area of about 10 m 2 / g under the trade name Orgasol ® 2002 DU Nat Cos Atochem SA, Paris).
  • spherical polymer powders which are suitable for the purpose according to the invention are, for example, the polymethacrylates (Micropearl M) from SEPPIC or (Plastic Powder A) from NIKKOL, the styrene-divinylbenzene copolymers (Plastic Powder FP) from NIKKOL, the polyethylene and polypropylene AKZO powder (ACCUREL EP 400) or silicone polymers (Silicone Powder X2-1605) from Dow Corning or spherical cellulose powders.
  • the polymethacrylates (Micropearl M) from SEPPIC or (Plastic Powder A) from NIKKOL
  • Plastic Powder FP styrene-divinylbenzene copolymers
  • ACCUREL EP 400 polyethylene and polypropylene AKZO powder
  • silicone polymers Silicone Powder X2-1605
  • the polymers are preferably contained in the agents used according to the invention in amounts of from 0.01 to 10% by weight, based on the total agent. Amounts of 0.1 to 5, in particular from 0.1 to 3 wt .-%, are particularly preferred.
  • agents according to the invention additionally comprise at least one further component which is selected from at least one member of the group which is formed from d) protein hydrolysates, c2) silicone derivatives and c3) (pseudo) ceramides.
  • the protein hydrolyzates d) are product mixtures which are obtained by acid, alkaline or enzymatically catalyzed degradation of proteins (proteins).
  • protein hydrolysates of both vegetable and animal origin can be used.
  • Animal protein hydrolysates are, for example, elastin, collagen, keratin, silk and milk protein protein hydrolysates, which may also be present in the form of salts.
  • Such products are, for example, under the trademarks keratin DEC ® (Vincience) Dehylan ® (Cognis), Promois® ® (Interorgana) Collapuron ® (Cognis), Nutrilan® ® (Cognis), Gelita-Sol ® (German Gelatinefabriken Stoess & Co) distributed Lexein ® (Inolex) and kerasol tm ® (Croda).
  • Preferred according to the invention is the use of protein hydrolysates of plant origin, eg. Soybean, almond, rice, pea, potato and wheat protein hydrolysates.
  • Such products are, for example, under the trademarks Gluadin ® (Cognis), diamine ® (Diamalt) ® (Inolex) and Crotein ® (Croda) available.
  • protein hydrolysates amino acid mixtures or individual amino acids obtained otherwise, such as, for example, arginine, lysine, histidine or pyrroglutamic acid, may also be used in their place.
  • derivatives of protein hydrolysates for example in the form of their fatty acid condensation products. Such products are marketed for example under the names Lamepon ® (Cognis), Gluadin ® (Cognis), Lexein ® (Inolex), Crolastin ® (Croda) or Crotein ® (Croda).
  • the protein hydrolysates in an amount of 0.05 to 5 wt .-%, particularly preferably from 0.5 to 2.0 wt .-%, each based on the weight of the ready-to-use agent included.
  • the silicone derivatives c2) when present in the agents used according to the invention, are preferably present in amounts of from 0.05 to 5% by weight, preferably from 0.2 to 5% by weight, based in each case on the ready-to-use agent ,
  • the silicones c2) are selected from at least one member of the list formed from:
  • polyalkyl siloxanes polyaryl siloxanes, polyalkylaryl siloxanes which are volatile or nonvolatile, straight chain, branched or cyclic, crosslinked or uncrosslinked;
  • grafted polysiloxane backbone silicone polymers having grafted thereto non-silicone-containing organic monomers having a polysiloxane backbone to which at least one organic macromer containing no silicone has been grafted in the chain, and optionally at least at one of its ends , such as the commercial product Abil B 8832 from Degussa marketed under the INCI name Bis-PEG / PPG-20/20 dimethicone;
  • Particularly preferred cosmetic or dermatological preparations according to the invention are characterized in that they contain at least one silicone of the formula (Si-1)
  • x is a number from 0 to 100, preferably from 0 to 50, more preferably from 0 to 20 and in particular 0 to 10.
  • the preferred cosmetic or dermatological preparations used according to the invention comprise a silicone of the above formula (Si-1). These silicones are referred to as dimethicones according to the INCI nomenclature. It is in the context of the present invention as the silicone of the formula (Si-1), preferably the compounds:
  • mixtures of o.g. Silicones may be included in the preferred compositions of the invention.
  • silicones have viscosities at 20 0 C for from 0.2 to 2 mmV 1, wherein silicones having viscosities of 0.5 to 1 mmV 1 are particularly preferred.
  • Particularly preferred agents according to the invention contain one or more amino-functional silicones.
  • Such silicones may e.g. by the formula (Si-2)
  • R is a hydrocarbon or a hydrocarbon radical having from 1 to about 6
  • Q is a polar radical of the general formula -R 1 HZ, wherein
  • R 1 is a divalent linking group bonded to hydrogen and the radical Z composed of carbon and hydrogen atoms, carbon, hydrogen and oxygen atoms or carbon, hydrogen and nitrogen atoms, and
  • Z is an organic, amino-functional group containing at least one amino-functional group; a assumes values in the range of about 0 to about 2, b takes values in the range of about 1 to about 3, a + b is less than or equal to 3, and c is a number in the range of about 1 to about 3, and x a number ranging from 1 to about 2,000, preferably from about 3 to about 50, and most preferably from about 3 to about 25; and y is a number ranging from about 20 to about 10,000, preferably from about 125 to about 10,000 and most preferably from about 150 to about 1000, and M is a suitable silicone end group as known in the art, preferably trimethylsiloxy.
  • Non-limiting examples of the groups represented by R in formula (Si-2) include alkyl groups such as methyl, ethyl, propyl, isopropyl, isopropyl, butyl, isobutyl, amyl, isoamyl, hexyl, isohexyl and the like; Alkenyl radicals such as vinyl, halovinyl, alkylvinyl, allyl, haloallyl, alkylallyl; Cycloalkyl radicals such as cyclobutyl, cyclopentyl, cyclohexyl and the like; Phenyl radicals, benzyl radicals, halohydrocarbon radicals such as 3-chloropropyl, 4-bromobutyl, 3,3,3-trifluoropropyl, chlorocyclohexyl, bromophenyl, chlorophenyl and the like, and sulfur-containing radicals such as mercaptoethyl, mer
  • R 1 examples include methylene, ethylene, propylene, hexamethylene, decamethylene, - CH 2 CH (CH 3 ) CH 2 -, phenylene, naphthylene, -CH 2 CH 2 SCH 2 CH 2 -, -CH 2 CH 2 OCH 2 - , -OCH 2 CH 2 -, - OCH 2 CH 2 CH 2 -, -CH 2 CH (CH 3 ) C (O) OCH 2 -, - (CHz) 3 CC (O) OCH 2 CH 2 -, -C 6 H 4 C 6 H 4 -, -C 6 H 4 CH 2 C 6 H 4 -; and - (CH 2 ) 3 C (O) SCH 2 CH 2 -.
  • Z is according to formula (Si-2) an organic, amino-functional radical containing at least one functional amino group.
  • a possible formula for said Z is NH (CH 2 ) Z NH 2 , where z is an integer greater than or equal to 1.
  • Another possible formula for said Z is -NH (CH 2 ) Z (CH 2 ) ZZ NH, wherein both z and zz independently of one another are an integer greater than or equal to 1, this structure comprising diamino ring structures, such as piperazinyl.
  • Said Z is most preferably an -NHCH 2 CH 2 NH 2 radical.
  • Z is -N (CH 2 ) Z (CH 2 ) ZZ NX 2 or -NX 2 , wherein each X of X 2 is independently selected from the group consisting of hydrogen and alkyl groups of 1 to 12 carbon atoms, and zz is O
  • Q according to formula (Si-2) is most preferably a polar amino-functional radical of formula - CH 2 CH 2 CH 2 NH 2 CH 2 CH 2 NH 2 .
  • ⁇ takes values in the range of 0 to 2
  • b takes values in the range of 2 to 3
  • a + b is less than or equal to 3
  • c is a number in the range of 1 to 3.
  • the molar ratio of the R a Q b SiO (4 a a b) / 2 units to the R 0 SiO (4 C) / 2 units in formula (Si-2) is in the range of about 1: From 2 to 1: 65, preferably from about 1: 5 to about 1:65, and most preferably from about 1:15 to about 1: 20. If one or more of the above formula (Si-2) silicones are used then the various variable substituents in the above formula may be different for the various silicone components present in the silicone blend.
  • Preferred cosmetic or dermatological preparations used according to the invention comprise an amino-functional silicone of the formula (Si-3)
  • G is -H, a phenyl group, -OH, -O-CH 3 , -CH 3 , -O-CH 2 CH 3 , -CH 2 CH 3 , -O-CH 2 CH 2 CH 3 , -CH 2 CH 2 CH 3 , -O-CH (C ⁇ 3 ) 2 , -CH (CH 3 ) 2 , -O-CH 2 CH 2 CH 2 CH 3 , -CH 2 CH 2 CH 2 CH 3 , -O-CH 2 CH ( CH 3 ) 2 , -CH 2 CH (CH 3 ) 2 , -O-CH (CH 3 ) CH 2 CH 3 , -CH (CH 3 ) CH 2 CH 3 , -CH (CH 3 ) CH 2 CH 3 , -O-C (CH 3 ) 3 , - C (CH 3 ) 3 ; a is a number between O and 3, in particular O; b is a number between O and 1, in particular 1, m and n are numbers
  • R ' is a monovalent radical selected from -QN (R ") - CH 2 -CH 2 -N (R") 2 -QN (FT) 2 -QN + (R ") 3 A- -QN + H (R" ) 2 a "QN + H 2 (R") a "-QN (R") - CH 2 -CH 2 -N + R "H 2 a", each Q is a chemical bond, -CH 2 -, -CH 2 -CH 2 -, -CH 2 CH 2 CH 2 -, -C (CH 2 ) 2 -, -CH 2 CH 2 CH 2 CH 2 -, -CH 2 C (CH 3 ) 2 -, -CH ( CHs) CH 2 CH 2 -, R "represents identical or different radicals from the group -H, -phenyl, -benzyl, -CH 2 - (CH CH 3) Ph, the C-
  • A represents an anion, which is preferably selected from chloride, bromide, iodide or methosulfate.
  • Cationic silicone oils such as the commercially available Dow Corning 929 emulsion (containing a hydroxylamino-modified silicone referred to as amodimethicone), DC 2-2078 (manufactured by Dow Corning, INCI: aminopropyl phenyl trimethicone), DC 5, are suitable according to the invention -7113 (manufacturer Dow Corning, INCI name: Silicone Quaternium 16), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil ® quat 3270 and 3272 (manufacturer: Th Goldschmidt; diquaternary. Polydimethylsiloxanes, quaternium-80).
  • Dow Corning 929 emulsion containing a hydroxylamino-modified silicone referred to as amodimethicone
  • DC 2-2078 manufactured by Dow Corning, INCI: aminopropyl phenyl trimethicone
  • DC 5 are
  • Particularly preferred agents according to the invention are characterized in that they contain at least one amino-functional silicone of the formula (Si 3-a)
  • silicones are referred to as trimethylsilylamodimethicones according to the INCI declaration and are available, for example, under the name Q2-7224 (manufacturer: Dow Corning, a stabilized trimethylsilylamodimethicone).
  • compositions according to the invention which contain at least one amino-functional silicone of the formula (Si-3b)
  • R is -OH, (optionally ethoxylated and / or propoxylated) (C 1 to C 20 ) -
  • R ' is -OH, a (C 1 to C 20 ) alkoxy group or a -CH 3 group and m, n1 and n2 are numbers whose sum (m + n1 + n2) is between 1 and 2,000, preferably between 50 and Is 150, wherein the sum (n1 + n2) preferably takes values from 0 to 1999 and in particular from 49 to 149 and m preferably values from 1 to 2000, in particular from 1 to 10.
  • silicones are according to the INCI declaration as Amodimethicone, or as functionalized Amodimethicone, such as bis (C13-15 alkoxy) PG Amodimethicone (for example, as a commercial product: DC 8500 from Dow Corning available), trideceth-9 PG-amodimethicones (for example as a commercial product Silcare Silicone SEA available from Clariant).
  • Amodimethicone or as functionalized Amodimethicone, such as bis (C13-15 alkoxy) PG Amodimethicone (for example, as a commercial product: DC 8500 from Dow Corning available), trideceth-9 PG-amodimethicones (for example as a commercial product Silcare Silicone SEA available from Clariant).
  • amino-functional silicones whose amine number is above 0.25 meq / g, preferably above 0.3 meq / g and in particular above 0 , 4 meq / g.
  • the amine number stands for the milliequivalents of amine per gram of the amino-functional silicone. It can be determined by titration and also expressed in mg KOH / g.
  • Cosmetic or dermatological preparations preferred according to the invention are characterized in that, based on their weight, they contain 0.01 to 10% by weight, preferably 0.1 to 8% by weight, particularly preferably 0.25 to 7.5% by weight and in particular from 0.5 to 5% by weight of amino-functional silicone (s).
  • the cyclic dimethicones designated as cyclomethicones according to INCI are also preferably used according to the invention.
  • cosmetic or dermatological preparations according to the invention are preferred which contain at least one silicone of the formula (Si-4)
  • x is a number from 0 to 200, preferably from 0 to 10, more preferably from 0 to 7 and in particular 0, 1, 2, 3, 4, 5 or 6 stands.
  • the silicones described above have a backbone composed of -Si-O-Si units.
  • these Si-O-Si units may also be interrupted by carbon chains.
  • Appropriate molecules are accessible by chain extension reactions and are preferably used in the form of silicone-in-water emulsions.
  • silicone-in-water emulsions which can be used according to the invention can be prepared by known processes, as disclosed, for example, in US Pat. No. 5,998,537 and EP 0 874 017 A1.
  • this method of preparation comprises the emulsifying mixture of components, one of which contains at least one polysiloxane, the other of which contains at least one organosilicone material which reacts with the polysiloxane in a chain extension reaction, with at least one metal ion-containing catalyst for the chain extension reaction, at least one surfactant and water present are.
  • the chain extension reaction may also include the reaction of an Si-OH group (e.g., a hydroxy-terminated polysiloxane) with an alkoxy group (e.g., alkoxysilanes, silicates, or alkoxysiloxanes) in the presence of a metal-containing catalyst to form polysiloxanes.
  • an Si-OH group e.g., a hydroxy-terminated polysiloxane
  • an alkoxy group e.g., alkoxysilanes, silicates, or alkoxysiloxanes
  • the polysiloxanes used in the chain extension reaction comprise a substantially linear polymer of the following structure: R-Si (R 2 MO-Si (R 2 Hn-O-SiR 3
  • each R independently represents a hydrocarbon radical having up to 20 carbon atoms, preferably having 1 to 6 carbon atoms, such as an alkyl group (for example, methyl, ethyl, propyl or butyl), an aryl group (for example, phenyl), or group required for the chain extension reaction ("reactive group", for example Si-bonded H atoms, aliphatically unsaturated groups such as vinyl, allyl or hexenyl, hydroxy, alkoxy, such as methoxy, ethoxy or propoxy, alkoxy-alkoxy, acetoxy, amino, etc.), with the proviso that on average one to two reactive groups are present per polymer, n is a positive number> 1.
  • n is numbers describing polysiloxanes having viscosities between 1 and 1,000,000 mm 2 / s, more preferably viscosities between 1,000 and 100,000 mm 2 / s.
  • the polysiloxanes may be branched to a low degree (for example, ⁇ 2 mol% of the siloxane units), but the polymers are substantially linear, more preferably fully linear.
  • the substituents R may in turn be substituted, for example with N-containing groups (for example amino groups), epoxy groups, S-containing groups, Si-containing groups, O-containing groups, etc.
  • N-containing groups for example amino groups
  • epoxy groups for example amino groups
  • S-containing groups for example amino groups
  • Si-containing groups for example O-containing groups
  • O-containing groups etc.
  • at least 80% of the radicals R are alkyl radicals, especially preferably methyl groups.
  • the organosilicone material that reacts with the polysiloxane in the chain extension reaction may be either a second polysiloxane or a molecule that acts as a chain extender.
  • the organosilicone material is a polysiloxane, it has the above-mentioned general structure. In these cases, one polysiloxane in the reaction has (at least) one reactive group, and a second polysiloxane has (at least) a second reactive group that reacts with the first.
  • the organosilicone material comprises a chain-extending agent
  • it may be a material such as a silane, a siloxane (e.g. disiloxane or trisiloxane) or a silazane.
  • a composition comprising a polysiloxane according to the general structure described above having at least one Si-OH group can be chain extended by reacting with an alkoxysilane (for example, a dialkoxysilane or trialkoxysilane) in the presence of tin or titanium-containing catalysts is reacted.
  • an alkoxysilane for example, a dialkoxysilane or trialkoxysilane
  • the metal-containing catalysts in the chain extension reaction are usually specific for a particular reaction.
  • Such catalysts are known in the art and include, for example, metals such as platinum, rhodium, tin, titanium, copper, lead, etc.
  • a polysiloxane having at least one aliphatically unsaturated group, preferably an end group is reacted with an organosilicone material
  • a hydrosilylation catalyst which reacts with a siloxane or polysiloxane is a (preferably terminal) Si-H group.
  • the polysiloxane has at least one aliphatically unsaturated group and satisfies the general formula given above in which R and n are as defined above, with an average of between 1 and 2 groups R having one aliphatically unsaturated group per polymer.
  • the organosilicone material having at least one Si-H group preferably has the above-mentioned structure, wherein R and n are as defined above and wherein, on average, between 1 and 2 groups R is hydrogen and n is 0 or a positive integer.
  • This material may be a polymer or a low molecular weight material such as a siloxane (for example, a disiloxane or a trisiloxane).
  • a siloxane for example, a disiloxane or a trisiloxane
  • the polysiloxane having at least one aliphatically unsaturated group and the organosilicone material having at least one Si-H group react in the presence of a hydrosilylation catalyst.
  • a hydrosilylation catalyst include, for example, platinum and rhodium-containing materials.
  • the catalysts may take any known form, for example platinum or rhodium coated on support materials (such as silica gel or activated carbon) or other suitable compounds such as platinum chloride, salts of platinum or chloroplatinic acids.
  • Chloroplatinic acid either as a commercially available hexahydrate or in anhydrous form is a preferred catalyst because of good dispersibility in organosilicone systems and low color change.
  • a polysiloxane having at least one Si-OH group, preferably an end group is reacted with an organosilicone material having at least one alkoxy group, preferably a siloxane having at least one Si-OR group or an alkoxysilane having at least two alkoxy groups ,
  • the catalyst used is again a metal-containing catalyst.
  • organometallic compounds such as organotin salts, titanates or titanium chelates or complexes.
  • organometallic compounds such as organotin salts, titanates or titanium chelates or complexes.
  • organometallic compounds such as organotin salts, titanates or titanium chelates or complexes.
  • organometallic compounds such as organotin salts, titanates or titanium chelates or complexes.
  • organometallic compounds such as organotin salts, titanates or titanium chelates or complexes.
  • organometallic compounds such as organotin salts, titanates or titanium chelates or complexes.
  • examples include stannous octoate, dibutyltin dilaurate, dibutyltin diacetate, dimethyltin dineodecanoate, dibutyltin dimethoxide, isobutyltin triceroate, dimethyltin dibutyrate, dimethyltin dineo
  • R is identical or different radicals from the group -H, -phenyl, -benzyl, -CH 2 -CH (CH 3 ) Ph, the C-
  • the silicones are preferably water-soluble.
  • Agents of the embodiment with a silicone c2) preferably used according to the invention are characterized in that the silicone c2) is water-soluble.
  • Corresponding hydrophilic silicones are selected, for example, from the compounds of the formulas (Si-6) and / or (Si-7).
  • Particularly preferred water-soluble silicone-based surfactants are selected from the group of dimethicone copolyols which are preferably alkoxylated, in particular polyethoxylated or polypropoxylated.
  • Dimethicone copolyols are understood according to the invention as meaning preferably polyoxyalkylene-modified dimethylpolysiloxanes of the general formulas (Si-6) or (Si-7):
  • radical R is a hydrogen atom, an alkyl group having 1 to 12 C atoms, an alkoxy group having 1 to 12 C atoms or a hydroxyl group
  • radicals R 'and R denote alkyl groups having 1 to 12 C atoms
  • x is an integer from 1 to 100, preferably from 20 to 30
  • y is an integer from 1 to 20, preferably from 2 to 10
  • a and b are integers from 0 to 50, preferably from 10 to 30.
  • dimethicone copolyols according to the invention are, for example, the products sold commercially under the trade name SILWET (Union Carbide Corporation) and DOW CORNING (Dow).
  • Dimethicone copolyols particularly preferred according to the invention are Dow Corning 190 and Dow Corning 193 (Dow).
  • the sphingolipids of the formula (CE-I) are preferably used,
  • R 1 is a linear C 12 - to C 30 alkyl group or a saturated or unsaturated ⁇ - (C 12 - to C 2 o) acyloxy (Ci 2 -C 3 o) alkyl group (as preferred tricosanyl, heptadecanyl or ⁇ -
  • R 2 is a saturated or unsaturated C 15 alkyl group or a saturated or unsaturated C 15 hydroxyalkyl group (such as pentadeca-1-en-1-yl, 3 -
  • Preferred compounds according to formula VI according to the invention are the compounds ceramides I, ceramides II, ceramides 1, ceramides 2, ceramides 3, ceramides 5 and ceramides 6 known under the INCI names as active ingredient (W).
  • Mixtures of the compounds of formula are particularly preferably used (CE-I) which are obtainable for example under the trade name of SK-Influx ® and Ceramide IM respectively by Degussa Care Specialties, and the commercial product Ceramide TIC-001, sold by the company Takasago International Corporation is marketed.
  • the compounds of the formula (CE-I) are preferably used in an amount of 0.01 to 1.0% by weight, based on the weight of the ready-to-use cosmetic product.
  • Pseodoceramide such as in particular the pseudoceramide N- (C 8-22 acyl) C 8-22 acyl hydroxyproline (such as cetyl-hydroxyproline Palmitamide according commercial product Sym Repair 153884 of the company Symrise) according to the invention pseudoceramides c3).
  • the ready-to-use agent according to the invention should preferably have a pH in the range from pH 5 to pH 12, in particular from pH 7 to pH 11. Particularly preferred is the use of the hair dye in a weakly alkaline medium in a pH range between pH 7 and pH 9.
  • the ingredients are preferably contained in a carrier.
  • a carrier are, for example, creams, emulsions, gels or surfactant-containing foaming solutions, such as shampoos, foam aerosols or other preparations which are particularly suitable for use on the hair.
  • the ingredients in a powdered or tablet-like formulation, which is dissolved in water before use.
  • the carriers may in particular be aqueous or aqueous-alcoholic.
  • An aqueous carrier contains at least 50% by weight of water.
  • aqueous-alcoholic carriers are aqueous solutions containing from 3 to 70% by weight of at least one C.sub.12 alcohol which is liquid at room temperature and atmospheric pressure and has at least one hydroxyl group (in particular ethanol, 1,2-propylene glycol, glycerol, isopropanol). to understand.
  • compositions of the invention may additionally contain other organic solvents, such as methoxybutanol, benzyl alcohol, or ethyl diglycol. Preference is given to all water-soluble organic solvents.
  • Agents described in the first subject of the invention are particularly well suited for use according to the invention on keratin-containing fibers, in particular human hair.
  • Keratin fibers are wool, furs, feathers and especially human hair to understand.
  • the combination of the invention may in principle but also on other natural fibers such.
  • As polyamide, polyacrylonitrile, polyurethane and polyester fibers are used.
  • a further subject of the present invention is therefore a method for treating keratin-containing fibers, in particular human hair, in which an agent of the first subject of the invention is applied to the fibers and rinsed off again after a contact time.
  • the application temperatures can be in a range between 15 and 40 0 C.
  • the hair dye is removed by Rinse away from the hair to be dyed.
  • the washing with a shampoo is omitted if a strong surfactant-containing carrier, such as a dyeing shampoo was used.
  • a third aspect of the invention is therefore the use of an agent of the first subject of the invention for coloring keratin-containing fibers, in particular human hair, which contain 1, 3-dihydroxyacetone and at least one natural dye.
  • an agent of the first subject of the invention for coloring keratin-containing fibers, in particular human hair, which contain 1, 3-dihydroxyacetone and at least one natural dye.
  • the agents according to the invention are preferably used for coloring keratin-containing fibers, in particular human hair.

Abstract

The invention relates to an agent, containing a combination of 1,3-dihydroxyacetone and at least one natural dye, particularly from the group of diaryloyl methane dyes, naphthoquinone dyes, flavonoid dyes, anthraquinone dyes, betalaine dyes, gallotannin dyes, and indigoid dyes, by means of which fibers containing keratin, particularly human hair, can be died naturally, intensively, and wash fast.

Description

„Färbemittel mit Naturfarbstoffen und 1,3-Dihydroxyaceton" "Dyes with natural dyes and 1,3-dihydroxyacetone"
Die Erfindung betrifft Mittel zur Färbung keratinhaltiger Fasern, insbesondere menschlicher Haare, enthaltend Naturfarbstoffe und 1 ,3-Dihydroxyaceton, sowie dessen Verwendung zur Färbung keratinhaltiger Fasern und ein Färbeverfahren, in dem diese Mittel zur Anwendung kommen.The invention relates to agents for coloring keratin fibers, in particular human hair, containing natural dyes and 1, 3-dihydroxyacetone, and its use for coloring keratin fibers and a dyeing process in which these agents are used.
Zur Bereitstellung farbverändernder kosmetischer Mittel, insbesondere für die Haut oder keratinhaltige Fasern wie beispielsweise menschliche Haare, kennt der Fachmann je nach Anforderungen an die Färbung diverse Färbesysteme.To provide color-changing cosmetic agents, in particular for the skin or keratin-containing fibers such as human hair, the skilled person knows various dyeing systems depending on the requirements of the dyeing.
Für permanente, intensive Färbungen mit entsprechenden Echtheitseigenschaften werden sogenannte Oxidationsfärbemittel verwendet. Solche Färbemittel enthalten üblicherweise Oxidationsfarbstoffvorprodukte, sogenannte Entwicklerkomponenten und Kupplerkomponenten. Die Entwicklerkomponenten bilden unter dem Einfluss von Oxidationsmitteln oder von Luftsauerstoff untereinander oder unter Kupplung mit einer oder mehreren Kupplerkomponenten die eigentlichen Farbstoffe aus. Die Oxidationsfärbemittel zeichnen sich zwar durch hervorragende, lang anhaltende Färbeergebnisse aus. Für natürlich wirkende Färbungen muss aber üblicherweise eine Mischung aus einer größeren Zahl von Oxidationsfarbstoffvorprodukten eingesetzt werden; in vielen Fällen werden weiterhin direktziehende Farbstoffe zur Nuancierung verwendet.For permanent, intensive colorations with corresponding fastness properties, so-called oxidation colorants are used. Such colorants usually contain oxidation dye precursors, so-called developer components and coupler components. The developer components form under the influence of oxidizing agents or of atmospheric oxygen with one another or with coupling with one or more coupler components, the actual dyes. The oxidation dyes are characterized by excellent, long-lasting dyeing results. For naturally acting dyeings, however, usually a mixture of a larger number of oxidation dye precursors must be used; In many cases, direct dyes are still used for shading.
Als Entwicklerkomponenten werden üblicherweise primäre aromatische Amine mit einer weiteren, in para- oder ortho-Position befindlichen, freien oder substituierten Hydroxy- oder Aminogruppe, heterozyklische Hydrazone, Diaminopyrazolderivate sowie 2,4,5,6-Tetraaminopyrimidin und dessen Derivate eingesetzt.The developer components used are usually primary aromatic amines having a further, in the para or ortho position, free or substituted hydroxy or amino group, heterocyclic hydrazones, diaminopyrazole derivatives and 2,4,5,6-tetraaminopyrimidine and its derivatives.
Spezielle Vertreter sind beispielsweise p-Phenylendiamin, p-Toluylendiamin, 2,4,5,6-Tetraamino- pyrimidin, p-Aminophenol, N,N-Bis(2-hydroxyethyl)-p-phenylendiamin, 2-(2,5-Diaminophenyl)- ethanol, 2-(2,5-Diaminophenoxy)-ethanol, 4-Amino-3-methylphenol, 2-Aminomethyl-4- aminophenol, 4,5-Diamino-1-(2-hydroxyethyl)pyrazol, 2-Hydroxy-4,5,6-triaminopyrimidin, 2,4- Dihydroxy-5,6-diaminopyrimidin, 2,5,6-Triamino-4-hydroxypyrimidin und 1 ,3-N,N'-Bis(2-hydroxy- ethyl)-N,N'-bis(4-aminophenyl)-diamino-propan-2-ol.Specific representatives are, for example, p-phenylenediamine, p-toluenediamine, 2,4,5,6-tetraaminopyrimidine, p-aminophenol, N, N-bis (2-hydroxyethyl) -p-phenylenediamine, 2- (2,5-) Diaminophenyl) ethanol, 2- (2,5-diaminophenoxy) ethanol, 4-amino-3-methylphenol, 2-aminomethyl-4-aminophenol, 4,5-diamino-1- (2-hydroxyethyl) pyrazole, 2- Hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine, 2,5,6-triamino-4-hydroxypyrimidine and 1,3-N, N'-bis (2-hydroxyethyl ) -N, N'-bis (4-aminophenyl) -diamino-propan-2-ol.
Als Kupplerkomponenten werden in der Regel m-Phenylendiaminderivate, Naphthole, Pyridinderivate, Resorcin und Resorcinderivate, Pyrazolone und m-Aminophenole verwendet. Als Kupplersubstanzen eignen sich insbesondere 1-Naphthol, 1 ,5-Dihydroxynaphthalin, 2,7- Dihydroxynaphthalin, 1 ,7-Dihydroxynaphthalin, 5-Amino-2-methylphenol, m-Aminophenol, Resorcin, Resorcinmonomethylether, m-Phenylendiamin, 1-Phenyl-3-methyl-pyrazol-5-on, 2,4-Di- chlor-3-aminophenol, 1 ,3-Bis-(2,4-diaminophenoxy)-propan, 2-Amino-3-hydroxypyridin, A- Chlorresorcin, 2-Chlor-6-methyl-3-aminophenol, 2-Methylresorcin, 5-Methylresorcin und 2-Methyl- 4-chlor-5-aminophenol.As coupler components m-phenylenediamine derivatives, naphthols, pyridine derivatives, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenols are generally used. Particularly suitable as coupler substances are 1-naphthol, 1,5-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinomonomethyl ether, m-phenylenediamine, 1-phenyl 3-methyl-pyrazol-5-one, 2,4-dichloro-3-aminophenol, 1, 3-bis- (2,4-diaminophenoxy) -propane, 2-amino-3-hydroxypyridine, A- Chlororesorcinol, 2-chloro-6-methyl-3-aminophenol, 2-methylresorcinol, 5-methylresorcinol and 2-methyl-4-chloro-5-aminophenol.
Für temporäre Färbungen werden üblicherweise Färbe- oder Tönungsmittel verwendet, die als färbende Komponente sogenannte Direktzieher enthalten. Hierbei handelt es sich um Farbstoffmoleküle, die direkt auf das Substrat aufziehen und keinen oxidativen Prozess zur Ausbildung der Farbe benötigen. Zu diesen Farbstoffen gehört beispielsweise das bereits aus dem Altertum zur Färbung von Körper und Haaren bekannte Henna. Diese Färbungen sind gegen Shampoonieren in der Regel deutlich empfindlicher als die oxidativen Färbungen, so dass dann sehr viel schneller eine vielfach unerwünschte Nuancenverschiebung oder gar ein sichtbarer homogener Farbverlust eintritt.For temporary dyeings usually dyeing or tinting agents are used which contain so-called direct drawers as a coloring component. These are dye molecules that attach directly to the substrate and do not require an oxidative process to form the paint. These dyes include, for example, the henna already known from antiquity for coloring body and hair. These dyeings are generally much more sensitive to shampooing than the oxidative dyeings, so that a much more undesirable change in shade or even a visible, homogeneous color loss occurs much more quickly.
Schließlich hat ein weiteres Färbe verfahren große Beachtung gefunden. Bei diesem Verfahren werden Vorstufen des natürlichen Haarfarbstoffes Melanin auf das Substrat, z.B. Haare, aufgebracht; diese bilden dann im Rahmen oxidativer Prozesse im Haar naturanaloge Farbstoffe aus. Bei, insbesondere mehrfacher, Anwendung von Mitteln mit 5,6-Dihydroxyindolin ist es möglich, Menschen mit ergrauten Haaren die natürliche Haarfarbe wiederzugeben. Die Ausfärbung kann dabei mit Luftsauerstoff als einzigem Oxidationsmittel erfolgen, so dass auf keine weiteren Oxidationsmittel zurückgegriffen werden muss. Bei Personen mit ursprünglich mittelblondem bis braunem Haar kann das Indolin als alleinige Farbstoffvorstufe eingesetzt werden. Für die Anwendung bei Personen mit ursprünglich roter und insbesondere dunkler bis schwarzer Haarfarbe können dagegen befriedigende Ergebnisse häufig nur durch Mitverwendung weiterer Farbstoffkomponenten, insbesondere spezieller Oxidationsfarbstoffvorprodukte, erzielt werden.Finally, another dyeing process has received much attention. In this method, precursors of the natural hair dye melanin are applied to the substrate, e.g. Hair, applied; These then form naturally-analogous dyes in the course of oxidative processes in the hair. In particular, multiple use of agents with 5,6-dihydroxyindoline, it is possible to reproduce natural hair color to people with graying hair. The coloration can be done with atmospheric oxygen as the sole oxidant, so that no further oxidizing agents must be used. In individuals with originally medium blond to brown hair, the indoline can be used as the sole dye precursor. On the other hand, satisfactory results can often only be achieved for use in persons with originally red and, in particular, dark to black hair color, by using other dye components, in particular special oxidation dye precursors.
Eine weitere Möglichkeit zur Färb Veränderung bietet die Verwendung von Färbemitteln, welche sogenannte Oxofarbstoffvorprodukte enthalten. Eine erste Klasse der Oxofarbstoffvorprodukte sind Verbindungen mit mindestens einer reaktiven Carbonylgruppe. Diese erste Klasse wird als Komponente (Oxo1 ) bezeichnet. Eine zweite Klasse der Oxofarbstoffvorprodukte bilden CH-acide Verbindungen und Verbindungen mit primärer oder sekundärer Aminogruppe oder Hydroxygruppe, die wiederum ausgewählt werden aus Verbindungen der Gruppe, die gebildet wird aus primären oder sekundären aromatischen Aminen, stickstoffhaltigen heterozyklischen Verbindungen sowie aromatischen Hydroxyverbindungen. Diese zweite Klasse wird als Komponente (Oxo2) bezeichnet. Die vorgenannten Komponenten (Oxo1 ) und (Oxo2) sind im Allgemeinen selbst keine Farbstoffe, und eignen sich daher jede für sich genommen allein nicht zur Färbung keratinhaltiger Fasern. In Kombination bilden sie in einem nichtoxidativen Prozess der sogenannten Oxofärbung Farbstoffe aus. Die resultierenden Färbungen besitzen teilweise Farbechtheiten auf der keratinhaltigen Faser, die mit denen der Oxidationsfärbung vergleichbar sind. Das mit der schonenden Oxofärbung erzielbare Nuancenspektrum ist sehr breit und die erhaltene Färbung weist oftmals eine akzeptable Brillanz und Farbtiefe auf. Unter Verbindungen der Komponente (Oxo2) können allerdings auch entsprechende Oxidationsfarbstoffvorprodukte vom Entwickler- und/oder Kupplertyp mit oder ohne Einsatz eines Oxidationsmittels Verwendung finden. Somit lässt sich die Methode der Oxofärbung ohne weiteres mit dem oxidativen Färbesystem kombinieren.Another possibility for dyeing change is the use of colorants which contain so-called Oxofarbstoffvorprodukte. A first class of oxo dye precursors are compounds having at least one reactive carbonyl group. This first class is called a component (Oxo1). A second class of oxo dye precursors form CH-acidic compounds and compounds having primary or secondary amino groups or hydroxy groups, which in turn are selected from compounds of the group formed from primary or secondary aromatic amines, nitrogen-containing heterocyclic compounds and aromatic hydroxy compounds. This second class is called a component (Oxo2). The aforementioned components (oxo1) and (oxo2) are generally not themselves dyes, and therefore are not in themselves suitable for coloring keratin-containing fibers. In combination, they form dyes in a non-oxidative process of so-called oxo dyeing. The resulting dyeings have partially color fastness on the keratin-containing fiber, which are comparable to those of the oxidation dyeing. The Nuancenspektrum achievable with the gentle oxo staining is very broad and the color obtained often has an acceptable brilliance and color depth. However, it is also possible to use corresponding developer and / or coupler-type oxidation dye precursors with or without the use of an oxidizing agent in compounds of the component (oxo2). Thus, the method of oxo staining can be readily combined with the oxidative staining system.
Sollen Substrate aufgehellt oder gar gebleicht werden, werden die das Substrat färbenden Farbstoffe meist oxidativ unter Einsatz von entsprechenden Oxidationsmitteln, wie beispielsweise Wasserstoffperoxid, entfärbt.If substrates are to be lightened or even bleached, the dyes coloring the substrate are usually decolorized oxidatively using appropriate oxidizing agents, for example hydrogen peroxide.
Färbemittel zur Färbung keratinhaltiger Fasern, insbesondere menschlicher Haare, bei denen auf den Einsatz synthetischer Farbstoffe oder Farbstoffvorstufen verzichtet wird, basieren im wesentlichen auf Henna als Naturfarbstoff. Mit Henna ist für den Fachmann aber nur ein begrenztes Spektrum an Färbenuancen zu erreichen, vorwiegend im Bereich der roten Farbtöne. Dahingegen ist der Bereich der natürlichen Haarfarbenuancen bei Verwendung von natürlich vorkommenden Farbstoffen nur sehr schwer zugänglich. Insbesondere für den natürlichen Blond- und Braunbereich kommt erschwerend hinzu, dass in jüngerer Vergangenheit auf den Einsatz einiger natürlicher Farbstoffe aufgrund von toxikologischen Bedenken verzichtet wurde.Colorants for coloring keratin-containing fibers, in particular human hair, in which the use of synthetic dyes or dye precursors is dispensed with are based essentially on henna as a natural dye. With henna, however, the specialist is only able to achieve a limited spectrum of color nuances, predominantly in the area of red shades. In contrast, the range of natural hair shades is very difficult to access when using naturally occurring dyes. In particular, for natural blond and brown areas, it is aggravating that in recent years the use of some natural dyes has been dispensed with because of toxicological concerns.
Es ist ein Bestreben, die mit Naturfarbstoffen erzielbaren Färbungen in Ihrem Farbergebnis zu intensivieren. Eine hohe Färbekraft trägt zur Wirtschaftlichkeit von Färbemitteln bei. Außerdem sollen die erzielten Färbungen ein hohes Maß an Farbechtheit z.B. gegen Schweiß, Waschen, Licht oder Reibung aufweisen und müssen insbesondere im Rahmen der Haarpflege kompatibel mit anderen Haarbehandlungsmitteln sein.It is an effort to intensify the achievable with natural dyes dyes in your color result. A high tinting strength contributes to the cost-effectiveness of colorants. In addition, the dyeings obtained should have a high degree of color fastness, e.g. against sweat, washing, light or friction and must be compatible with other hair treatment products, especially in the context of hair care.
Die Bereitstellung eines Färbemittels, mit dem gerade die hellen, natürlichen Nuancen bei gleichzeitigem Verzicht auf synthetische Farbstoffe zugänglich werden, ist daher als äußerst wünschenswert anzusehen.The provision of a colorant, with the just the bright, natural nuances are accessible while dispensing with synthetic dyes, therefore, is to be regarded as highly desirable.
Es wurde nun überraschend gefunden, dass natürliche Haarfärbeergebnisse durch Kombination von 1 ,3-Dihydroxyaceton mit Naturfarbstoffen möglich werden. Speziell im Braun- und Blondbereich konnte durch Kombination von 1 ,3-Dihydroxyaceton mit einem oder mehreren Naturfarbstoffen eine breite natürliche Nuancenpalette mit intensiven und farbechten Färbungen zugänglich gemacht werden.It has now surprisingly been found that natural hair dyeing results by combining 1, 3-dihydroxyacetone with natural dyes are possible. Especially in the brown and blond range, a broad range of natural shades with intensive and colourfast dyeings could be made accessible by combining 1,3-dihydroxyacetone with one or more natural dyes.
Dem Fachmann sind bereits Färbemittel für das menschliche Haar bekannt, bei denen eine Kombination von Dihydroxyaceton mit verschiedenen synthetischen Oxidationsfarbstoff- vorprodukten eingesetzt wird, wie beispielsweise in EP1250908 B1 bis EP1250912 B1 sowie in EP1293192 A2 beschrieben. Der Einsatz von Dihydroxyaceton mit verschiedenen synthetischen Oxidationsfarbstoff- vorprodukten in Kombination mit weiteren Inhaltsstoffen ist insbesondere aus US20050210606 A1 sowie aus EP1237817 A2 und EP1237818 A2 bekannt.Colorants for human hair are already known to the person skilled in the art, in which a combination of dihydroxyacetone with various synthetic oxidation dye precursors is used, as described, for example, in EP1250908 B1 to EP1250912 B1 and in EP1293192 A2. The use of dihydroxyacetone with various synthetic oxidation dye precursors in combination with other ingredients is known in particular from US20050210606 A1 and EP1237817 A2 and EP1237818 A2.
Ebenso wurde der Einsatz von Küpenfarbstoffen zusammen mit Dihydroxyaceton zum Färben von Haaren in WO2005094762 A1 und WO2005094763 A1 beschrieben. Alle diese Färbemittel enthalten jedoch synthetische Farbstoffe oder Farbstoffvorprodukte.Likewise, the use of vat dyes together with dihydroxyacetone for dyeing hair has been described in WO2005094762 A1 and WO2005094763 A1. However, all these colorants contain synthetic dyes or dye precursors.
Ein erster Gegenstand der Erfindung ist daher ein Mittel zum Färben keratinhaltiger Fasern, insbesondere menschlicher Haare, dadurch gekennzeichnet, dass es 1 ,3-Dihydroxyaceton und mindestens einen Naturfarbstoff enthält.A first subject of the invention is therefore an agent for dyeing keratin-containing fibers, in particular human hair, characterized in that it contains 1, 3-dihydroxyacetone and at least one natural dye.
Es ist erfindungsgemäß bevorzugt, wenn das erfindungsgemäße Mittel 1 ,3-Dihydroxyaceton in einer Menge von 0,1 bis 10,0 Gew.-%, insbesondere in einer Menge von 1 ,0 bis 5,0 Gew.-%, jeweils bezogen auf das Gewicht des Mittels, enthält.It is inventively preferred if the inventive agent 1, 3-dihydroxyacetone in an amount of 0.1 to 10.0 wt .-%, in particular in an amount of 1, 0 to 5.0 wt .-%, each based on the weight of the agent contains.
Es ist erfindungsgemäß bevorzugt, wenn das erfindungsgemäße Mittel mindestens einen Naturfarbstoff in einer Menge von 0,001 bis 20,0 Gew.-%, insbesondere in einer Menge von 0,01 bis 15,0 Gew.-%, jeweils bezogen auf das Gewicht des Mittels, enthält.It is inventively preferred if the agent according to the invention at least one natural dye in an amount of 0.001 to 20.0 wt .-%, in particular in an amount of 0.01 to 15.0 wt .-%, each based on the weight of the composition , contains.
Im Sinne der Erfindung sind Naturfarbstoffe aus Pflanzenteilen gewinnbare Verbindungen, die einerseits Farbstoffe als solche darstellen (d.h. von sich aus farbig sind), oder aus Pflanzenteilen gewinnbare Verbindungen, die Farbstoffvorstufen darstellen, welche durch nachfolgende chemische Reaktion den eigentlichen Farbstoff ausbilden. Genannt sei hier insbesondere die Oxidation mit Luftsauerstoff zur Ausbildung des Chromophors.For the purposes of the invention, natural dyes are harvestable compounds from plant parts which on the one hand represent dyes (i.e., are inherently colored) or compounds recoverable from plant parts which are dye precursors which form the actual dye by subsequent chemical reaction. Mentioned here in particular the oxidation with atmospheric oxygen to form the chromophore.
Zur Gewinnung der Naturfarbstoffe eignen sich bevorzugt unterschiedliche Pflanzenteile, je nach gewünschtem Farbstoff. Es versteht sich jedoch, dass ein Farbstoff aus mehr als einem Pflanzenteil gewonnen werden kann. Die bevorzugten Pflanzenteile zur Gewinnung von Naturfarbstoffen sind in der Gruppe enthalten, die gebildet wird aus Wurzel, Stengel, Rinde, Kernholz, Harz, Blüte, Blatt, Frucht und/oder Pflanzensaft.To obtain the natural dyes are preferably different parts of plants, depending on the desired dye. It is understood, however, that a dye can be obtained from more than one plant part. The preferred plant parts for obtaining natural dyes are included in the group formed from root, stem, bark, heartwood, resin, flower, leaf, fruit and / or sap.
Es ist insbesondere im Sinne der Erfindung nicht erforderlich, dass die Naturfarbstoffe beziehungsweise Naturfarbstoffvorstufen jeweils einheitliche Verbindungen darstellen. Bedingt durch unterschiedliche, nicht einheitliche Gewinnungsverfahren wie beispielsweise unterschiedliche Extraktions- oder Fermentationsbedingungen oder durch Nutzung verschiedener, regionaler Unterarten und verschiedener Pflanzenteile oder teilweise auch aus kultur-historischer Tradition enthalten manche genannten Naturfarbstoffe bewusst keine einheitlichen Verbindungen, sondern Gemische aus Farbstoffen, Farbstoffvorstufen und weiteren Komponenten, wie insbesondere Gerbstoffen. Im Sinne der Erfindung als Naturfarbstoff wird selbstverständlich auch ein aus einem solchen Gemisch isolierter, diskreter Farbstoff oder gegebenenfalls auch mehrere, aus einem solchen Gemisch isolierte, diskrete, farbgebende Verbindungen verstanden.It is not necessary, in particular for the purposes of the invention, for the natural dyes or natural dye precursors to be each one of the same compounds. Due to different, non-uniform extraction methods such as different extraction or fermentation conditions or by using different, regional subspecies and different parts of plants or partly from culture-historical tradition, some natural dyes mentioned deliberately contain no uniform compounds, but mixtures of dyes, dye precursors and other components , in particular tannins. For the purposes of the invention, a natural dye is understood to mean, of course, a discrete dye isolated from such a mixture, or optionally also a plurality of discrete, coloring compounds isolated from such a mixture.
Folgende Klassen von Naturfarbstoffen finden in den erfindungsgemäßen kosmetischen Mitteln als Färbemittel für keratinische Fasern bevorzugte Anwendung:The following classes of natural dyes are preferred in the cosmetic compositions according to the invention as colorants for keratinic fibers:
a) Diaryloylmethanfarbstoffe, wie beispielsweise enthalten in der Wurzel von Kurkuma (Gelbwurzel; Cl. Natural Yellow 3) - Curcuma domestica mit den färbenden Inhaltsstoffen Curcumin (Cl. 75300), Demethoxycurcumin und Bisdemethoxycurcumin.a) Diaryloylmethane dyes, such as, for example, contained in the root of turmeric (Turmeric, Cl.Natural Yellow 3) - Curcuma domestica with the coloring ingredients curcumin (Cl.75300), demethoxycurcumin and bisdemethoxycurcumin.
Curcumin (R = R' =OMe) Demethoxycurcumin (R = H; R' = OMe) Bisdemethoxycurcumin (R = R' =H)
Figure imgf000006_0001
Curcumin (R = R '= OMe) Demethoxycurcumin (R = H; R' = OMe) Bisdemethoxycurcumin (R = R '= H)
Figure imgf000006_0001
b) Naphthochinonfarbstoffe, wie beispielsweise enthalten in Henna, rot (Cl. Natural Orange 6) aus den Blättern des Hennastrauchs - Lawsonia inermis L mit dem färbenden Inhaltsstoff Lawson (Cl. 75480):b) Naphthoquinone dyes, such as contained in henna, red (Cl. Natural Orange 6) from the leaves of henna - Lawsonia inermis L with the coloring ingredient Lawson (Cl.75480):
Figure imgf000006_0002
Figure imgf000006_0002
in Fruchtschalen und Blättern (Cl. Natural Brown 7) aus dem Walnussbaum - Juglus regia L. mit dem färbenden Inhaltsstoff Juglon (Cl. 75500):in fruit peel and leaves (Cl. Natural Brown 7) from the walnut tree - Juglus regia L. with the coloring ingredient Juglon (Cl.
Figure imgf000006_0003
Figure imgf000006_0003
in Alkannawurzel oder Shikoninwurzel (Cl. Natural Red 20) - Alkanna tinctoria beziehungsweise Lithospermum erythrorhizon mit dem färbenden Inhaltsstoffen Alkannan (Cl. 75520) und Alkannin (Cl. 75530) beziehungsweise Shikonin (Cl. 75535):
Figure imgf000007_0001
in alkana root or shikonin root (Cl.Natural Red 20) - Alkanna tinctoria or Lithospermum erythrorhizon with the coloring ingredients alkannane (Cl.75520) and alkannine (Cl.75530) or shikonin (Cl.75535):
Figure imgf000007_0001
in Lapachoholz von Tecoma ipe, Tecoma lapacho, Tecoma leucoxylon oder Tecoma achracea (Cl. Natural Yellow 16) mit dem färbenden Inhaltsstoffen Lapachol (Cl. 75490), sowie untergeordnet Desoxylapachol, α-Lapachon, ß-Lapachon, Melchinon I, Lapachononund Dehydro- α-lapachon:in Lapacho wood from Tecoma ipe, Tecoma lapacho, Tecoma leucoxylon or Tecoma achracea (Cl., Natural Yellow 16) with the coloring ingredient lapachol (Cl.75490), as well as subordinate desoxylapachol, α-lapachone, β-lapachone, melchinone I, lapachonone and dehydro- α-lapachone:
Figure imgf000007_0002
α-Lapachon Dehydro-α-Lapachon ß-Lapachon
Figure imgf000007_0002
α-lapachone dehydro-α-lapachone β-lapachone
c) Anthrachinonfarbstoffe, wie beispielsweise in Krapp-Wurzeln (Cl. Natural Red 8) - Rubia peregrina und Rubia tinctorum mit den färbenden Inhaltsstoffen Purpurin (Cl. 75410), Pseudopurpurin (Cl. 75420; Cl. 58220-snythetisch), Alizarin (Cl. 75330), Rubiadin (Cl. 75350) und Munjistin (Cl. 75370): Purpurin (R = H; R' = R" = OH) Pseudopurpurin (R = CO2H; R' = R" = OH) Alizarin (R =OH, R' = R" = H) Rubiadin (R = CH3; R' = OH; R" = H) Munijistin (R = CO2H; R' = OH; R" = H)
Figure imgf000007_0003
c) anthraquinone dyes, such as, for example, madder roots (Cl., Natural Red 8), Rubia peregrina and Rubia tinctorum with the coloring constituents purpurin (Cl.75410), pseudopurpurine (Cl.75420, Cl. 58220-synthetic), alizarin (Cl 75330), rubiadin (CI 75350) and munjistine (CI 75370): purpurin (R = H; R '= R "= OH) pseudopurpurin (R = CO 2 H; R' = R" = OH) alizarin ( R = OH, R '= R "= H) Rubiadine (R = CH 3 , R' = OH, R" = H) Munijistine (R = CO 2 H, R '= OH, R "= H)
Figure imgf000007_0003
in den Wurzeln und Stengeln des Indischen Krapp (Cl. Natural Red 16) - Rubia cordifolia und Rubia sikkimensis mit den färbenden Inhaltsstoffen Purpurin (Cl. 75410), Pseudopurpurin (Cl. 75420; Cl. 58220-snythetisch), Alizarin (Cl. 75330), und Munjistin (Cl. 75370) sowie Nordamnacanthal, Physcion und Purpuroxanthin (Cl. 75340):
Figure imgf000008_0001
in the roots and stems of the Indian madder (Cl.Natural Red 16) - Rubia cordifolia and Rubia sikkimensis with the coloring ingredients purpurin (Cl.75410), pseudopurpurine (cl.75420, Cl.58220-snythetic), alizarin (Cl.75330 Munjistin (Cl.75370) as well as Nordamnacanthal, Physcion and Purpuroxanthin (Cl.75340):
Figure imgf000008_0001
in Rharbarber-Wurzeln - Rheum undulatum L, Rheum palmatum L und weitere Rheum- Spezies mit den färbenden Inhaltsstoffen Emodin, Chrystophanol (Cl. 75400; Cl. Natural Yellow 23), Aloe-emodin, Physcion, Rhein, den Heterodianthronen Rheidin A, B, C, Palmidin A, B, C, D und Sennidin C sowie davon abgeleitete Anthra- und Diglykoside:in Rharbarber roots - Rheum undulatum L, Rheum palmatum L and other Rheum species with the coloring constituents Emodin, Chrystophanol (Cl.75400, CI Natural Yellow 23), Aloe-emodin, Physcion, Rhine, the heterodianthrones Rheidin A, B , C, palmidin A, B, C, D and sennidine C as well as derived anthra- and diglycosides:
Emodin (R = OH, R' = CH3) Chrysophanol (R = H, R' = CH3) Aloe-emodin (R = CH2OH, R' = H) Rhein (R = CO2H, R' = H)
Figure imgf000008_0002
Emodin (R = OH, R '= CH 3 ) Chrysophanol (R = H, R' = CH 3 ) Aloe-emodin (R = CH 2 OH, R '= H) Rhein (R = CO 2 H, R' = H)
Figure imgf000008_0002
in den Wurzeln des Echten Labkraut - Galium verum L, Gemeinen Labkraut - Galium mollugo L, Klebkraut - Galium aparine L, Waldmeister - Galium odoratum (Cl. Natural Red 14) mit den färbenden Inhaltsstoffen Purpurin (Cl. 75410), Pseudopurpurin (Cl. 75420; Cl. 58220- snythetisch), Alizarin (Cl. 75330), Rubiadin (Cl. 75350), Purpuroxanthin (Cl. 75340), Lucidin, Alizarin-1-methylether, Alizarin-2-methylether, 2-Hydroxyanthrachinon und 1-Hydroxy-2- methylanthrachinon:in the roots of the genus Labiata - Galium verum L, Common labweed - Galium mollugo L, Catchstraw - Galium aparine L, Woodruff - Galium odoratum (Cl. Natural Red 14) with the coloring constituents Purpurin (Cl.75410), Pseudopurpurin (Cl. 75420, Cl. 58220 (synthetic)), alizarin (CI 75330), rubiadin (CI 75350), purpuroxanthin (CI 75340), lucidin, alizarin 1-methyl ether, alizarin 2-methyl ether, 2-hydroxyanthraquinone and 1- Hydroxy-2-methylanthraquinone:
Lucidin (R' = CH2OH; R = R" = OH) Alizarin-1-methylether (R =0Me, R' = OH; R" = H) Alizarin-2-methylether (R =OH, R' = OMe; R" = H) 2-Hydroxyanthrachinon (R' = OH; R = R" = H) 1-Hydroxy-2-methylanthrachinon (R = OH; R' = CH3; R" = H)
Figure imgf000008_0003
Lucidine (R '= CH 2 OH; R = R "= OH) Alizarin 1-methyl ether (R = 0 Me, R' = OH; R" = H) Alizarin 2-methyl ether (R = OH, R '= OMe R "= H) 2-hydroxyanthraquinone (R '= OH; R = R" = H) 1-hydroxy-2-methylanthraquinone (R = OH; R' = CH 3 ; R "= H)
Figure imgf000008_0003
in Färbermeisterwurzel (Cl. Natural Red 13) - Asperula tinctoria mit den färbenden Inhaltsstoffen Purpurin (Cl. 75410), Pseudopurpurin (Cl. 75420; Cl. 58220-snythetisch) und Alizarin (Cl. 75330),in Dyer's Master's Root (Cl.Natural Red 13) - Asperula tinctoria with the coloring ingredients purpurin (Cl.75410), pseudopurpurine (Cl.75420, Cl.S 58220-synthetic) and alizarin (Cl.75330),
in der Rinde des Faulbaum - Rhamnus fragula L. tinctoria mit den färbenden Inhaltsstoffen Emodin, 4 Emodin-Glukoside: Glucofragulin A, Glucofrangulin B, Frangulin A, Frangulin B, Physcion und Chrysophanol (Cl. 75400): Glucofrangulin A (R = O-3-ß-L-rhamno-1-ß-Din the bark of the decay tree - Rhamnus fragula L. tinctoria with the coloring constituents Emodin, 4 emodin glucosides: glucofragulin A, glucofrangulin B, frangulin A, frangulin B, physcion and chrysophanol (Cl.75400): glucofrangulin A (R = O) 3-beta-L-rhamno-1-ß-D
Glucofrangulin B (R = O-L-rhamno-D-glucosii Frangulin A (R = O-3-ß-L-rhamnosid) Frangulin B (R = O-3-α-L-rhamnosid)
Figure imgf000008_0004
d) Indigoide Farbstoffe, wie beispielsweise in den Blättern und teilweise Stengeln des Indischem Indigo - Indigofera tinctoria (Indigofera argentea), Färberwaid - lsatis tinctoria, Färberoleander - Wrightia tinctoria und Wildem Indigo - Baptisia tinctoria (Cl. Natural Blue 1 ) mit den Farbstoffvorprodukten lsatan B und Indican, welche durch einen Gärungsprozess oxidativ in den eigentlichen Farbstoff Indigo (Cl. 75780; Cl. 73000) sowie untergeordnet lndirubin (Cl. 75790; Cl. 73200) und lsatin überführt werden:Glucofangulin B (R = OL-rhamno-D-glucosii frangulin A (R = O-3-β-L-rhamnoside) frangulin B (R = O-3-α-L-rhamnoside)
Figure imgf000008_0004
d) Indigoid dyes, such as, for example, in the leaves and partial stems of Indian Indigo Indigo Farmera (Indigofera argentea), Fawnwort lsatis tinctoria, Dyeing Colanders - Wrightia tinctoria and Wild Indigo - Baptisia tinctoria (CI Natural Blue 1) with the dye precursors lsatan B and Indican, which are oxidatively converted by a fermentation process into the actual dye indigo (Cl.75780, Cl.73000) and subordinated indirubin (Cl.75790, Cl.73200) and isatin:
Figure imgf000009_0001
lndirubin Isatin unter anderem unter den Namen Indigofera folium oder Henna, schwarz als Handelsprodukt, zumeist in Kombination mit Extrakten von Lawsonia Inermis, erhältlich,
Figure imgf000009_0001
Indirine isatin, inter alia, under the name Indigofera folium or Henna, black as a commercial product, mostly in combination with extracts of Lawsonia Inermis, available,
e) Flavonoidfarbstoffe, wie beispielsweise in den Blütenköpfen von Römischer Kamille - Chamaemelum nobile (Cl. Natural Yellow 1 ) und Deutscher Kamille - Chamomilla recutica mit den färbenden Inhaltsstoffen Apigenin (Cl. 75580; Cl. Natural Yellow 1 ,2), Rutin (Cl. 75730; Natural Yellow 10), sowie untergeordnet Luteolin (Cl. 75590), Kampferöl (Cl. 75460, Cl. Natural Yellow 13, 10) und Quercetin (Cl. 75670; Cl. Natural Yellow 10,13; Cl. Natural Red 1 ) und davon abgeleitete Glukoside:e) flavonoid dyes, such as, for example, in the flower heads of Roman chamomile - Chamaemelum nobile (Cl., Natural Yellow 1) and German chamomile - Chamomilla recutica with the coloring constituents apigenin (Cl.75580, CI Natural Yellow 1, 2), rutin (Cl 75530, Natural Yellow 10) and camphor oil (Cl.75460, Cl.Natural Yellow 13, 10) and quercetin (Cl.75670, CI Natural Yellow 10, 13; Cl. Natural Red 1) and glucosides derived therefrom:
Figure imgf000009_0002
Figure imgf000009_0002
Apigenin (R = R' = H) Luteolin (R = OH; R' = H) Kampferöl (R = H, R' = OH)
Figure imgf000009_0003
Quercetin (R = R' = OH) Rutin in den Blättern und Stengeln von Salbei - Salvia tribola L mit den färbenden Inhaltsstoffen Luteolin (Cl. 75590) und Salvigenin:Apigenin (R = R '= H) Luteolin (R = OH, R' = H) Camphor oil (R = H, R '= OH)
Figure imgf000009_0003
Quercetin (R = R '= OH) rutin in the leaves and stems of sage - Salvia tribola L with the coloring ingredients luteolin (Cl. 75590) and salvigenin:
Figure imgf000010_0001
Figure imgf000010_0001
in den Blättern und Stengeln von Rosmarin - Rosmarinus Officinalis mit den färbenden Inhaltsstoffen Luteolin (Cl. 75590) und Apigenin (Cl. 75580; Cl. Natural Yellow 1 ,2) sowie weiteren Flavonoiden,in the leaves and stems of rosemary - Rosmarinus Officinalis with the coloring ingredients luteolin (Cl.75590) and apigenin (Cl.75580, Cl. Natural Yellow 1, 2) and other flavonoids,
f) Neoflavanoidfarbstoffe, wie beispielsweise in Blauholz (Cl. Natural Black 1 ), Kernholz von Haematoxylum campechianum L mit dem färbenden Flavonoid Quercetin und dem Farbstoffvorprodukt Hämatoxylin, welches oxidativ in den Farbstoff Hämatein (Cl. 75290, Cl. Natural Black 1 und 2) umgewandelt wird:f) neoflavanoid dyes, such as, for example, in bluewood (Cl.Natural Black 1), heartwood of Haematoxylum campechianum L with the coloring flavonoid quercetin and the dye precursor hematoxylin, which oxidatively binds to hematin dye (CI 75290, CI Natural Black 1 and 2) is converted:
Figure imgf000010_0002
Figure imgf000010_0002
in Sappanholz - Caesalpinia sappan L, Brazilienholz - Caesalpinia brasiliensis L, Nicaraguaholz - Caesalpinia echinata, Pernambunkholz - Caesalpinia crista L, Brasilietteholz - Haematoxylum braziletto , jeweils als Kernholz (Cl. Natural Red 24), mit dem Farbstoffvorprodukt Brasilin, welches oxidativ in den Farbstoff Brasilein (Cl. 75280, Cl. Natural Red 24) umgewandelt wird:in sappan wood - Caesalpinia sappan L, brazil wood - Caesalpinia brasiliensis L, Nicaraguan wood - Caesalpinia echinata, pernambunk wood - Caesalpinia crista L, braziliette wood - Haematoxylum braziletto, each as heartwood (Cl.Natural Red 24), with the dye precursor Brasilin, which is oxidative in the dye Brasilein (Cl.75280, Cl. Natural Red 24) is converted:
Figure imgf000010_0003
Figure imgf000010_0003
g) .unlösliche Rotholz'-Farbstoffe, wie beispielsweise in Rotem Sandelholz, Kernholz von Pterocarpus santalinus L, Narraholz - Pterocarpus indicus L, Barholz - Pterocarpus soyauxii L, Camholz - Bahia nitida (Cl. Natural Red 22) mit den färbenden Inhaltsstoffen Santalin A, Santalin B, Tetra-O-methyl- santarubin, Hompterocarpin, Pterocarpin, Maackiain, den Isoflavioniden Formononetin und Santal, sowie dem Chalkon Isoliquiritigenin und dem Flavon Liquiritigenin:g) "insoluble redwood" dyes, as for example in red sandalwood, heartwood of Pterocarpus santalinus L, Narrawood - Pterocarpus indicus L, Barwood - Pterocarpus soyauxii L, Camwood - Bahia nitida (Cl. Natural Red 22) with the coloring ingredients Santalin A, Santalin B, Tetra-O-methyl - santarubin, hompterocarpine, pterocarpine, maackiain, the isoflavionides formononetin and santal, and the chalcone isoliquiritigenin and the flavone liquiritigenin:
Figure imgf000011_0001
Isoliquiritigenin Liquiritigenin
Figure imgf000011_0001
Isoliquiritigenin Liquiritigenin
h) Betalainfarbstoffe wie beispielsweise in Rote Beete Wurzeln - Beta vulgaris mit den färbenden Hauptinhaltsstoffen Betanidin und Praebetanin sowie untergeordnet weiteren Betacyaninen, Betaxanthinen, Vulgaxanthinen, Anthocyanen und Eisen- und Kupfer-Komplexen:
Figure imgf000012_0001
h) Betaine dyes such as beetroot roots - Beta vulgaris containing the main coloring constituents betanidine and prebetanine and subordinate further betacyanines, betaxanthines, vulgaxanthines, anthocyanins and iron and copper complexes:
Figure imgf000012_0001
i) Gallotanninfarbstoffe wie beispielsweise in der Rinde von Stiel- oder Sommereiche - Quercus robur L. mit den färbenden Hauptinhaltsstoffen aus der Gruppe der Gallotannine und Ellagentannine (Glykoside der Gallussäure beziehungsweise der Ellagsäure; Cl. 75270):i) Gallotannin dyes, for example in the bark of stalk or summer areas - Quercus robur L. with the main coloring constituents from the group of gallotannins and ellagannins (glycosides of gallic acid or ellagic acid, Cl.75270):
Figure imgf000012_0002
Figure imgf000012_0002
Gallussäure
Figure imgf000012_0003
gallic acid
Figure imgf000012_0003
j) Farbstoffe aus kondensierten Gerbstoffen, wie beispielsweise in Catechu (Cl. Natural Brown 3), eine Mischung aus Extrakten von Färbe pflanzen, vorzugsweise Acacia catechu, Areca catechu und Uncaria gambier, mit einem hohen Anteil von kondensierten Gerbstoffen (,Proanthocyanidine') vom Catechin-Typ:j) condensed tannin dyes, as for example in Catechu (CI Natural Brown 3), a mixture of extracts of staining plants, preferably Acacia catechu, Areca catechu and Uncaria gambier, with a high proportion of condensed tannins ('proanthocyanidins') of catechin type:
Figure imgf000012_0004
(+)-Catechin
Figure imgf000012_0004
(+) - catechin
wie in den Blättern von grünem und schwarzem (= fermentiertem grünen) Tee - Camellia sinensis, mit den Inhaltsstoffen Gallussäure, m-Digallussäure, Catechin, Glykosiden von Flavonoiden wie, unter anderen, Luteolin, Apigenin, Kampferöl, Quercetin, Myriecetin, sowie Thearubingenine (,Proanthocyanidine'), Theaflavin und Isotheaflavin: Theaflavin
Figure imgf000013_0001
Isotheaflavinas in the leaves of green and black (= fermented green) tea - Camellia sinensis, with the ingredients gallic acid, m-digallic acid, catechin, glycosides of flavonoids such as, among others, luteolin, apigenin, camphor oil, quercetin, myriecetine, and thearubingenins ( Proanthocyanidins), theaflavin and isotheaflavin: theaflavin
Figure imgf000013_0001
Isotheaflavin
Insbesondere enthalten die erfindungsgemäßen kosmetischen Mittel mindestens einen Naturfarbstoff aus der Gruppe, umfassend Diaryloylmethanfarbstoffe, Naphthochinonfarbstoffe, Flavonoidfarbstoffe, Anthrachinonfarbstoffe, Betalainfarbstoffe, Gallotanninfarbstoffe und indigoide Farbstoffe.In particular, the cosmetic compositions according to the invention contain at least one natural dye from the group comprising diaryloylmethane dyes, naphthoquinone dyes, flavonoid dyes, anthraquinone dyes, betalain dyes, gallotannin dyes and indigoid dyes.
Erfindungsgemäß bevorzugte Naturfarbstoffe sind solche, die aus einer Pflanze erhalten wurde, die aus der Gruppe ausgewählt wird, die gebildet wird aus Indigofera tinctoria, Curcuma longa, Lawsonia inermis, Chamomilla recutita, Quercus robur, Rosmarinus officinalis, Rheum undulatum und Beta vulgaris.Natural dyes preferred according to the present invention are those obtained from a plant selected from the group consisting of Indigofera tinctoria, Curcuma longa, Lawsonia inermis, Chamomilla recutita, Quercus robur, Rosmarinus officinalis, Rheum undulatum and Beta vulgaris.
Besonders bevorzugt ist dabei die Gruppe, die gebildet wird aus Diaryloylmethanfarbstoffen, Naphthochinonfarbstoffen und indigoiden Farbstoffen.Particularly preferred is the group which is formed from Diaryloylmethanfarbstoffen, naphthoquinone dyes and indigoid dyes.
Ganz besonders bevorzugt sind in den erfindungsgemäßen kosmetischen Mitteln Naturfarbstoffe von Pflanzen enthalten, die ausgewählt sind aus der Gruppe, zusammengesetzt aus Curcuma longa (Kurkuma; Cl. Natural Yellow 3), Lawsonia inermis (Henna, rot; Cl. Natural Orange 6) und Indigofera tinctoria (Henna, schwarz; Cl. Natural Blue 1 ).Very particular preference is given in the cosmetic compositions according to the invention to natural dyes of plants selected from the group consisting of Curcuma longa (turmeric, CI Natural Yellow 3), Lawsonia inermis (Henna, red, CI Natural Orange 6) and Indigofera tinctoria (Henna, black, Cl. Natural Blue 1).
Die Naturfarbstoffe werden jeweils bevorzugt in einer Menge von 0, 01 bis 20 Gew.-%, bezogen auf die gesamte Anwendungszubereitung, eingesetzt. Die Gesamtmenge an Naturfarbstoffen beträgt vorzugsweise höchstens 20 Gew.-%.The natural dyes are each preferably used in an amount of from 0.01 to 20% by weight, based on the total application preparation. The total amount of natural dyes is preferably at most 20% by weight.
Als besonders vorteilhaft hat sich in der vorliegenden Erfindung die zusätzliche Verwendung mindestens eines weiteren Kohlenhydrates der allgemeinen Formel (I) dargestellt:In the present invention, the additional use of at least one further carbohydrate of the general formula (I) has proven particularly advantageous:
Figure imgf000013_0002
Figure imgf000013_0002
worin n für 1 oder 2 steht undwherein n is 1 or 2 and
R für ein Wasserstoffatom oder eine Hydroxymethylgruppe steht, Alle Stereoisomere der Kohlehydrate Formel (I) sowie deren Gemische eignen sich zur Lösung der erfindungsgemäßen Aufgabe.R is a hydrogen atom or a hydroxymethyl group, All stereoisomers of the carbohydrate formula (I) and mixtures thereof are suitable for achieving the object according to the invention.
Bevorzugt werden die Verbindungen der Formel (I) aus einer oder mehrerer Verbindungen der Formeln (1-1 ) bis (1-12) ausgewählt:The compounds of the formula (I) are preferably selected from one or more compounds of the formulas (1-1) to (1-12):
Figure imgf000014_0001
(D-erythro-2-pentulose) (L-erythro-2-pentulose) (D-threo-2-pentulose)
Figure imgf000014_0001
(D-erythro-2-pentulose) (L-erythro-2-pentulose) (D-threo-2-pentulose)
Figure imgf000014_0002
Figure imgf000014_0002
(L-threo-2-pentulose) (D-Erythrulose) (L-Erythrulose)(L-threo-2-pentulose) (D-erythrulose) (L-erythrulose)
Figure imgf000014_0003
Figure imgf000014_0003
(D-Erythrose) (L-Erythrose) (D-Threose)(D-erythrose) (L-erythrose) (D-Threose)
Figure imgf000014_0004
(L-Threose) (D-Glyceraldehyd) (L-Glyceraldehyd)
Figure imgf000014_0004
(L-Threose) (D-Glyceraldehyde) (L-Glyceraldehyde)
Wiederum besonders eignen sich solche Verbindungen der Formel (I), die im Molekül mindestens drei Hydroxygruppen tragen.Again, particularly suitable are compounds of the formula (I) which carry at least three hydroxyl groups in the molecule.
Verbindungen der Formel (I), die ausgewählt werden aus mindestens einer Verbindung aus der Gruppe, die gebildet wird aus D-Erythrulose, L-Erythrulose, DL-Erythrulose, D-Ribulose und 2,3,4-Trihydroxybutanal, insbesondere aus der Gruppe D-Erythrulose, L-Erythrulose, DL- Erythrulose, sind besonders bevorzugt. Es ist erfindungsgemäß bevorzugt, wenn das erfindungsgemäße Mittel das zusätzliche Kohlenhydrat gemäß Formel (I) in einer Menge von 0,1 bis 10,0 Gew.-%, insbesondere in einer Menge von 2,0 bis 6,0 Gew.-%, jeweils bezogen auf das Gewicht des Mittels, enthält.Compounds of the formula (I) which are selected from at least one compound from the group formed from D-erythrulose, L-erythrulose, DL-erythrulose, D-ribulose and 2,3,4-trihydroxybutanal, in particular from the group D-erythrulose, L-erythrulose, DL-erythrulose are particularly preferred. It is preferred according to the invention if the agent according to the invention contains the additional carbohydrate according to formula (I) in an amount of 0.1 to 10.0% by weight, in particular in an amount of 2.0 to 6.0% by weight, each based on the weight of the agent contains.
Wenngleich im Sinne der Erfindung solche erfindungsgemäßen Mittel bevorzugt sind, die auf weitere Farbstoffe nicht natürlichen Ursprungs verzichten, können die erfindungsgemäßen Mittel in einer weiteren Ausführungsform zusätzlich mindestens eine farbve rändernde Komponente enthalten, die von den erfindungsgemäßen Naturfarbstoffen verschieden sind. Die zusätzlichen farbve rändernden Komponenten im Sinne der vorliegenden Erfindung werden bevorzugt ausgewähltAlthough agents according to the invention are preferred for the purposes of the invention which do not dispense with further dyes of non-natural origin, in a further embodiment the agents according to the invention may contain at least one color-changing component which is different from the natural dyes according to the invention. The additional color-changing components in the sense of the present invention are preferably selected
(1 ) aus mindestens einem Oxidationsfarbstoffvorprodukt vom Typ der Entwicklerkomponenten und gegebenenfalls zusätzlich mindestens einer Kupplerkomponente und/oder(1) at least one oxidation dye precursor of the type of developer components and optionally additionally at least one coupler component and / or
(2) aus Oxofarbstoffvorprodukten und/oder(2) from oxo dye precursors and / or
(3) aus mindestens einem direktziehenden Farbstoff und/oder(3) from at least one direct dye and / or
(4) aus mindestens einem Oxidationsmittel und gegebenenfalls mindestens einem Bleichverstärker.(4) from at least one oxidizing agent and optionally at least one bleach booster.
Es kann erfindungsgemäß bevorzugt sein, als Entwicklerkomponente ein p- Phenylendiaminderivat oder eines seiner physiologisch verträglichen Salze einzusetzen. Besonders bevorzugt sind p-Phenylendiaminderivate der Formel (E1 )It may be preferred according to the invention to use as the developer component a p-phenylenediamine derivative or one of its physiologically acceptable salts. Particular preference is given to p-phenylenediamine derivatives of the formula (E1)
Figure imgf000015_0001
wobei
Figure imgf000015_0001
in which
G1 steht für ein Wasserstoffatom, einen (C1 bis C4)-Alkylrest, einen (C1 bis C4)- Monohydroxyalkylrest, einen (C2 bis C4)-Polyhydroxyalkylrest, einen (C1 bis C4)-Alkoxy-(C-ι bis C4)-alkylrest, einen 4'-Aminophenylrest oder einen (C1 bis C4)-Alkylrest, der mit einer stickstoffhaltigen Gruppe, einem Phenyl- oder einem 4'-Aminophenylrest substituiert ist; G2 steht für ein Wasserstoffatom, einen (C1 bis C4)-Alkylrest, einen (C1 bis C4)- Monohydroxyalkylrest, einen (C2 bis C4)-Polyhydroxyalkylrest, einen (C1 bis C4)-Alkoxy-(C-ι bis C4)-alkylrest oder einen (C1 bis C4)-Alkylrest, der mit einer stickstoffhaltigen Gruppe substituiert ist;G 1 represents a hydrogen atom, a (C 1 to C 4 ) -alkyl radical, a (C 1 to C 4 ) monohydroxyalkyl radical, a (C 2 to C 4 ) -polyhydroxyalkyl radical, a (C 1 to C 4 ) -alkoxy - (C 1 -C 4 ) -alkyl radical, a 4'-aminophenyl radical or a (C 1 to C 4 ) -alkyl radical which is substituted by a nitrogen-containing group, a phenyl or a 4'-aminophenyl radical; G 2 represents a hydrogen atom, a (C 1 to C 4 ) -alkyl radical, a (C 1 to C 4 ) monohydroxyalkyl radical, a (C 2 to C 4 ) -polyhydroxyalkyl radical, a (C 1 to C 4 ) -alkoxy - (C 1 -C 4 ) -alkyl radical or a (C 1 to C 4 ) -alkyl radical which is substituted by a nitrogen-containing group;
G3 steht für ein Wasserstoffatom, ein Halogenatom, wie ein Chlor-, Brom-, lod- oder Fluoratom, einen (C1 bis C4)-Alkylrest, einen (C1 bis C4)-Monohydroxyalkylrest, einen (C2 bis C4)-Polyhydroxyalkylrest, einen (C1 bis C4)-Hydroxyalkoxyrest, einen (C1 bis C4)- Acetylaminoalkoxyrest, einen Mesylamino-(Ci bis C4)-alkoxyrest oder einen (Ci bis C4)-G 3 represents a hydrogen atom, a halogen atom such as a chlorine, bromine, iodine or fluorine atom, a (C 1 to C 4 ) alkyl radical, a (C 1 to C 4 ) monohydroxyalkyl radical, a (C 2 to C 4 ) -polyhydroxyalkyl radical, a (C 1 to C 4 ) -hydroxyalkoxy radical, a (C 1 to C 4 ) - Acetylaminoalkoxy, a Mesylamino- (Ci to C 4 ) alkoxy or a (Ci to C 4 ) -
Carbamoylaminoalkoxyrest;Carbamoylaminoalkoxyrest;
G4 steht für ein Wasserstoffatom, ein Halogenatom oder einen (C1 bis C4)-Alkylrest oder wenn G3 und G4 in ortho-Stellung zueinander stehen, können sie gemeinsam eine verbrückende α,ω-Alkylendioxogruppe, wie beispielsweise eine Ethylendioxygruppe bilden.G 4 represents a hydrogen atom, a halogen atom or a (C 1 to C 4 ) -alkyl radical or, when G 3 and G 4 are ortho to each other, they may together form a bridging α, ω-alkylenedioxo group, such as, for example, an ethylenedioxy group ,
Besonders bevorzugte p-Phenylendiamine der Formel (E1 ) werden ausgewählt aus einer oder mehrerer Verbindungen der Gruppe, die gebildet wird, aus p-Phenylendiamin, p-Toluylendiamin, 2-Chlor-p-phenylendiamin, 2,3-Dimethyl-p-phenylendiamin, 2,6-Dimethyl-p-phenylendiamin, 2,6- Diethyl-p-phenylendiamin, 2,5-Dimethyl-p-phenylendiamin, N,N-Dimethyl-p-phenylendiamin, N, N- Diethyl-p-phenylendiamin, N,N-Dipropyl-p-phenylendiamin, 4-Amino-3-methyl-(N,N-diethyl)-anilin, N,N-Bis-(ß-hydroxyethyl)-p-phenylendiamin, 4-N,N-Bis-(ß-hydroxyethyl)-amino-2-methylanilin, A- N,N-Bis-(ß-hydroxyethyl)-amino-2-chloranilin, 2-(ß-Hydroxyethyl)-p-phenylendiamin, 2-(α,ß- Dihydroxyethyl)-p-phenylendiamin, 2-Fluor-p-phenylendiamin, 2-lsopropyl-p-phenylendiamin, N- (ß-Hydroxypropyl)-p-phenylendiamin, 2-Hydroxymethyl-p-phenylendiamin, N,N-Dimethyl-3- methyl-p-phenylendiamin, N,N-(Ethyl,ß-hydroxyethyl)-p-phenylendiamin, N-(ß,γ-Dihydroxypropyl)- p-phenylendiamin, N-(4'-Aminophenyl)-p-phenylendiamin, N-Phenyl-p-phenylendiamin, 2-(ß- Hydroxyethyloxy)-p-phenylendiamin, 2-(ß-Acetylaminoethyloxy)-p-phenylendiamin, N-(ß- Methoxyethyl)-p-phenylendiamin, N-(4-Amino-3-methylphenyl)-N-[3-(1 H-imidazol-1- yl)propyl]amin, 5,8-Diaminobenzo-1 ,4-dioxan sowie ihren physiologisch verträglichen Salzen.Particularly preferred p-phenylenediamines of formula (E1) are selected from one or more compounds of the group formed from p-phenylenediamine, p-toluenediamine, 2-chloro-p-phenylenediamine, 2,3-dimethyl-p-phenylenediamine , 2,6-dimethyl-p-phenylenediamine, 2,6-diethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, N, N-dimethyl-p-phenylenediamine, N, N-diethyl-p-phenylenediamine , N, N-dipropyl-p-phenylenediamine, 4-amino-3-methyl- (N, N-diethyl) -aniline, N, N-bis (β-hydroxyethyl) -p-phenylenediamine, 4-N, N Bis (β-hydroxyethyl) amino-2-methylaniline, A-N, N-bis (β-hydroxyethyl) amino-2-chloroaniline, 2- (β-hydroxyethyl) -p-phenylenediamine, 2- (β-hydroxyethyl) -p-phenylenediamine α, β-dihydroxyethyl) -p-phenylenediamine, 2-fluoro-p-phenylenediamine, 2-isopropyl-p-phenylenediamine, N- (β-hydroxypropyl) -p-phenylenediamine, 2-hydroxymethyl-p-phenylenediamine, N, N Dimethyl 3-methyl-p-phenylenediamine, N, N- (ethyl, β-hydroxyethyl) -p-phenylenediamine, N- (β, γ-dihydroxypropyl) -p-phenylenediamine, N- (4'-aminophenyl) p-phenylenediamine, N-phenyl p-phenylenediamine, 2- (β-hydroxyethyloxy) -p-phenylenediamine, 2- (β-acetylaminoethyloxy) -p-phenylenediamine, N- (β-methoxyethyl) -p-phenylenediamine, N- (4-amino-3-methylphenyl ) -N- [3- (1H-imidazol-1-yl) propyl] amine, 5,8-diaminobenzo-1, 4-dioxane and their physiologically acceptable salts.
Erfindungsgemäß ganz besonders bevorzugte p-Phenylendiaminderivate der Formel (E1 ) sind ausgewählt aus mindestens einer Verbindung der Gruppe p-Phenylendiamin, p-Toluylendiamin, 2-(ß-Hydroxyethyl)-p-phenylendiamin, 2-(α,ß-Dihydroxyethyl)-p-phenylendiamin, N,N-Bis-(ß- hydroxyethyl)-p-phenylendiamin, N-(4-Amino-3-methylphenyl)-N-[3-(1 H-imidazol-1-yl)propyl]amin, sowie den physiologisch verträglichen Salzen dieser Verbindungen.Very particularly preferred according to the invention p-phenylenediamine derivatives of the formula (E1) are selected from at least one compound of the group p-phenylenediamine, p-toluenediamine, 2- (ß-hydroxyethyl) -p-phenylenediamine, 2- (α, ß-dihydroxyethyl) - p-phenylenediamine, N, N-bis- (β-hydroxyethyl) -p-phenylenediamine, N- (4-amino-3-methylphenyl) -N- [3- (1H-imidazol-1-yl) propyl] amine , as well as the physiologically acceptable salts of these compounds.
Es kann erfindungsgemäß weiterhin bevorzugt sein, als Entwicklerkomponente Verbindungen einzusetzen, die mindestens zwei aromatische Kerne enthalten, die mit Amino- und/oder Hydroxylgruppen substituiert sind.It may further be preferred according to the invention to use as developer component compounds which contain at least two aromatic nuclei which are substituted by amino and / or hydroxyl groups.
Unter den zweikernigen Entwicklerkomponenten, die in den Färbezusammensetzungen gemäß der Erfindung verwendet werden können, kann man insbesondere die Verbindungen nennen, die der folgenden Formel (E2) entsprechen, sowie ihre physiologisch verträglichen Salze:Among the binuclear developer components which can be used in the dyeing compositions according to the invention, mention may be made in particular of the compounds corresponding to the following formula (E2) and their physiologically tolerated salts:
Figure imgf000016_0001
wobei: Z1 und Z2 stehen unabhängig voneinander für einen Hydroxyl- oder NH2-ReSt, der gegebenenfalls durch einen (C1 bis C4)-Alkylrest, durch einen (C1 bis C4)-Hydroxyalkylrest und/oder durch eine Verbrückung Y substituiert ist oder der gegebenenfalls Teil eines verbrückenden Ringsystems ist, die Verbrückung Y steht für eine Alkylengruppe mit 1 bis 14 Kohlenstoffatomen, wie beispielsweise eine lineare oder verzweigte Alkylenkette oder einen Alkylenring, die von einer oder mehreren stickstoffhaltigen Gruppen und/oder einem oder mehreren Heteroatomen wie Sauerstoff-, Schwefel- oder Stickstoffatomen unterbrochen oder beendet sein kann und eventuell durch einen oder mehrere Hydroxyl- oder (C1 bis C8)-Alkoxyreste substituiert sein kann, oder eine direkte Bindung,
Figure imgf000016_0001
in which: Z 1 and Z 2 independently of one another represent a hydroxyl or NH 2 radical optionally substituted by a (C 1 to C 4 ) -alkyl radical, by a (C 1 to C 4 ) -hydroxyalkyl radical and / or by a bridge Y The bridging Y is an alkylene group having 1 to 14 carbon atoms, such as a linear or branched alkylene chain or an alkylene ring, which of one or more nitrogen-containing groups and / or one or more heteroatoms such as Oxygen, sulfur or nitrogen atoms may be interrupted or terminated and may be substituted by one or more hydroxyl or (C 1 to C 8 ) alkoxy, or a direct bond,
G5 und G6 stehen unabhängig voneinander für ein Wasserstoff- oder Halogenatom, einen (C1 bis C4)-Alkylrest, einen (C1 bis C4)-Monohydroxyalkylrest, einen (C2 bis C4)- Polyhydroxyalkylrest, einen (C1 bis C4)-Aminoalkylrest oder eine direkte Verbindung zur Verbrückung Y,G 5 and G 6 independently of one another represent a hydrogen or halogen atom, a (C 1 to C 4 ) -alkyl radical, a (C 1 to C 4 ) -monohydroxyalkyl radical, a (C 2 to C 4 ) -hydroxyalkyl radical, a ( C 1 to C 4 ) -aminoalkyl radical or a direct compound for bridging Y,
G7, G8, G9, G10, G11 und G12 stehen unabhängig voneinander für ein Wasserstoffatom, eine direkte Bindung zur Verbrückung Y oder einen (C1 bis C4)-Alkylrest, mit der Maßgabe, dass die Verbindungen der Formel (E2) nur eine Verbrückung Y pro Molekül enthalten.G 7 , G 8 , G 9 , G 10 , G 11 and G 12 independently represent a hydrogen atom, a direct bond to the bridge Y or a (C 1 to C 4 ) alkyl radical, with the proviso that the compounds of the Formula (E2) contain only one bridge Y per molecule.
Die in Formel (E2) verwendeten Substituenten sind erfindungsgemäß analog zu den obigen Ausführungen definiert.The substituents used in formula (E2) are defined according to the invention analogously to the above statements.
Bevorzugte zweikernige Entwicklerkomponenten der Formel (E2) werden insbesondere aus mindestens einer der folgenden Verbindungen ausgewählt: N,N'-Bis-(ß-hydroxyethyl)-N,N'-bis-(4'- aminophenyl)-1 ,3-diamino-propan-2-ol, N,N'-Bis-(ß-hydroxyethyl)-N,N'-bis-(4'-aminophenyl)- ethylendiamin, N,N'-Bis-(4'-aminophenyl)-tetramethylendiamin, N,N'-Bis-(ß-hydroxyethyl)-N,N'- bis-(4'-aminophenyl)-tetramethylendiamin, N,N'-Bis-(4-(methylamino)phenyl)- tetramethylendiamin, N,N'-Diethyl-N,N'-bis-(4'-amino-3'-methylphenyl)-ethylendiamin, Bis-(2- hydroxy-5-aminophenyl)-methan, N,N'-Bis-(4'-aminophenyl)-1 ,4-diazacycloheptan, N,N'-Bis-(2- hydroxy-5-aminobenzyl)-piperazin, N-(4'-Aminophenyl)-p-phenylendiamin und 1 ,10-Bis-(2',5'- diaminophenyl)-1 ,4,7,10-tetraoxadecan sowie ihre physiologisch verträglichen Salze.Preferred binuclear developer components of the formula (E2) are in particular selected from at least one of the following compounds: N, N'-bis- (β-hydroxyethyl) -N, N'-bis- (4'-aminophenyl) -1,3-diamino -propan-2-ol, N, N'-bis (β-hydroxyethyl) -N, N'-bis (4'-aminophenyl) ethylenediamine, N, N'-bis (4'-aminophenyl) - tetramethylenediamine, N, N'-bis (β-hydroxyethyl) -N, N'-bis (4'-aminophenyl) tetramethylenediamine, N, N'-bis (4- (methylamino) phenyl) tetramethylenediamine, N , N'-diethyl-N, N'-bis (4'-amino-3'-methylphenyl) ethylenediamine, bis (2-hydroxy-5-aminophenyl) -methane, N, N'-bis (4 '-aminophenyl) -1, 4-diazacycloheptane, N, N'-bis (2-hydroxy-5-aminobenzyl) piperazine, N- (4'-aminophenyl) -p-phenylenediamine and 1, 10-bis ( 2 ', 5'-diaminophenyl) -1, 4,7,10-tetraoxadecane and their physiologically acceptable salts.
Ganz besonders bevorzugte zweikernige Entwicklerkomponenten der Formel (E2) werden ausgewählt unter N,N'-Bis-(ß-hydroxyethyl)-N,N'-bis-(4-aminophenyl)-1 ,3-diamino-propan-2-ol, Bis-(2-hydroxy-5-aminophenyl)-methan, 1 ,3-Bis-(2,5-diaminophenoxy)-propan-2-ol, N,N'-Bis-(4- aminophenyl)-1 ,4-diazacycloheptan, 1 , 10-Bis-(2,5-diaminophenyl)-1 ,4,7,10-tetraoxadecan oder eines der physiologisch verträglichen Salze dieser Verbindungen.Very particularly preferred binuclear developer components of the formula (E2) are selected from N, N'-bis (β-hydroxyethyl) -N, N'-bis (4-aminophenyl) -1,3-diamino-propan-2-ol , Bis (2-hydroxy-5-aminophenyl) -methane, 1, 3-bis (2,5-diaminophenoxy) -propan-2-ol, N, N'-bis (4-aminophenyl) -1, 4-diazacycloheptane, 1, 10-bis (2,5-diaminophenyl) -1, 4,7,10-tetraoxadecane or one of the physiologically acceptable salts of these compounds.
Weiterhin kann es erfindungsgemäß bevorzugt sein, als Entwicklerkomponente ein p- Aminophenolderivat oder eines seiner physiologisch verträglichen Salze einzusetzen. Besonders bevorzugt sind p-Aminophenolderivate der Formel (E3)
Figure imgf000018_0001
wobei:Furthermore, it may be preferred according to the invention to use as the developer component a p-aminophenol derivative or one of its physiologically tolerable salts. Particular preference is given to p-aminophenol derivatives of the formula (E3)
Figure imgf000018_0001
in which:
G13 steht für ein Wasserstoffatom, ein Halogenatom, einen (C1 bis C4)-Alkylrest, einen (C1 bis C4)-Monohydroxyalkylrest, einen (C2 bis C4)-Polyhydroxyalkylrest, einen (C1 bis C4)-Alkoxy- (C1 bis C4)-alkylrest, einen (C1 bis C4)-Aminoalkylrest, einen Hydroxy-(C-ι bis C4)- alkylaminorest, einen (C1 bis C4)-Hydroxyalkoxyrest, einen (C1 bis C4)-Hydroxyalkyl-(C-ι bis C4)-aminoalkylrest oder einen (DK(C1 bis C4)-alkyl]amino)-(C-ι bis C4)-alkylrest, und G14 steht für ein Wasserstoff- oder Halogenatom, einen (C1 bis C4)-Alkylrest, einen (C1 bis C4)-Monohydroxyalkylrest, einen (C2 bis C4)-Polyhydroxyalkylrest, einen (C1 bis C4)-Alkoxy- (C1 bis C4)-alkylrest, einen (C1 bis C4)-Aminoalkylrest oder einen (C1 bis C4)-Cyanoalkylrest, G15 steht für Wasserstoff, einen (C1 bis C4)-Alkylrest, einen (C1 bis C4)-Monohydroxyalkylrest, einen (C2 bis C4)-Polyhydroxyalkylrest, einen Phenylrest oder einen Benzylrest, und G16 steht für Wasserstoff oder ein Halogenatom.G 13 represents a hydrogen atom, a halogen atom, a (C 1 to C 4 ) -alkyl radical, a (C 1 to C 4 ) -monohydroxyalkyl radical, a (C 2 to C 4 ) -polyhydroxyalkyl radical, a (C 1 to C 4 ) Alkoxy (C 1 to C 4 ) -alkyl radical, a (C 1 to C 4 ) -aminoalkyl radical, a hydroxy (C 1 -C 4 ) -alkylamino radical, a (C 1 to C 4 ) -hydroxyalkoxy radical, a (C 1 to C 4 ) -hydroxyalkyl- (C 1 -C 4 ) -aminoalkyl radical or a (DK (C 1 to C 4 ) -alkyl] amino) - (C 1 -C 4 ) -alkyl radical, and G 14 represents a hydrogen or halogen atom, a (C 1 to C 4 ) -alkyl radical, a (C 1 to C 4 ) -monohydroxyalkyl radical, a (C 2 to C 4 ) -polyhydroxyalkyl radical, a (C 1 to C 4 ) -Alkoxy- (C 1 to C 4 ) -alkyl radical, a (C 1 to C 4 ) -aminoalkyl radical or a (C 1 to C 4 ) -cyanoalkyl radical, G 15 is hydrogen, a (C 1 to C 4 ) Alkyl radical, a (C 1 to C 4 ) monohydroxyalkyl radical, a (C 2 to C 4 ) polyhydroxyalkyl radical, a phenyl radical or a benzyl radical, and G 16 is Wa or a halogen atom.
Die in Formel (E3) verwendeten Substituenten sind erfindungsgemäß analog zu den obigen Ausführungen definiert.The substituents used in formula (E3) are defined according to the invention analogously to the above statements.
Bevorzugte p-Aminophenole der Formel (E3) sind insbesondere p-Aminophenol, N-Methyl-p- aminophenol, 4-Amino-3-methyl-phenol, 4-Amino-3-fluorphenol, 2-Hydroxymethylamino-4- aminophenol, 4-Amino-3-hydroxymethylphenol, 4-Amino-2-(ß-hydroxyethoxy)-phenol, 4-Amino-2- methylphenol, 4-Amino-2-hydroxymethylphenol, 4-Amino-2-methoxymethyl-phenol, 4-Amino-2- aminomethylphenol, 4-Amino-2-(ß-hydroxyethyl-aminomethyl)-phenol, 4-Amino-2-(α,ß- dihydroxyethyl)-phenol, 4-Amino-2-fluorphenol, 4-Amino-2-chlorphenol, 4-Amino-2,6- dichlorphenol, 4-Amino-2-(diethyl-aminomethyl)-phenol sowie ihre physiologisch verträglichen Salze.Preferred p-aminophenols of the formula (E3) are, in particular, p-aminophenol, N-methyl-p-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 2-hydroxymethylamino-4-aminophenol, 4 -Amino-3-hydroxymethylphenol, 4-amino-2- (β-hydroxyethoxy) -phenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethyl-phenol, 4-amino -2-aminomethylphenol, 4-amino-2- (β-hydroxyethyl-aminomethyl) phenol, 4-amino-2- (α, β-dihydroxyethyl) phenol, 4-amino-2-fluorophenol, 4-amino-2 -chlorophenol, 4-amino-2,6-dichlorophenol, 4-amino-2- (diethyl-aminomethyl) -phenol and their physiologically acceptable salts.
Ganz besonders bevorzugte Verbindungen der Formel (E3) sind p-Aminophenol, 4-Amino-3- methylphenol, 4-Amino-2-aminomethylphenol, 4-Amino-2-(α,ß-dihydroxyethyl)-phenol und A- Amino-2-(diethylaminomethyl)-phenol.Very particularly preferred compounds of the formula (E3) are p-aminophenol, 4-amino-3-methylphenol, 4-amino-2-aminomethylphenol, 4-amino-2- (α, β-dihydroxyethyl) -phenol and A-amino- 2- (diethylaminomethyl) -phenol.
Ferner kann die Entwicklerkomponente ausgewählt sein aus o-Aminophenol und seinen Derivaten, wie beispielsweise 2-Amino-4-methylphenol, 2-Amino-5-methylphenol oder 2-Amino-4- chlorphenol.Further, the developer component may be selected from o-aminophenol and its derivatives such as 2-amino-4-methylphenol, 2-amino-5-methylphenol or 2-amino-4-chlorophenol.
Weiterhin kann die Entwicklerkomponente ausgewählt sein aus heterocyclischen Entwicklerkomponenten, wie beispielsweise aus Pyrimidinderivaten, Pyrazolderivaten, Pyrazolopyrimidin-Derivaten bzw. ihren physiologisch verträglichen Salzen. Bevorzugte Pyrimidin-Derivate werden erfindungsgemäß ausgewählt aus Verbindungen gemäß Formel (E4) bzw. deren physiologisch verträglichen Salzen,Furthermore, the developer component may be selected from heterocyclic developer components, such as pyrimidine derivatives, pyrazole derivatives, pyrazolopyrimidine derivatives or their physiologically acceptable salts. Preferred pyrimidine derivatives are selected according to the invention from compounds of the formula (E4) or their physiologically tolerated salts,
worin wherein
G17, G18 und G19 unabhängig voneinander für ein Wasserstoffatom, eine Hydroxygruppe, eineG 17 , G 18 and G 19 independently represent a hydrogen atom, a hydroxy group, a
(Ci bis C4)-Alkoxygruppe oder eine Aminogruppe steht und(C 1 to C 4 ) alkoxy group or an amino group and
G20 für eine Hydroxygruppe oder eine Gruppe -NG21G22 steht, worin G21 und G22 unabhängig voneinander stehen für ein Wasserstoffatom, eine (C1 bis C4)-Alkylgruppe, eine (C1 bis C4)-G 20 represents a hydroxy group or a group -NG 21 G 22 , in which G 21 and G 22 independently of one another represent a hydrogen atom, a (C 1 to C 4 ) -alkyl group, a (C 1 to C 4 ) -
Monohydroxyalkylgruppe, mit der Maßgabe, dass maximal zwei der Gruppen aus G17, G18, G19 und G20 eine Hydroxygruppe bedeuten und höchstens zwei der Reste G17, G18 und G19 für ein Wasserstoffatom stehen. Dabei ist es wiederum bevorzugt, wenn gemäß Formel (E4) mindestens zwei Gruppen aus G17, G18, G19 und G20 für eine Gruppe -NG21G22 stehen und höchstens zwei Gruppen aus G17, G18, G19 und G20 für eine Hydroxygruppe stehen.Monohydroxyalkylgruppe, with the proviso that a maximum of two of the groups of G 17 , G 18 , G 19 and G 20 is a hydroxy group and at most two of the radicals G 17 , G 18 and G 19 is a hydrogen atom. In this case, it is again preferred if, according to formula (E4), at least two groups of G 17 , G 18 , G 19 and G 20 represent a group -NG 21 G 22 and at most two groups of G 17 , G 18 , G 19 and G 20 represent a hydroxy group.
Besonders bevorzugte Pyrimidin-Derivate sind insbesondere die Verbindungen 2,4,5,6-Tetra- aminopyrimidin, 4-Hydroxy-2,5,6-triaminopyrimidin, 2-Hydroxy-4,5,6-triaminopyrimidin, 2- Dimethylamino-4,5,6-triaminopyrimidin, 2,4-Dihydroxy-5,6-diaminopyrimidin und 2,5,6- Triaminopyrimidin.Particularly preferred pyrimidine derivatives are in particular the compounds 2,4,5,6-tetra-aminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2-dimethylamino-4 , 5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine and 2,5,6-triaminopyrimidine.
Bevorzugte Pyrazol-Derivate werden erfindungsgemäß ausgewählt aus Verbindungen gemäß Formel (E5),Preferred pyrazole derivatives are selected according to the invention from compounds of the formula (E5),
Figure imgf000019_0002
worin
Figure imgf000019_0002
wherein
G23, G24, G25 stehen unabhängig voneinander für ein Wasserstoffatom, eine (C1 bis C4)- Alkylgruppe, eine (C1 bis C4)-Monohydroxyalkylgruppe, eine (C2 bis C4)-Polyhydroxy- alkylgruppe, eine gegebenenfalls substituierte Arylgruppe oder eine gegebenenfalls substituierte AIyI-(C1 bis C4)-alkylgruppe, mit der Maßgabe dass, wenn G25 für ein Wasserstoffatom steht, G26 neben den vorgenannten Gruppen zusätzlich für eine Gruppe - NH2 stehen kann,G 23, G 24, G 25 are each independently a hydrogen atom, a (C 1 to C 4) - alkyl group, a (C 1 to C 4) monohydroxyalkyl, a (C 2 to C 4) alkyl group -Polyhydroxy-, an optionally substituted aryl group or an optionally substituted AlyI- (C 1 to C 4 ) -alkyl group, with the proviso that when G 25 is a hydrogen atom, G 26 may additionally be a group - NH 2 in addition to the abovementioned groups,
G26 steht für ein Wasserstoffatom, eine (C1 bis C4)-Alkylgruppe, eine (C1 bis C4)- Monohydroxyalkylgruppe oder eine (C2 bis C4)-Polyhydroxyalkylgruppe und G27 steht für ein Wasserstoffatom, eine gegebenenfalls substituierte Arylgruppe, eine (Ci bis C4)-Alkylgruppe oder eine (C1 bis C4)-Monohydroxyalkylgruppe, insbesondere für ein Wasserstoffatom oder eine Methylgruppe.G 26 represents a hydrogen atom, a (C 1 to C 4 ) alkyl group, a (C 1 to C 4 ) monohydroxyalkyl group or a (C 2 to C 4 ) polyhydroxyalkyl group and G 27 represents a hydrogen atom, an optionally substituted aryl group, a (Ci to C 4) alkyl group or a (C 1 to C 4) -monohydroxyalkyl, especially for a hydrogen atom or a methyl group.
Bevorzugt bindet in Formel (E5) der Rest -NG25G26 an die 5 Position und der Rest G27 an die 3 Position des Pyrazolzyklus.Preferably in formula (E5) the radical -NG 25 G 26 binds to the 5 position and the radical G 27 to the 3 position of the pyrazole cycle.
Besonders bevorzugte Pyrazol-Derivate sind insbesondere die Verbindungen, die ausgewählt werden unter 4,5-Diamino-1-methylpyrazol, 4,5-Diamino-1-(ß-hydroxyethyl)-pyrazol, 3,4- Diaminopyrazol, 4,5-Diamino-1-(4'-chlorbenzyl)-pyrazol, 4,5-Diamino-1 ,3-dimethylpyrazol, 4,5- Diamino-3-methyl-1-phenylpyrazol, 4,5-Diamino-1-methyl-3-phenylpyrazol, 4-Amino-1 ,3-dimethyl- 5-hydrazinopyrazol, 1-Benzyl-4,5-diamino-3-methylpyrazol, 4,5-Diamino-3-tert.-butyl-1- methylpyrazol, 4,5-Diamino-1-tert.-butyl-3-methylpyrazol, 4,5-Diamino-1-(ß-hydroxyethyl)-3- methylpyrazol, 4,5-Diamino-1-ethyl-3-methylpyrazol, 4,5-Diamino-1-ethyl-3-(4'-methoxyphenyl)- pyrazol, 4,5-Diamino-1-ethyl-3-hydroxymethylpyrazol, 4,5-Diamino-3-hydroxymethyl-1-methyl- pyrazol, 4,5-Diamino-3-hydroxymethyl-1-isopropylpyrazol, 4,5-Diamino-3-methyl-1-isopropyl- pyrazol, 4-Amino-5-(ß-aminoethyl)amino-1 ,3-dimethylpyrazol, sowie deren physiologisch verträglichen Salze.Particularly preferred pyrazole derivatives are in particular the compounds which are selected from 4,5-diamino-1-methylpyrazole, 4,5-diamino-1- (β-hydroxyethyl) pyrazole, 3,4-diaminopyrazole, 4,5- Diamino-1- (4'-chlorobenzyl) -pyrazole, 4,5-diamino-1,3-dimethylpyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole, 4,5-diamino-1-methyl-3 phenylpyrazole, 4-amino-1,3-dimethyl-5-hydrazinopyrazole, 1-benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3-tert-butyl-1-methylpyrazole, 4 5-diamino-1-tert-butyl-3-methylpyrazole, 4,5-diamino-1- (β-hydroxyethyl) -3-methylpyrazole, 4,5-diamino-1-ethyl-3-methylpyrazole, 4.5 Diamino-1-ethyl-3- (4'-methoxyphenyl) pyrazole, 4,5-diamino-1-ethyl-3-hydroxymethylpyrazole, 4,5-diamino-3-hydroxymethyl-1-methylpyrazole, 4, 5-diamino-3-hydroxymethyl-1-isopropylpyrazole, 4,5-diamino-3-methyl-1-isopropylpyrazole, 4-amino-5- (β-aminoethyl) amino-1,3-dimethylpyrazole, and their physiological compatible salts.
Bevorzugte Pyrazolopyrimidin-Derivate sind insbesondere die Derivate des Pyrazolo[1 ,5- a]pyrimidin der folgenden Formel (E6) und dessen tautomeren Formen, sofern ein tautomeres Gleichgewicht besteht:Preferred pyrazolopyrimidine derivatives are, in particular, the derivatives of the pyrazolo [1,5-a] pyrimidine of the following formula (E6) and their tautomeric forms, if a tautomeric equilibrium exists:
Figure imgf000020_0001
wobei:
Figure imgf000020_0001
in which:
G28, G29 und G30, G31unabhängig voneinander stehen für ein Wasserstoffatom, einen (Ci bis C4)-Alkylrest, einen Aryl-Rest, einen (Ci bis C4)-Monohydroxyalkylrest, einen (C2 bis C4)- Polyhydroxyalkylrest einen (Ci bis C4)-Alkoxy-(Ci bis C4)-alkylrest, einen (Ci bis C4)- Aminoalkylrest, der gegebenenfalls durch ein Acetyl-Ureid- oder einen Sulfonyl-Rest geschützt sein kann, einen (C1 bis C4)-Alkylamino-(C-ι bis C4)-alkylrest, einen Di-[(C-ι bis C4)- alkyl]-(C-ι bis C4)-aminoalkylrest, wobei die Dialkyl-Reste gegebenenfalls einen Kohlenstoffzyklus oder einen Heterozyklus mit 5 oder 6 Kettengliedern bilden, einen (C1 bis C4)-Monohydroxyalkyl- oder einen Di[(C-ι bis C4)-Hydroxyalkyl]-(C-ι bis C4)-aminoalkylrest, die X-Reste stehen unabhängig voneinander für ein Wasserstoffatom, einen (C1 bis C4)- Alkylrest, einen Aryl-Rest, einen (C1 bis C4)-Monohydroxyalkylrest, einen (C2 bis C4)- Polyhydroxyalkylrest, einen (C1 bis C4)-Aminoalkylrest, einen (C1 bis C4)-Alkylamino-(C-ι bis C4)-alkylrest, einen DK(C1 bis C4)alkyl]-(C-ι bis C4)-aminoalkylrest, wobei die Dialkyl-Reste gegebenenfalls einen Kohlenstoffzyklus oder einen Heterozyklus mit 5 oder 6 Kettengliedern bilden, einen (C1 bis C4)-Hydroxyalkyl- oder einen Di-[(C-ι bis C4)-hydroxyalkyl]amino-(C-ι bisG 28 , G 29 and G 30 , G 31 independently of one another represent a hydrogen atom, a (C 1 to C 4 ) -alkyl radical, an aryl radical, a (C 1 to C 4 ) -monohydroxyalkyl radical, a (C 2 to C 4 ) - Polyhydroxyalkylrest a (Ci to C 4 ) -Alkoxy- (Ci to C 4 ) -alkylrest, a (Ci to C 4 ) - Aminoalkylrest, which can be protected if necessary by a Acetyl Ureid or a Sulfonyl remainder, one (C 1 to C 4) alkylamino (C-ι-C 4) alkyl, a di - [(C-ι-C 4) - alkyl] - (C-ι-C 4) aminoalkyl radical, wherein the Dialkyl radicals optionally form a carbon cycle or a heterocycle having 5 or 6 chain members, a (C 1 to C 4 ) monohydroxyalkyl or a di [(C 1 -C 4 ) -hydroxyalkyl] - (C 1 to C 4 ) aminoalkyl, the X radicals are each independently a hydrogen atom, a (C 1 to C 4) - alkyl radical, an aryl radical, a (C 1 to C 4) monohydroxyalkyl, a (C 2 to C 4) - Polyhydroxyalkylrest, a (C 1 to C 4 ) -Aminoalkylres t, a (C 1 to C 4 ) -alkylamino- (C 1 -C 4 ) -alkyl radical, a DK (C 1 to C 4 ) alkyl] - (C 1 -C 4 ) -aminoalkyl radical, where the dialkyl radicals optionally form a carbocycle or a heterocycle with 5 or 6 chain links, a (C 1 to C 4) hydroxyalkyl or a di - [(C-ι-C 4) hydroxyalkyl] amino- (C-ι to
C4)-alkylrest, einen Aminorest, einen (C1 bis C4)-Alkyl- oder Di-[(C-ι bis C4)- hydroxyalkyl]aminorest, ein Halogenatom, eine Carboxylsäuregruppe oder eineC 4) alkyl, an amino group, a (C 1 to C 4) alkyl or di - [(C-ι-C 4) - hydroxyalkyl] amino group, a halogen atom, a carboxylic acid group or
Sulfonsäuregruppe, i hat den Wert 0, 1 , 2 oder 3, p hat den Wert 0 oder 1 , q hat den Wert 0 oder 1 und n hat den Wert 0 oder 1 , mit der Maßgabe, dass die Summe aus p + q ungleich 0 ist, - wenn p + q gleich 2 ist, n den Wert 0 hat, und die Gruppen NG28G29 und NG30G31 belegen dieSulfonic acid group, i has the value 0, 1, 2 or 3, p has the value 0 or 1, q has the value 0 or 1 and n has the value 0 or 1, with the proviso that the sum of p + q unequal 0 is - if p + q is 2, n is 0, and the groups NG 28 G 29 and NG 30 G 31 occupy the
Positionen (2,3); (5,6); (6,7); (3,5) oder (3,7); wweennnn pp ++ qq gglleeiicchh 11 iisstt,, nn ddeenn WWeerrtt 11 hhaatt,, uurnd die Gruppen NG28G29 (oder NG30G31) und diePositions (2,3); (5,6); (6,7); (3,5) or (3,7); wweennnn pp ++ qq gglleeiicchh 11 uisstt ,, nn ddeenn WWeerrtt 11 hhaatt, and the groups NG 28 G 29 (or NG 30 G 31 ) and the
Gruppe OH belegen die Positionen (2,3); (5,6); (6,7); (3,5) oder (3,7).Group OH occupy the positions (2,3); (5,6); (6,7); (3,5) or (3,7).
Die in Formel (E6) verwendeten Substituenten sind erfindungsgemäß analog zu den obigen Ausführungen definiert.The substituents used in formula (E6) are defined according to the invention analogously to the above statements.
Wenn das Pyrazolo[1 ,5-a]pyrimidin der obenstehenden Formel (E6) eine Hydroxygruppe an einer der Positionen 2, 5 oder 7 des Ringsystems enthält, besteht ein tautomeres Gleichgewicht, das zum Beispiel im folgenden Schema dargestellt wird:When the pyrazolo [1,5-a] pyrimidine of the above formula (E6) contains a hydroxy group at one of the 2, 5 or 7 positions of the ring system, there is a tautomeric equilibrium shown, for example, in the following scheme:
Figure imgf000021_0001
Figure imgf000021_0001
Unter den Pyrazolo[1 ,5-a]pyrimidinen der obenstehenden Formel (E6) kann man insbesondere nennen:Among the pyrazolo [1, 5-a] pyrimidines of the above formula (E6) may be mentioned in particular:
Pyrazolo[1 ,5-a]pyrimidin-3,7-diamin;Pyrazolo [1,5-a] pyrimidine-3,7-diamine;
2,5-Dimethyl-pyrazolo[1 ,5-a]pyrimidin-3,7-diamin;2,5-dimethyl-pyrazolo [1,5-a] pyrimidine-3,7-diamine;
Pyrazolo[1 ,5-a]pyrimidin-3,5-diamin;Pyrazolo [1,5-a] pyrimidine-3,5-diamine;
2,7-Dimethyl-pyrazolo[1 ,5-a]pyrimidin-3,5-diamin;2,7-dimethyl-pyrazolo [1,5-a] pyrimidine-3,5-diamine;
3-Aminopyrazolo[1 ,5-a]pyrimidin-7-ol;3-aminopyrazolo [1,5-a] pyrimidin-7-ol;
3-Aminopyrazolo[1 ,5-a]pyrimidin-5-ol;3-aminopyrazolo [1,5-a] pyrimidin-5-ol;
2-(3-Aminopyrazolo[1 ,5-a]pyrimidin-7-ylamino)-ethanol;2- (3-aminopyrazolo [1,5-a] pyrimidin-7-ylamino) ethanol;
2-(7-Aminopyrazolo[1 ,5-a]pyrimidin-3-ylamino)-ethanol;2- (7-aminopyrazolo [1,5-a] pyrimidin-3-ylamino) ethanol;
2-[(3-Aminopyrazolo[1 ,5-a]pyrimidin-7-yl)-(2-hydroxy-ethyl)-amino]-ethanol;2 - [(3-aminopyrazolo [1,5-a] pyrimidin-7-yl) - (2-hydroxy-ethyl) -amino] -ethanol;
2-[(7-Aminopyrazolo[1 ,5-a]pyrimidin-3-yl)-(2-hydroxy-ethyl)-amino]-ethanol; 5,6-Dimethylpyrazolo[1 ,5-a]pyrimidin-3,7-diamin;2 - [(7-aminopyrazolo [1,5-a] pyrimidin-3-yl) - (2-hydroxy-ethyl) -amino] -ethanol; 5,6-dimethylpyrazolo [1,5-a] pyrimidine-3,7-diamine;
2,6-Dimethylpyrazolo[1 ,5-a]pyrimidin-3,7-diamin;2,6-dimethylpyrazolo [1,5-a] pyrimidine-3,7-diamine;
3-Amino-7-dimethylamino-2,5-dimethylpyrazolo[1 ,5-a]pyrimidin; sowie ihre physiologisch verträglichen Salze und ihre tautomeren Formen, wenn ein tautomers Gleichgewicht vorhanden ist.3-amino-7-dimethylamino-2,5-dimethylpyrazolo [1,5-a] pyrimidine; and their physiologically acceptable salts and their tautomeric forms when a tautomeric equilibrium is present.
Die Pyrazolo[1 ,5-a]pyrimidine der obenstehenden Formel (E6) können wie in der Literatur beschrieben durch Zyklisierung ausgehend von einem Aminopyrazol oder von Hydrazin hergestellt werden.The pyrazolo [1, 5-a] pyrimidines of the above formula (E6) can be prepared as described in the literature by cyclization from an aminopyrazole or from hydrazine.
Ganz besonders bevorzugte Entwicklerkomponenten werden ausgewählt, aus mindestens einer Verbindung aus der Gruppe, die gebildet wird aus p-Phenylendiamin, p-Toluylendiamin, 2-(ß- Hydroxyethyl)-p-phenylendiamin, 2-(α,ß-Dihydroxyethyl)-p-phenylendiamin, N,N-Bis-(ß- hydroxyethyl)-p-phenylendiamin, N-(4-Amino-3-methylphenyl)-N-[3-(1 H-imidazol-1-yl)propyl]amin, N,N'-Bis-(ß-hydroxyethyl)-N,N'-bis-(4-aminophenyl)-1 ,3-diamino-propan-2-ol, Bis-(2-hydroxy-5- aminophenyl)-methan, 1 ,3-Bis-(2,5-diaminophenoxy)-propan-2-ol, N,N'-Bis-(4-aminophenyl)-1 ,4- diazacycloheptan, 1 ,10-Bis-(2,5-diaminophenyl)-1 ,4,7,10-tetraoxadecan, p-Aminophenol, A- Amino-3-methylphenol, 4-Amino-2-aminomethylphenol, 4-Amino-2-(α,ß-dihydroxyethyl)-phenol und 4-Amino-2-(diethylaminomethyl)-phenol, 4,5-Diamino-1-(ß-hydroxyethyl)-pyrazol, 2,4,5,6- Tetraaminopyrimidin, 4-Hydroxy-2,5,6-triaminopyrimidin, 2-Hydroxy-4,5,6-triaminopyrimidin, sowie den physiologisch verträglichen Salzen dieser Verbindungen.Very particularly preferred developer components are selected from at least one compound from the group formed from p-phenylenediamine, p-toluenediamine, 2- (β-hydroxyethyl) -p-phenylenediamine, 2- (α, β-dihydroxyethyl) -p phenylenediamine, N, N-bis (β-hydroxyethyl) -p-phenylenediamine, N- (4-amino-3-methylphenyl) -N- [3- (1 H -imidazol-1-yl) propyl] amine, N, N'-bis (β-hydroxyethyl) -N, N'-bis (4-aminophenyl) -1, 3-diamino-propan-2-ol, bis (2-hydroxy-5-aminophenyl) - methane, 1,3-bis- (2,5-diaminophenoxy) -propan-2-ol, N, N'-bis (4-aminophenyl) -1, 4-diazacycloheptane, 1, 10-bis- (2, 5-diaminophenyl) -1, 4,7,10-tetraoxadecane, p-aminophenol, A-amino-3-methylphenol, 4-amino-2-aminomethylphenol, 4-amino-2- (α, β-dihydroxyethyl) phenol and 4-amino-2- (diethylaminomethyl) phenol, 4,5-diamino-1- (β-hydroxyethyl) pyrazole, 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine , 2-hydroxy-4,5,6-triaminopyrimidine, and the physiologically acceptable salts of these compounds.
Im folgenden werden Beispiele für die als Substituenten der Verbindungen der Formeln (E1 ) bisThe following are examples of the substituents of the compounds of the formulas (E1) to
(E6) genannten Reste aufgezählt: Beispiele für (C1 bis C4)-Alkylreste sind die Gruppen -CH3, -(E6) mentioned radicals: Examples of (C 1 to C 4 ) -alkyl radicals are the groups -CH 3 , -
CH2CH3, -CH2CH2CH3, -CH(CH3)2, -CH2CH2CH2CH3, -CH2CH(CH3)2, -CH(CH3)CH2CH3, -C(CH3)3.CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH (CH 3 ) 2 , -CH 2 CH 2 CH 2 CH 3 , -CH 2 CH (CH 3 ) 2 , -CH (CH 3 ) CH 2 CH 3 , -C (CH 3 ) 3 .
Erfindungsgemäße Beispiele für (C1 bis C4)-Alkoxyreste sind -OCH3, -OCH2CH3,Examples of (C 1 to C 4 ) -alkoxy radicals according to the invention are -OCH 3 , -OCH 2 CH 3 ,
-OCH2CH2CH3, -OCH(CHs)2, -OCH2CH2CH2CH3, -OCH2CH(CH3)2, -OCH(CH3)CH2CH3, --OCH 2 CH 2 CH 3 , -OCH (CH 2 ) 2 , -OCH 2 CH 2 CH 2 CH 3 , -OCH 2 CH (CH 3 ) 2 , -OCH (CH 3 ) CH 2 CH 3 ,
OC(CH3)3, insbesondere eine Methoxy- oder eine Ethoxygruppe.OC (CH 3 ) 3 , in particular a methoxy or an ethoxy group.
Weiterhin können als bevorzugte Beispiele für eine (C1 bis C4)-Monohydroxyalkylgruppe -CH2OH,Furthermore, as preferred examples of a (C 1 to C 4 ) monohydroxyalkyl group, -CH 2 OH,
-CH2CH2OH, -CH2CH2CH2OH, -CHCH(OH)CH3, -CH2CH2CH2CH2OH, wobei die Gruppe --CH 2 CH 2 OH, -CH 2 CH 2 CH 2 OH, -CHCH (OH) CH 3 , -CH 2 CH 2 CH 2 CH 2 OH, where the group
CH2CH2OH bevorzugt ist.CH 2 CH 2 OH is preferred.
Ein besonders bevorzugtes Beispiel einer (C2 bis C4)-Polyhydroxyalkylgruppe ist die 1 ,2-A particularly preferred example of a (C 2 to C 4 ) polyhydroxyalkyl group is 1, 2
Dihyd roxyethylg ru ppe.Dihydroxyethylprep.
Beispiele für Halogenatome sind F-, Cl- oder Br-Atome, Cl-Atome sind ganz besonders bevorzugte Beispiele.Examples of halogen atoms are F, Cl or Br atoms, Cl atoms are very particularly preferred examples.
Beispiele für stickstoffhaltige Gruppen sind insbesondere -NH2, (C1 bis C4)-Examples of nitrogen-containing groups are in particular -NH 2 , (C 1 to C 4 ) -
Monoalkylaminogruppen, (C1 bis C4)-Dialkylaminogruppen, (C1 bis C4)-Monoalkylamino groups, (C 1 to C 4 ) -dialkylamino groups, (C 1 to C 4 ) -
Trialkylammoniumgruppen, (C1 bis C4)-Monohydroxyalkylaminogruppen, Imidazolinium und -Trialkylammonium groups, (C 1 to C 4 ) monohydroxyalkylamino groups, imidazolinium and
NH3 +.NH 3 + .
Beispiele für (C1 bis C4)-Monoalkylaminogruppen sind -NHCH3, -NHCH2CH3, -NHCH2CH2CH3,Examples of (C 1 to C 4 ) -monoalkylamino groups are -NHCH 3 , -NHCH 2 CH 3 , -NHCH 2 CH 2 CH 3 ,
-NHCH(CH3)2. Beispiele für (Ci bis C4)-Dialkylaminogruppe sind -N(CH3)2, -N(CH2CH3)2.-NHCH (CH 3 ) 2 . Examples of (C 1 to C 4 ) -dialkylamino groups are -N (CH 3 ) 2 , -N (CH 2 CH 3 ) 2 .
Beispiele für (C1 bis C4)-Trialkylammoniumgruppen sind -N+(CH3)3, -N+(CH3)2(CH2CI-I3), -N+(CH3)(CH2CH3)2.Examples of (C 1 to C 4 ) trialkylammonium groups are -N + (CH 3 ) 3 , -N + (CH 3 ) 2 (CH 2 Cl-I 3 ), -N + (CH 3 ) (CH 2 CH 3 2 .
Beispiele für (C1 bis C4)-Hydroxyalkylaminoreste sind -NH-CH2CH2OH, -NH-CH2CH2OH, -NH-CH2CH2CH2OH 1 -NH-CH2CH2CH2OH .Examples of (C 1 to C 4 ) -hydroxyalkylamino radicals are -NH-CH 2 CH 2 OH, -NH-CH 2 CH 2 OH, -NH-CH 2 CH 2 CH 2 OH 1 -NH-CH 2 CH 2 CH 2 OH.
Beispiele für (C1 bis C4)-Alkoxy-(C-ι bis C4)-alkylgruppen sind die Gruppen -CH2CH2-O-CH3, -CH2CH2CH2-O-CH3, -CH2CH2-O-CH2CH3, -CH2CH2CH2-O-CH2CH3, -CH2CH2-O-CH(CH3), -CH2CH2CH2-O-CH(CH3).Examples of (C 1 to C 4 ) -alkoxy- (C 1 -C 4 ) -alkyl groups are the groups -CH 2 CH 2 -O-CH 3 , -CH 2 CH 2 CH 2 -O-CH 3 , - CH 2 CH 2 -O-CH 2 CH 3 , -CH 2 CH 2 CH 2 -O-CH 2 CH 3 , -CH 2 CH 2 -O-CH (CH 3 ), -CH 2 CH 2 CH 2 -O -CH (CH 3 ).
Beispiele für Hydroxy-(C-ι bis C4)-alkoxyreste sind -0-CH2OH, -0-CH2CH2OH, -0-CH2CH2CH2OH, -0-CHCH(OH)CH3, -0-CH2CH2CH2CH2OH.Examples of hydroxy (C 1 -C 4 ) -alkoxy radicals are -O-CH 2 OH, -O-CH 2 CH 2 OH, -O-CH 2 CH 2 CH 2 OH, -O-CHCH (OH) CH 3 , -O-CH 2 CH 2 CH 2 CH 2 OH.
Beispiele für (C1 bis C4)-Acetylaminoalkoxyreste sind -0-CH2NHC(O)CH3, -O- CH2CH2NHC(O)CH3,Examples of (C 1 to C 4 ) -acetylaminoalkoxy radicals are -O-CH 2 NHC (O) CH 3 , -O-CH 2 CH 2 NHC (O) CH 3 ,
-0-CH2CH2CH2NHC(O)CH31 -O-CH2CH(NHC(O)CH3)CH31 -O-CH2CH2CH2CH2NHC(O)CH3. Beispiele für (C1 bis C4)-Carbamoylaminoalkoxyreste sind -0-CH2CH2-NH-C(O)-NH2, -0-CH2CH2CH2-NH-C(O)-NH21 -O-CH2CH2CH2CH2-NH-C(O)-NH2.-O-CH 2 CH 2 CH 2 NHC (O) CH 31 -O-CH 2 CH (NHC (O) CH 3 ) CH 31 -O-CH 2 CH 2 CH 2 CH 2 NHC (O) CH 3 . Examples of (C 1 to C 4 ) carbamoylaminoalkoxy radicals are -O-CH 2 CH 2 -NH-C (O) -NH 2 , -O-CH 2 CH 2 CH 2 -NH-C (O) -NH 21 - O-CH 2 CH 2 CH 2 CH 2 -NH-C (O) -NH 2 .
Beispiele für (C1 bis C4)-Aminoalkylreste sind -CH2NH2, -CH2CH2NH2, -CH2CH2CH2NH2, -CH2CH(NH2)CH31 -CH2CH2CH2CH2NH2.Examples of (C 1 to C 4 ) -aminoalkyl radicals are -CH 2 NH 2 , -CH 2 CH 2 NH 2 , -CH 2 CH 2 CH 2 NH 2 , -CH 2 CH (NH 2 ) CH 31 -CH 2 CH 2 CH 2 CH 2 NH 2 .
Beispiele für (C1 bis C4)-Cyanoalkylreste sind -CH2CN1 -CH2CH2CN1 -CH2CH2CH2CN. Beispiele für (C1 bis C4)-Hydroxyalkylamino-(C-i bis C4)-alkylreste sind -CH2CH2NH-CH2CH2OH1 -CH2CH2CH2NH-CH2CH2OH 1 -CH2CH2NH-CH2CH2CH2OH1 -CH2CH2CH2NH-CH2CH2CH2OH. Beispiele für Di[(d bis C4)-Hydroxyalkyl]amino-(C-ι bis C4)-alkylreste sind CH2CH2N(CH2CH2OH)21 Examples of (C 1 to C 4 ) -cyanoalkyl radicals are -CH 2 CN 1 -CH 2 CH 2 CN 1 -CH 2 CH 2 CH 2 CN. Examples of (C 1 to C 4) -Hydroxyalkylamino- (Ci to C 4) alkyl groups are -CH 2 CH 2 NH-CH 2 CH 2 OH 1 -CH 2 CH 2 CH 2 NH-CH 2 CH 2 OH 1 - CH 2 CH 2 NH-CH 2 CH 2 CH 2 OH 1 -CH 2 CH 2 CH 2 NH-CH 2 CH 2 CH 2 OH. Examples of di [(d to C 4 ) -hydroxyalkyl] amino- (C 1 -C 4 ) -alkyl radicals are CH 2 CH 2 N (CH 2 CH 2 OH) 21
-CH2CH2CH2N(CH2CH2OH)21 -CH2CH2N(CH2CH2CH2OH)21 -CH2CH2CH2N(CH2CH2CH2OH)2. Ein Beispiel für Arylgruppen ist die Phenylgruppe. Beispiele für Aryl-(C-ι bis C4)-alkylgruppen sind die Benzylgruppe und die 2-Phenylethylgruppe.-CH 2 CH 2 CH 2 N (CH 2 CH 2 OH) 21 -CH 2 CH 2 N (CH 2 CH 2 CH 2 OH) 21 -CH 2 CH 2 CH 2 N (CH 2 CH 2 CH 2 OH) 2 , An example of aryl groups is the phenyl group. Examples of aryl (C 1 -C 4 ) -alkyl groups are the benzyl group and the 2-phenylethyl group.
Als eine spezielle Farbstoffvorstufe vom Entwicklertyp werden als naturanaloge Farbstoffe bevorzugt solche Indole und Indoline eingesetzt, die mindestens zwei Gruppen ausgewählt aus Hydroxy- und/oder oder Aminogruppen, bevorzugt als Substituent am Sechsring, aufweisen. Diese Gruppen können weitere Substituenten tragen, z. B. in Form einer Veretherung oder Veresterung der Hydroxygruppe oder eine Alkylierung der Aminogruppe. In einer weiteren Ausführungsform enthalten die Färbemittel mindestens ein Indol- und/oder Indolinderivat. Erfindungsgemäße Zusammensetzungen, die Vorstufen naturanaloger Farbstoffe enthalten, werden bevorzugt als luftoxidative Färbemittel verwendet. In dieser Ausführungsform werden die besagten Zusammensetzungen folglich nicht mit einem zusätzlichen Oxidationsmittel versetzt.As a special dye precursor of the developer type are used as nature analog dyes preferably such indoles and indolines having at least two groups selected from hydroxy and / or or amino groups, preferably as a substituent on the six-membered ring. These groups may carry further substituents, e.g. Example in the form of etherification or esterification of the hydroxy group or alkylation of the amino group. In a further embodiment, the colorants contain at least one indole and / or indoline derivative. Compositions according to the invention which comprise precursors of naturally-analogous dyes are preferably used as air-oxidative colorants. Consequently, in this embodiment said compositions are not added with an additional oxidizing agent.
Besonders gut als Vorstufen naturanaloger Haarfarbstoffe geeignet sind Derivate des 5,6- Dihydroxyindolins der Formel (E7),
Figure imgf000024_0001
in der unabhängig voneinanderParticularly suitable precursors of naturally-analogous hair dyes are derivatives of 5,6-dihydroxyindoline of the formula (E7),
Figure imgf000024_0001
in the independently of each other
R1 steht für Wasserstoff, eine d-C4-Alkylgruppe oder eine Ci-C4-Hydroxy-alkylgruppe, R2 steht für Wasserstoff oder eine -COOH-Gruppe, wobei die -COOH-Gruppe auch als Salz mit einem physiologisch verträglichen Kation vorliegen kann, R3 steht für Wasserstoff oder eine Ci-C4-Alkylgruppe,R 1 is hydrogen, a C 1 -C 4 -alkyl group or a C 1 -C 4 -hydroxy-alkyl group, R 2 is hydrogen or a -COOH group, where the -COOH group may also be present as a salt with a physiologically compatible cation R 3 is hydrogen or a C 1 -C 4 -alkyl group,
R4 steht für Wasserstoff, eine d-C4-Alkylgruppe oder eine Gruppe -CO-R6, in der R6 steht für eine C-|-C4-Alkylgruppe, und R5 steht für eine der unter R4 genannten Gruppen, sowie physiologisch verträgliche Salze dieser Verbindungen mit einer organischen oder anorganischen Säure.R 4 is hydrogen, a dC 4 alkyl group or a group -CO-R 6 , in which R 6 is a C- | C 4 alkyl group, and R 5 is one of the groups mentioned under R 4 , and physiologically acceptable salts of these compounds with an organic or inorganic acid.
Besonders bevorzugte Derivate des Indolins sind das 5,6-Dihydroxyindolin, N-Methyl-5,6- dihydroxyindolin, N-Ethyl-5,6-dihydroxyindolin, N-Propyl-5,6-dihydroxyindolin, N-Butyl-5,6- dihydroxyindolin sowie 5,6-Dihydroxyindolin-2-carbonsäure.Particularly preferred derivatives of indoline are 5,6-dihydroxyindoline, N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6 - Dihydroxyindolin and 5,6-dihydroxyindoline-2-carboxylic acid.
Besonders hervorzuheben sind innerhalb dieser Gruppe N-Methyl-5,6-dihydroxyindolin, N-Ethyl- 5,6-dihydroxyindolin, N-Propyl-5,6-dihydroxyindolin, N-Butyl-5,6-dihydroxyindolin und insbesondere das 5,6-Dihydroxyindolin.Particularly noteworthy within this group are N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline and especially 5, 6-Dihydroxyindolin.
Als Vorstufen naturanaloger Haarfarbstoffe hervorragend geeignet sind weiterhin Derivate des 5,6-Dihydroxyindols der Formel (E8),Also suitable as precursors of naturally-analogous hair dyes are derivatives of the 5,6-dihydroxyindole of the formula (E8),
Figure imgf000024_0002
in der unabhängig voneinander
Figure imgf000024_0002
in the independently of each other
R1 steht für Wasserstoff, eine d-C4-Alkylgruppe oder eine Ci-C4-Hydroxyalkylgruppe,R 1 is hydrogen, a C 1 -C 4 -alkyl group or a C 1 -C 4 -hydroxyalkyl group,
R2 steht für Wasserstoff oder eine -COOH-Gruppe, wobei die -COOH-Gruppe auch als Salz mit einem physiologisch verträglichen Kation vorliegen kann,R 2 is hydrogen or a -COOH group, wherein the -COOH group may also be present as a salt with a physiologically compatible cation,
R3 steht für Wasserstoff oder eine Ci-C4-Alkylgruppe,R 3 is hydrogen or a C 1 -C 4 -alkyl group,
R4 steht für Wasserstoff, eine d-C4-Alkylgruppe oder eine Gruppe -CO-R6, in der R6 steht für eine C-|-C4-Alkylgruppe, undR 4 is hydrogen, a dC 4 alkyl group or a group -CO-R 6 , in which R 6 is a C- | -C 4 alkyl group, and
R5 steht für eine der unter R4 genannten Gruppen, sowie physiologisch verträgliche Salze dieser Verbindungen mit einer organischen oder anorganischen Säure. Besonders bevorzugte Derivate des Indols sind 5,6-Dihydroxyindol, N-Methyl-5,6-dihydroxyindol, N-Ethyl-5,6-dihydroxyindol, N-Propyl-5,6-dihydroxyindol, N-Butyl-5,6-dihydroxyindol, 5,6- Dihydroxyindol-2-carbonsäure.R 5 represents one of the groups mentioned for R 4, and physiologically compatible salts of these compounds with an organic or inorganic acid. Particularly preferred derivatives of indole are 5,6-dihydroxyindole, N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6- dihydroxyindole, 5,6-dihydroxyindole-2-carboxylic acid.
Innerhalb dieser Gruppe hervorzuheben sind N-Methyl-5,6-dihydroxyindol, N-Ethyl-5,6- dihydroxyindol, N-Propyl-5,6-dihydroxyindol, N-Butyl-5,6-dihydroxyindol sowie insbesondere das 5,6-Dihydroxyindol.Emphasized within this group are N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole, and especially the 5,6 -Dihydroxyindol.
Die Indolin- beziehungsweise die Indol-Derivate können sowohl als freie Basen als auch in Form ihrer physiologisch verträglichen Salze mit anorganischen oder organischen Säuren, z. B. der Hydrochloride, der Sulfate und Hydrobromide, eingesetzt werden.The indoline or the indole derivatives can be used both as free bases and in the form of their physiologically acceptable salts with inorganic or organic acids, eg. As the hydrochlorides, sulfates and hydrobromides are used.
Kupplerkomponenten bilden im Rahmen der oxidativen Färbung allein keine signifikante Färbung aus, sondern benötigen stets die Gegenwart von Entwicklerkomponenten. Daher ist es erfindungsgemäß bevorzugt, dass bei Verwendung mindestens einer Entwicklerkomponente zusätzlich mindestens eine Kupplerkomponente zum Einsatz kommt.Coupler components do not form a significant color within the framework of the oxidative dyeing alone, but always require the presence of developer components. Therefore, it is preferred according to the invention that at least one coupler component is additionally used when using at least one developer component.
Kupplerkomponenten im Sinne der Erfindung erlauben mindestens eine Substitution eines chemischen Restes des Kupplers durch die oxidierte Form der Entwicklerkomponente. Dabei bildet sich eine kovalente Bindung zwischen Kuppler- und Entwicklerkomponente aus. Kuppler sind bevorzugt zyklische Verbindungen, die am Zyklus mindestens zwei Gruppen tragen, ausgewählt aus (i) gegebenenfalls substituierten Aminogruppen und/oder (ii) Hydroxygruppen. Wenn die zyklische Verbindung ein Sechsring (bevorzugt aromatisch) ist, so befinden sich die besagten Gruppen bevorzugt in ortho-Position oder meta-Position zueinander.Coupler components according to the invention allow at least one substitution of a chemical residue of the coupler by the oxidized form of the developer component. This forms a covalent bond between the coupler and the developer component. Couplers are preferably cyclic compounds which carry on cycle at least two groups selected from (i) optionally substituted amino groups and / or (ii) hydroxy groups. When the cyclic compound is a six-membered ring (preferably aromatic), said groups are preferably in ortho position or meta position to each other.
Erfindungsgemäße Kupplerkomponenten werden bevorzugt als mindestens eine Verbindung aus einer der folgenden Klassen ausgewählt:Coupler components according to the invention are preferably selected as at least one compound from one of the following classes:
- m-Aminophenol und/oder dessen Derivate,m-aminophenol and / or its derivatives,
- m-Diaminobenzol und/oder dessen Derivate,m-diaminobenzene and / or its derivatives,
- o-Diaminobenzol und/oder dessen Derivate,o-diaminobenzene and / or its derivatives,
- o-Aminophenolderivate, wie beispielsweise o-Aminophenol,o-aminophenol derivatives, such as o-aminophenol,
- Naphthalinderivate mit mindestens einer Hydroxygruppe,Naphthalene derivatives having at least one hydroxy group,
- Di- beziehungsweise Trihydroxybenzol und/oder deren Derivate,Di- or trihydroxybenzene and / or derivatives thereof,
- Pyridinderivate,- pyridine derivatives,
- Pyrimidinderivate,- pyrimidine derivatives,
- Monohydroxyindol-Derivate und/oder Monoaminoindol-Derivate,Monohydroxyindole derivatives and / or monoamine indole derivatives,
- Monohydroxyindolin-Derivate und/oder Monoaminoindolin-Derivate,Monohydroxyindoline derivatives and / or monoaminoindoline derivatives,
- Pyrazolonderivate, wie beispielsweise 1-Phenyl-3-methylpyrazol-5-on,Pyrazolone derivatives such as 1-phenyl-3-methylpyrazol-5-one,
- Morpholinderivate wie beispielsweise 6-Hydroxybenzomorpholin oder 6-Amino-benzomorpholin,Morpholine derivatives such as, for example, 6-hydroxybenzomorpholine or 6-aminobenzomorpholine,
- Chinoxalinderivate wie beispielsweise 6-Methyl-1 ,2,3,4-tetrahydrochinoxalin, Gemische aus zwei oder mehrer Verbindungen aus einer oder mehrerer dieser Klassen sind im Rahmen dieser Ausführungsform ebenso erfindungsgemäß.Quinoxaline derivatives such as 6-methyl-1,2,3,4-tetrahydroquinoxaline, Mixtures of two or more compounds from one or more of these classes are also within the scope of this embodiment according to the invention.
Die erfindungsgemäß verwendbaren m-Aminophenole bzw. deren Derivate werden bevorzugt ausgewählt aus mindestens einer Verbindung der Formel (K1 ) und/oder aus mindestens einem physiologisch verträglichen Salz einer Verbindung gemäß Formel (K1 ),The m-aminophenols or derivatives thereof which can be used according to the invention are preferably selected from at least one compound of the formula (K1) and / or from at least one physiologically tolerated salt of a compound of the formula (K1),
Figure imgf000026_0001
) worin
Figure imgf000026_0001
in which
G1 und G2 unabhängig voneinander stehen für ein Wasserstoffatom, eine (Ci bis C4)- Alkylgruppe, eine (C3 bis C6)-Cycloalkylgruppe, eine (C2 bis C4)-Alkenylgruppe, eine (C1 bis C4)-Monohydroxyalkylgruppe, eine (C2 bis C4)-Polyhydroxyalkylgruppe, eine (C2 bis C4)-Perfluoracylgruppe, eine Aryl-(C-ι bis C6)-alkylgruppe, eine AmJnO-(C1 bis C6)-alkylgruppe, eine (C1 bis C6)-Dialkylamino-(C-ι bis C6)-alkylgruppe oder eine (C1 bis C6)-Alkoxy-(C-ι bis C6)-alkylgruppe, wobei G1 und G2 gemeinsam mit dem Stickstoffatom einen fünfgliedrigen, sechsgliedrigen oder siebengliedrigen Ring bilden können,G 1 and G 2 independently represent a hydrogen atom, a (Ci to C 4) - alkyl group, a (C 3 -C 6) cycloalkyl group, a (C 2 to C 4) alkenyl group, a (C 1 to C 4) monohydroxyalkyl, a (C 2 to C 4) -polyhydroxyalkyl group, a (C 2 to C 4) -Perfluoracylgruppe, an aryl (C-ι-C 6) alkyl group, a AmJnO- (C 1 to C 6 ) alkyl group, a (C 1 to C 6) dialkylamino (C-ι alkyl to C 6) or a (C 1 to C 6) alkoxy (C-ι-C 6) alkyl group, wherein G 1 and G 2 together with the nitrogen atom can form a five-membered, six-membered or seven-membered ring,
G3 und G4 unabhängig voneinander stehen für ein Wasserstoffatom, ein Halogenatom, eine (C1 bis C4)-Alkylgruppe, eine (C1 bis C4)-Alkoxygruppe, eine Hydroxygruppe, eine (C1 bis C4)-Monohydroxyalkylgruppe, eine (C2 bis C4)-Polyhydroxyalkylgruppe, eine Hydroxy- (C1 bis C4)-alkoxygruppe, eine (C1 bis C6)-Alkyox-(C2 bis C6)-alkoxygruppe, eine Arylgruppe oder eine Heteroarylgruppe.G 3 and G 4 independently represent a hydrogen atom, a halogen atom, a (C 1 to C 4 ) alkyl group, a (C 1 to C 4 ) alkoxy group, a hydroxy group, a (C 1 to C 4 ) monohydroxyalkyl group , a (C 2 to C 4 ) polyhydroxyalkyl group, a hydroxy (C 1 to C 4 ) alkoxy group, a (C 1 to C 6 ) -alkoxy (C 2 to C 6 ) alkoxy group, an aryl group or a heteroaryl.
Besonders bevorzugte m-Aminophenol-Kupplerkomponenten werden ausgewählt aus mindestens einer Verbindung aus der Gruppe, die gebildet wird aus m-Aminophenol, 5-Amino-2- methylphenol, N-Cyclopentyl-3-aminophenol, 3-Amino-2-chlor-6-methylphenol, 2-Hydroxy-4- aminophenoxyethanol, 2,6-Dimethyl-3-aminophenol, 3-Trifluoroacetylamino-2-chlor-6- methylphenol, 5-Amino-4-chlor-2-methylphenol, 5-Amino-4-methoxy-2-methylphenol, 5-(2'- Hydroxyethyl)-amino-2-methylphenol, 3-(Diethylamino)-phenol, N-Cyclopentyl-3-aminophenol, 1 ,3-Dihydroxy-5-(methylamino)-benzol, 3-Ethylamino-4-methylphenol, 2,4-Dichlor-3-aminophenol und den physiologisch verträglichen Salzen aller vorstehend genannten Verbindungen.Particularly preferred m-aminophenol coupler components are selected from at least one compound selected from the group consisting of m-aminophenol, 5-amino-2-methylphenol, N-cyclopentyl-3-aminophenol, 3-amino-2-chloro-6 -methylphenol, 2-hydroxy-4-aminophenoxyethanol, 2,6-dimethyl-3-aminophenol, 3-trifluoroacetylamino-2-chloro-6-methylphenol, 5-amino-4-chloro-2-methylphenol, 5-amino-4 -methoxy-2-methylphenol, 5- (2'-hydroxyethyl) amino-2-methylphenol, 3- (diethylamino) -phenol, N-cyclopentyl-3-aminophenol, 1, 3-dihydroxy-5- (methylamino) - benzene, 3-ethylamino-4-methylphenol, 2,4-dichloro-3-aminophenol and the physiologically acceptable salts of all the abovementioned compounds.
Die erfindungsgemäß verwendbaren m-Diaminobenzole bzw. deren Derivate werden bevorzugt ausgewählt aus mindestens einer Verbindung der Formel (K2) und/oder aus mindestens einem physiologisch verträglichen Salz einer Verbindung gemäß Formel (K2),
Figure imgf000027_0001
worinThe m-diaminobenzenes or derivatives thereof which can be used according to the invention are preferably selected from at least one compound of the formula (K2) and / or from at least one physiologically tolerated salt of a compound of the formula (K2),
Figure imgf000027_0001
wherein
G5, G6, G7 und G8 unabhängig voneinander stehen für ein Wasserstoffatom, eine (Ci bis C4)- Alkylgruppe, eine (C3 bis C6)-Cycloalkylgruppe, eine (C2 bis C4)- Alkenylgruppe, eine (Ci bis C4)-Monohydroxyalkylgruppe, eine (C2 bis C4)- Polyhydroxyalkylgruppe, eine (C1 bis C4)-Alkoxy-(C-ι bis C4)-alkylgruppe, eine Aryl-(C-ι bis C4)-alkylgruppe, eine Heteroaryl-(C-ι bis C4)-alkylgruppe, eine (C2 bis C4)-Perfluoracylgruppe, oder gemeinsam mit dem Stickstoffatom einen fünfgliedrigen oder sechsgliedrigen Heterozyklus bildenG 5, G 6, G 7 and G 8 are independently a hydrogen atom, a (Ci to C 4) - alkyl group, a (C 3 -C 6) cycloalkyl group, a (C 2 to C 4) - alkenyl group, a (Ci to C 4) monohydroxyalkyl, a (C 2 to C 4) - polyhydroxyalkyl group, a (C 1 to C 4) alkoxy alkyl (C-ι-C 4), aryl (C-ι to C 4 ) alkyl group, a heteroaryl (C 1 -C 4 ) -alkyl group, a (C 2 to C 4 ) perfluoroacyl group, or together with the nitrogen atom form a five-membered or six-membered heterocycle
G9 und G10 unabhängig voneinander stehen für ein Wasserstoffatom, ein Halogenatom, eine (C1 bis C4)-Alkylgruppe, eine ω-(2,4-Diaminophenyl)-(C-ι bis C4)- alkylgruppe, eine ω-(2,4-Diaminophenyloxy)-(C-ι bis C4)-alkoxygruppe, eine (C1 bis C4)-Alkoxygruppe, eine Hydroxygruppe, eine (C1 bis C4)-Alkoxy-(C2 bis C4)-alkoxygruppe, eine Arylgruppe, eine Heteroarylgruppe, eine (C1 bis C4)-Monohydroxyalkylgruppe, eine (C2 bis C4)-Polyhydroxyalkylgruppe, eine Hydroxy-(C-ι bis C4)-alkoxygruppe.G 9 and G 10 independently of one another represent a hydrogen atom, a halogen atom, a (C 1 to C 4 ) -alkyl group, an ω- (2,4-diaminophenyl) - (C 1 -C 4 ) -alkyl group, an ω - (2,4-Diaminophenyloxy) - (C- 1 to C 4 ) alkoxy, a (C 1 to C 4 ) alkoxy, a hydroxy group, a (C 1 to C 4 ) alkoxy (C 2 to C 4) alkoxy group, an aryl group, a heteroaryl group, a (C 1 to C 4) monohydroxyalkyl, a (C 2 to C 4) -polyhydroxyalkyl group, a hydroxy (C-ι-C 4) alkoxy.
Besonders bevorzugte m-Diaminobenzol-Kupplerkomponenten werden ausgewählt aus mindestens einer Verbindung aus der Gruppe, die gebildet wird aus m-Phenylendiamin, 2-(2,4- Diaminophenoxy)ethanol, 1 ,3-Bis(2,4-diaminophenoxy)propan, 1-Methoxy-2-amino-4-(2'- hydroxyethylamino)benzol, 1 ,3-Bis(2,4-diaminophenyl)propan, 2,6-Bis(2'-hydroxyethylamino)-1- methylbenzol, 2-({3-[(2-Hydroxyethyl)amino]-4-methoxy-5-methylphenyl}amino)ethanol, 2-({3-[(2- Hydroxyethyl)amino]-2-methoxy-5-methylphenyl}amino)ethanol, 2-({3-[(2-Hydroxyethyl)amino]- 4,5-dimethylphenyl}amino)ethanol, 2-[3-Morpholin-4-ylphenyl)amino]ethanol, 3-Amino-4-(2- methoxyethoxy)-5-methylphenylamin, 1-Amino-3-bis-(2'-hydroxyethyl)-aminobenzol und den physiologisch verträglichen Salzen aller vorstehend genannten Verbindungen.Particularly preferred m-diaminobenzene coupler components are selected from at least one compound from the group formed from m-phenylenediamine, 2- (2,4-diaminophenoxy) ethanol, 1, 3-bis (2,4-diaminophenoxy) propane, 1-Methoxy-2-amino-4- (2'-hydroxyethylamino) benzene, 1, 3-bis (2,4-diaminophenyl) propane, 2,6-bis (2'-hydroxyethylamino) -1-methylbenzene, 2- ({3 - [(2-hydroxyethyl) amino] -4-methoxy-5-methylphenyl} amino) ethanol, 2 - ({3 - [(2-hydroxyethyl) amino] -2-methoxy-5-methylphenyl} amino) ethanol, 2 - ({3 - [(2-hydroxyethyl) amino] -4,5-dimethylphenyl} amino) ethanol, 2- [3-morpholin-4-ylphenyl) amino] ethanol, 3-amino-4- (2 - Methoxyethoxy) -5-methylphenylamine, 1-amino-3-bis (2'-hydroxyethyl) aminobenzene and the physiologically acceptable salts of all the compounds mentioned above.
Die erfindungsgemäß verwendbaren o-Diaminobenzole bzw. deren Derivate werden bevorzugt ausgewählt aus mindestens einer Verbindung der Formel (K3) und/oder aus mindestens einem physiologisch verträglichen Salz einer Verbindung gemäß Formel (K3),
Figure imgf000028_0001
worinThe o-diaminobenzenes or their derivatives which can be used according to the invention are preferably selected from at least one compound of the formula (K3) and / or from at least one physiologically tolerated salt of a compound of the formula (K3),
Figure imgf000028_0001
wherein
G11 , G12, G13 und G14 unabhängig voneinander stehen für ein Wasserstoffatom, eine (Ci bis C4)- Alkylgruppe, eine (C3 bis C6)-Cycloalkylgruppe, eine (C2 bis C4)- Alkenylgruppe, eine (C1 bis C4)-Monohydroxyalkylgruppe, eine (C2 bis C4)- Polyhydroxyalkylgruppe, eine (C1 bis C4)-Alkoxy-(C-ι bis C4)-alkylgruppe, eine Aryl-(d bis C4)-alkylgruppe, eine Heteroaryl-(C-ι bis C4)-alkylgruppe, eine (C2 bis C4)-Perfluoracylgruppe, oder gemeinsam mit dem Stickstoffatom einen fünfgliedrigen oder sechsgliedrigen Heterozyklus bildenG 11, G 12, G 13 and G 14 are independently a hydrogen atom, a (Ci to C 4) - alkyl group, a (C 3 -C 6) cycloalkyl group, a (C 2 to C 4) - alkenyl group, a (C 1 to C 4) monohydroxyalkyl, a (C 2 to C 4) - polyhydroxyalkyl group, a (C 1 to C 4) alkoxy alkyl (C-ι-C 4), aryl (d to C 4 ) alkyl group, a heteroaryl (C-1 to C 4 ) alkyl group, a (C 2 to C 4 ) perfluoroacyl group, or together with the nitrogen atom form a five-membered or six-membered heterocycle
G15 und G16 unabhängig voneinander stehen für ein Wasserstoffatom, einG 15 and G 16 independently represent a hydrogen atom, a
Halogenatom, eine Carboxylgruppe, eine (C1 bis C4)-Alkylgruppe, eine (C1 bis C4)-Alkoxygruppe, eine Hydroxygruppe, eine (C1 bis C4)- Monohydroxyalkylgruppe, eine (C2 bis C4)-Polyhydroxyalkylgruppe, eine Hydroxy-(C-ι bis C4)-alkoxygruppe.Halogen atom, a carboxyl group, a (C 1 to C 4 ) alkyl group, a (C 1 to C 4 ) alkoxy group, a hydroxy group, a (C 1 to C 4 ) monohydroxyalkyl group, a (C 2 to C 4 ) - Polyhydroxyalkyl group, a hydroxy (C-ι to C 4 ) alkoxy group.
Besonders bevorzugte o-Diaminobenzol-Kupplerkomponenten werden ausgewählt aus mindestens einer Verbindung aus der Gruppe, die gebildet wird aus 3,4-Diaminobenzoesäure und 2,3-Diamino-1-methylbenzol und den physiologisch verträglichen Salzen aller vorstehend genannten Verbindungen.Particularly preferred o-diaminobenzene coupler components are selected from at least one compound selected from the group consisting of 3,4-diaminobenzoic acid and 2,3-diamino-1-methylbenzene and the physiologically acceptable salts of all of the aforementioned compounds.
Bevorzugte Di- beziehungsweise Trihydroxybenzole und deren Derivate werden ausgewählt aus mindestens einer Verbindung der Gruppe, die gebildet wird aus Resorcin, Resorcinmonomethylether, 2-Methylresorcin, 5-Methylresorcin, 2,5-Dimethylresorcin, 2- Chlorresorcin, 4-Chlorresorcin, Pyrogallol und 1 ,2,4-Trihydroxybenzol.Preferred di- or trihydroxybenzenes and their derivatives are selected from at least one compound of the group formed from resorcinol, resorcinol monomethyl ether, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 2-chlororesorcinol, 4-chlororesorcinol, pyrogallol and 1 , 2,4-trihydroxybenzene.
Die erfindungsgemäß verwendbaren Pyridinderivate werden bevorzugt ausgewählt aus mindestens einer Verbindung der Formel (K4) und/oder aus mindestens einem physiologisch verträglichen Salz einer Verbindung gemäß Formel (K4),The pyridine derivatives which can be used according to the invention are preferably selected from at least one compound of the formula (K4) and / or from at least one physiologically tolerable salt of a compound of the formula (K4),
Figure imgf000028_0002
worin
Figure imgf000028_0002
wherein
G17 und G18 stehen unabhängig voneinander für eine Hydroxygruppe oder eine Gruppe - NG21G22, worin G21 und G22 unabhängig voneinander stehen für ein Wasserstoffatom, eine (C1 bis C4)-Alkylgruppe, eine (C3 bis C6)-Cycloalkylgruppe, eine (C2 bis C4)-Alkenylgruppe, eine Arylgruppe, eine (C1 bis C4)-Monohydroxyalkylgruppe, eine (C2 bis C4)-Polyhydroxyalkylgruppe, eine (C1 bis C4)-Alkoxy-(C-ι bis C4)- alkylgruppe, eine Aryl-(d bis C4)-alkylgruppe, eine Heteroaryl-(C-ι bis C4)- alkylgruppe,G 17 and G 18 independently of one another represent a hydroxyl group or a group - NG 21 G 22 , wherein G 21 and G 22 are independently a hydrogen atom, a (C 1 to C 4 ) alkyl group, a (C 3 to C 6 ) cycloalkyl group, a (C 2 to C 4 ) alkenyl group, an aryl group, a (C 1 to C 4) monohydroxyalkyl, a (C 2 to C 4) -polyhydroxyalkyl group, a (C 1 to C 4) alkoxy (C-ι-C 4) - alkyl group, an aryl (d-C 4 ) -alkyl group, a heteroaryl (C 1 -C 4 ) -alkyl group,
G19 und G20 stehen unabhängig voneinander für ein Wasserstoffatom, ein Halogenatom, eine (C1 bis C4)-Alkylgruppe oder eine (C1 bis C4)-Alkoxygruppe.G 19 and G 20 independently of one another represent a hydrogen atom, a halogen atom, a (C 1 to C 4 ) -alkyl group or a (C 1 to C 4 ) -alkoxy group.
Es ist bevorzugt, wenn gemäß Formel (K4) die Reste G17 und G18 in ortho-Position oder in metaPosition zueinander stehen.It is preferred if, according to formula (K4), the radicals G 17 and G 18 are in the ortho position or in the meta position relative to one another.
Besonders bevorzugte Pyridinderivate werden ausgewählt aus mindestens einer Verbindung der Gruppe, die gebildet wird aus 2,6-Dihydroxypyridin, 2-Amino-3-hydroxypyridin, 2-Amino-5-chlor-3- hydroxypyridin, 3-Amino-2-methylamino-6-methoxypyridin, 2,6-Dihydroxy-3,4-dimethylpyridin, 2,6- Dihydroxy-4-methylpyridin, 2,6-Diaminopyridin, 2,3-Diamino-6-methoxypyridin, 3,5-Diamino-2,6- dimethoxypyridin, 3,4-Diaminopyridin, 2-(2-Methoxyethyl)amino-3-amino-6-methoxypyridin, 2-(4'- Methoxyphenyl)amino-3-aminopyridin, und den physiologisch verträglichen Salzen der vorgenannten Verbindungen.Particularly preferred pyridine derivatives are selected from at least one compound of the group formed from 2,6-dihydroxypyridine, 2-amino-3-hydroxypyridine, 2-amino-5-chloro-3-hydroxypyridine, 3-amino-2-methylamino 6-methoxypyridine, 2,6-dihydroxy-3,4-dimethylpyridine, 2,6-dihydroxy-4-methylpyridine, 2,6-diaminopyridine, 2,3-diamino-6-methoxypyridine, 3,5-diamino-2, 6-dimethoxypyridine, 3,4-diaminopyridine, 2- (2-methoxyethyl) amino-3-amino-6-methoxypyridine, 2- (4'-methoxyphenyl) amino-3-aminopyridine, and the physiologically acceptable salts of the aforementioned compounds.
Bevorzugte Naphthalinderivate mit mindestens einer Hydroxygruppe werden ausgewählt aus mindestens einer Verbindung der Gruppe, die gebildet wird aus 1-Naphthol, 2-Methyl-1-naphthol, 2-Hydroxymethyl-1-naphthol, 2-Hydroxyethyl-1-naphthol, 1 ,3-Dihydroxynaphthalin, 1 ,5- Dihydroxynaphthalin, 1 ,6-Dihydroxynaphthalin, 1 ,7-Dihydroxynaphthalin, 1 ,8-Dihydroxynaphthalin, 2,7-Dihydroxynaphthalin und 2,3-Dihydroxynaphthalin.Preferred naphthalene derivatives having at least one hydroxy group are selected from at least one compound of the group formed from 1-naphthol, 2-methyl-1-naphthol, 2-hydroxymethyl-1-naphthol, 2-hydroxyethyl-1-naphthol, 1, 3 Dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,7-dihydroxynaphthalene and 2,3-dihydroxynaphthalene.
Die erfindungsgemäß verwendbaren Indolderivate werden bevorzugt ausgewählt aus mindestens einer Verbindung der Formel (K5) und/oder aus mindestens einem physiologisch verträglichen Salz einer Verbindung gemäß Formel (K5),The indole derivatives which can be used according to the invention are preferably selected from at least one compound of the formula (K5) and / or from at least one physiologically tolerated salt of a compound of the formula (K5),
Figure imgf000029_0001
worin
Figure imgf000029_0001
wherein
G23 steht für ein Wasserstoffatom, eine (C1 bis C4)-Alkylgruppe, eine (C3 bis C6)-G 23 is a hydrogen atom, a (C 1 to C 4 ) -alkyl group, a (C 3 to C 6 ) -
Cycloalkylgruppe, eine (C2 bis C4)-Alkenylgruppe, eine (C1 bis C4)-Cycloalkyl group, a (C 2 to C 4 ) alkenyl group, a (C 1 to C 4 ) -
Monohydroxyalkylgruppe, eine (C2 bis C4)-Polyhydroxyalkylgruppe, eine Aryl-(d bis C4)- alkylgruppe, G24 steht für eine Hydroxygruppe oder eine Gruppe -NG26G27, worin G26 und G27 unabhängig voneinander stehen für ein Wasserstoffatom, eine (C1 bis C4)-Alkylgruppe, eine (C3 bis C6)- Cycloalkylgruppe, eine (C2 bis C4)-Alkenylgruppe, eine (Ci bis C4)-Monohydroxyalkyl group, a (C 2 to C 4 ) polyhydroxyalkyl group, an aryl (d to C 4 ) alkyl group, G 24 represents a hydroxy group or a group -NG 26 G 27 , wherein G 26 and G 27 are independently a hydrogen atom, a (C 1 to C 4 ) alkyl group, a (C 3 to C 6 ) - Cycloalkyl group, a (C 2 to C 4 ) alkenyl group, a (Ci to C 4 ) -
Monohydroxyalkylgruppe, eine (C2 bis C4)-Polyhydroxyalkylgruppe, G25 Wasserstoffatom, ein Halogenatom oder eine (C1 bis C4)-Alkylgruppe, mit der Maßgabe, dass G24 in meta-Position oder ortho-Position zum Strukturfragment NG23 der Formel bindet.Monohydroxyalkyl group, a (C 2 to C 4 ) polyhydroxyalkyl group, G 25 hydrogen atom, a halogen atom or a (C 1 to C 4 ) alkyl group, with the proviso that G 24 is in the meta position or ortho position to the structural fragment NG 23 the formula binds.
Besonders bevorzugte Indolderivate werden ausgewählt aus mindestens einer Verbindung der Gruppe, die gebildet wird aus 4-Hydroxyindol, 6-Hydroxyindol und 7-Hydroxyindol und den physiologisch verträglichen Salzen der vorgenannten Verbindungen.Particularly preferred indole derivatives are selected from at least one compound of the group which is formed from 4-hydroxyindole, 6-hydroxyindole and 7-hydroxyindole and the physiologically acceptable salts of the abovementioned compounds.
Die erfindungsgemäß verwendbaren Indolinderivate werden bevorzugt ausgewählt aus mindestens einer Verbindung der Formel (K6) und/oder aus mindestens einem physiologisch verträglichen Salz einer Verbindung gemäß Formel (K6),The indoline derivatives which can be used according to the invention are preferably selected from at least one compound of the formula (K6) and / or from at least one physiologically tolerable salt of a compound of the formula (K6),
Figure imgf000030_0001
worin
Figure imgf000030_0001
wherein
G28 steht für ein Wasserstoffatom, eine (C1 bis C4)-Alkylgruppe, eine (C3 bis C6)- Cycloalkylgruppe, eine (C2 bis C4)-Alkenylgruppe, eine (C1 bis C4)- Monohydroxyalkylgruppe, eine (C2 bis C4)-Polyhydroxyalkylgruppe, eine Aryl-(C-ι bis C4)- alkylgruppe,G 28 represents a hydrogen atom, a (C 1 to C 4 ) alkyl group, a (C 3 to C 6 ) cycloalkyl group, a (C 2 to C 4 ) alkenyl group, a (C 1 to C 4 ) monohydroxyalkyl group , a (C 2 to C 4 ) -polyhydroxyalkyl group, an aryl- (C 1 -C 4 ) -alkyl group,
G29 steht für eine Hydroxygruppe oder eine Gruppe -NG31G32, worin G31 und G32 unabhängig voneinander stehen für ein Wasserstoffatom, eine (C1 bis C4)-Alkylgruppe, eine (C3 bis C6)- Cycloalkylgruppe, eine (C2 bis C4)-Alkenylgruppe, eine (C1 bis C4)- Monohydroxyalkylgruppe, eine (C2 bis C4)-Polyhydroxyalkylgruppe,G 29 represents a hydroxy group or a group -NG 31 G 32 , in which G 31 and G 32 independently of one another represent a hydrogen atom, a (C 1 to C 4 ) -alkyl group, a (C 3 to C 6 ) -cycloalkyl group, a (C 2 to C 4 ) alkenyl group, a (C 1 to C 4 ) monohydroxyalkyl group, a (C 2 to C 4 ) polyhydroxyalkyl group,
G30 Wasserstoffatom, ein Halogenatom oder eine (C1 bis C4)-Alkylgruppe, mit der Maßgabe, dass G29 in meta-Position oder ortho-Position zum Strukturfragment NG28 derG 30 is a hydrogen atom, a halogen atom or a (C 1 to C 4 ) alkyl group, with the proviso that G 29 in the meta position or ortho position to the structural fragment NG 28 of
Formel bindet.Formula binds.
Besonders bevorzugte Indolinderivate werden ausgewählt aus mindestens einer Verbindung der Gruppe, die gebildet wird aus 4-Hydroxyindolin, 6-Hydroxyindolin und 7-Hydroxyindolin und den physiologisch verträglichen Salzen der vorgenannten Verbindungen.Particularly preferred indoline derivatives are selected from at least one compound of the group formed from 4-hydroxyindoline, 6-hydroxyindoline and 7-hydroxyindoline and the physiologically acceptable salts of the aforementioned compounds.
Bevorzugte Pyrimidinderivate werden ausgewählt aus mindestens einer Verbindung der Gruppe, die gebildet wird aus 4,6-Diaminopyrimidin, 4-Amino-2,6-dihydroxypyrimidin, 2,4-Diamino-6- hydroxypyrimidin, 2,4,6-Trihydroxypyrimidin, 2-Amino-4-methylpyrimidin, 2-Amino-4-hydroxy-6- methylpyrimidin und 4,6-Dihydroxy-2-methylpyrimidin und den physiologisch verträglichen Salzen der vorgenannten Verbindungen. Erfindungsgemäß besonders bevorzugte Kupplerkomponenten werden ausgewählt unter m- Aminophenol, 5-Amino-2-methylphenol, 3-Amino-2-chlor-6-methylphenol, 2-Hydroxy-4- aminophenoxyethanol, 5-Amino-4-chlor-2-methylphenol, 5-(2'-Hydroxyethyl)-amino-2- methylphenol, 2,4-Dichlor-3-aminophenol, o-Aminophenol, m-Phenylendiamin, 2-(2,4- Diaminophenoxy)ethanol, 1 ,3-Bis(2,4-diaminophenoxy)propan, 1-Methoxy-2-amino-4-(2'- hydroxyethylamino)benzol, 1 ,3-Bis(2,4-diaminophenyl)propan, 2,6-Bis(2'-hydroxyethylamino)-1- methylbenzol, 2-({3-[(2-Hydroxyethyl)amino]-4-methoxy-5-methylphenyl}amino)ethanol, 2-({3-[(2- Hydroxyethyl)amino]-2-methoxy-5-methylphenyl}amino)ethanol, 2-({3-[(2-Hydroxyethyl)amino]- 4,5-dimethylphenyl}amino)ethanol, 2-[3-Morpholin-4-ylphenyl)amino]ethanol, 3-Amino-4-(2- methoxyethoxy)-5-methylphenylamin, 1-Amino-3-bis-(2'-hydroxyethyl)-aminobenzol, Resorcin, 2- Methylresorcin, 4-Chlorresorcin, 1 ,2,4-Trihydroxybenzol, 2-Amino-3-hydroxypyridin, 3-Amino-2- methylamino-6-methoxypyridin, 2,6-Dihydroxy-3,4-dimethylpyridin, 3,5-Diamino-2,6- dimethoxypyridin, 1-Phenyl-3-methylpyrazol-5-on, 1-Naphthol, 1 ,5-Dihydroxynaphthalin, 2,7- Dihydroxynaphthalin, 1 ,7-Dihydroxynaphthalin, 1 ,8-Dihydroxynaphthalin, 4-Hydroxyindol, 6- Hydroxyindol, 7-Hydroxyindol, 4-Hydroxyindolin, 6-Hydroxyindolin, 7-Hydroxyindolin oder Gemischen dieser Verbindungen oder den physiologisch verträglichen Salzen der vorgenannten Verbindungen.Preferred pyrimidine derivatives are selected from at least one compound of the group formed from 4,6-diaminopyrimidine, 4-amino-2,6-dihydroxypyrimidine, 2,4-diamino-6-hydroxypyrimidine, 2,4,6-trihydroxypyrimidine, 2 -Amino-4-methylpyrimidine, 2-amino-4-hydroxy-6-methylpyrimidine and 4,6-dihydroxy-2-methylpyrimidine and the physiologically acceptable salts of the aforementioned compounds. Particularly preferred coupler components according to the invention are selected from m-aminophenol, 5-amino-2-methylphenol, 3-amino-2-chloro-6-methylphenol, 2-hydroxy-4-aminophenoxyethanol, 5-amino-4-chloro-2-methylphenol , 5- (2'-hydroxyethyl) amino-2-methylphenol, 2,4-dichloro-3-aminophenol, o-aminophenol, m-phenylenediamine, 2- (2,4-diaminophenoxy) ethanol, 1,3-bis (2,4-diaminophenoxy) propane, 1-methoxy-2-amino-4- (2'-hydroxyethylamino) benzene, 1, 3-bis (2,4-diaminophenyl) propane, 2,6-bis (2'-bis) hydroxyethylamino) -1-methylbenzene, 2 - ({3 - [(2-hydroxyethyl) amino] -4-methoxy-5-methylphenyl} amino) ethanol, 2 - ({3 - [(2-hydroxyethyl) amino] -2 -methoxy-5-methylphenyl} amino) ethanol, 2- ({3 - [(2-hydroxyethyl) amino] -4,5-dimethylphenyl} amino) ethanol, 2- [3-morpholin-4-ylphenyl) amino] ethanol , 3-amino-4- (2-methoxyethoxy) -5-methylphenylamine, 1-amino-3-bis (2'-hydroxyethyl) aminobenzene, resorcinol, 2-methylresorcinol, 4-chlororesorcinol, 1, 2,4- Trihydroxybenzene, 2-amino-3-hydroxypyridine, 3-amino-2-methylamino-6-methoxypyride in, 2,6-dihydroxy-3,4-dimethylpyridine, 3,5-diamino-2,6-dimethoxypyridine, 1-phenyl-3-methylpyrazol-5-one, 1-naphthol, 1, 5-dihydroxynaphthalene, 2, 7- Dihydroxynaphthalene, 1, 7-dihydroxynaphthalene, 1, 8-dihydroxynaphthalene, 4-hydroxyindole, 6-hydroxyindole, 7-hydroxyindole, 4-hydroxyindoline, 6-hydroxyindoline, 7-hydroxyindoline or mixtures of these compounds or the physiologically acceptable salts of the aforementioned Links.
Die Kupplerkomponenten werden bevorzugt in einer Menge von 0,005 bis 20 Gew.-%, vorzugsweise 0,1 bis 5 Gew.-%, jeweils bezogen auf das anwendungs bereite Oxidationsfärbemittel, verwendet.The coupler components are preferably used in an amount of 0.005 to 20 wt .-%, preferably 0.1 to 5 wt .-%, each based on the ready oxidation dye.
Dabei werden Entwicklerkomponenten und Kupplerkomponenten im Allgemeinen in etwa molaren Mengen zueinander eingesetzt. Wenn sich auch der molare Einsatz als zweckmäßig erwiesen hat, so ist ein gewisser Überschuss einzelner Oxidationsfarbstoffvorprodukte nicht nachteilig, so dass Entwicklerkomponenten und Kupplerkomponenten in einem Mol-Verhältnis von 1 :0,5 bis 1 :3, insbesondere 1 :1 bis 1 :2, stehen können.In this case, developer components and coupler components are generally used in approximately molar amounts to each other. Although the molar use has proven to be expedient, a certain excess of individual oxidation dye precursors is not disadvantageous, so that developer components and coupler components in a molar ratio of 1: 0.5 to 1: 3, in particular 1: 1 to 1: 2 , can stand.
Im folgenden werden Beispiele für die als Substituenten der Verbindungen der Formeln (K1 ) bis (K6) genannten Reste aufgezählt: Beispiele für (Ci bis C4)-Alkylreste sind die Gruppen -CH3, - OH2OH3,The following are examples of the radicals mentioned as substituents of the compounds of the formulas (K1) to (K6): Examples of (C 1 to C 4 ) -alkyl radicals are the groups -CH 3 , - OH 2 OH 3 ,
-(-/H2(_/H2(-/H3, -(_/H((-/H3)2, -(-/H2(_/H2(-/H2(-/H3, -(_/H2(_/H((-/H3)2, -(-/H((_/H3)(-/H2(-/H3, -(_/(CΗ3)3.- (- / H 2 (_ / H 2 (- / H 3 , - (_ / H ((- / H 3 ) 2 , - (- / H 2 (_ / H 2 (- / H 2 (- / H 3 , - (H 2 / H 2 / H ((- / H 3 ) 2 , - (- / H ((- / H 3 ) (- / H 2 (- / H 3 , - (_ / ( CΗ 3 ) 3 .
Erfindungsgemäße Beispiele für (C3 bis C6)-Cycloalkylgruppen sind die Cyclopropyl, dieInventive examples of (C 3 to C 6 ) -cycloalkyl groups are the cyclopropyl, the
Cyclopentyl und die Cyclohexylgruppe.Cyclopentyl and the cyclohexyl group.
Erfindungsgemäße Beispiele für (C1 bis C4)-Alkoxyreste sind -OCH3, -OCH2CH3,Examples of (C 1 to C 4 ) -alkoxy radicals according to the invention are -OCH 3 , -OCH 2 CH 3 ,
-OCH2CH2CH3, -OCH(CHs)2, -OCH2CH2CH2CH3, -OCH2CH(CH3)2, -OCH(CH3)CH2CH3, --OCH 2 CH 2 CH 3 , -OCH (CH 2 ) 2 , -OCH 2 CH 2 CH 2 CH 3 , -OCH 2 CH (CH 3 ) 2 , -OCH (CH 3 ) CH 2 CH 3 ,
OC(CH3)3, insbesondere eine Methoxy- oder eine Ethoxygruppe.OC (CH 3 ) 3 , in particular a methoxy or an ethoxy group.
Weiterhin können als bevorzugte Beispiele für eine (C1 bis C4)-Monohydroxyalkylgruppe -CH2OH,Furthermore, as preferred examples of a (C 1 to C 4 ) monohydroxyalkyl group, -CH 2 OH,
-CH2CH2OH, -CH2CH2CH2OH, -CH2CH(OH)CH3, -CH2CH2CH2CH2OH genannt werden, wobei die-CH 2 CH 2 OH, -CH 2 CH 2 CH 2 OH, -CH 2 CH (OH) CH 3 , -CH 2 CH 2 CH 2 CH 2 OH, wherein the
Gruppe -CH2CH2OH bevorzugt ist. Ein besonders bevorzugtes Beispiel einer (C2 bis C4)-Polyhydroxyalkylgruppe ist die 1 ,2- Dihyd roxyethylg ru ppe.Group -CH 2 CH 2 OH is preferred. A particularly preferred example of a (C 2 to C 4 ) polyhydroxyalkyl group is the 1, 2-Dihyd roxyethylg ru ppe.
Beispiele für Halogenatome sind F-, Cl- oder Br-Atome, Cl-Atome sind ganz besonders bevorzugte Beispiele.Examples of halogen atoms are F, Cl or Br atoms, Cl atoms are very particularly preferred examples.
Beispiele für stickstoffhaltige Gruppen sind insbesondere -NH2, (C1 bis C4)- Monoalkylaminogruppen, (C1 bis C4)-Dialkylaminogruppen, (C1 bis C4)- Trialkylammoniumgruppen, (C1 bis C4)-Monohydroxyalkylaminogruppen, Imidazolinium und - NH3 +.Examples of nitrogen-containing groups are especially -NH 2, (C 1 to C 4) - monoalkylamino, (C 1 -C 4) -dialkylamino, (C 1 to C 4) - trialkylammonium groups, (C 1 to C 4) -Monohydroxyalkylaminogruppen, Imidazolinium and - NH 3 + .
Beispiele für (C1 bis C4)-Monoalkylaminogruppen sind -NHCH3, -NHCH2CH3, -NHCH2CH2CH3, -NHCH(CH3)2.Examples of (C 1 to C 4 ) monoalkylamino groups are -NHCH 3 , -NHCH 2 CH 3 , -NHCH 2 CH 2 CH 3 , -NHCH (CH 3 ) 2 .
Beispiele für (C1 bis C4)-Dialkylaminogruppe sind -N(CH3)2, -N(CH2CH3)2.Examples of (C 1 to C 4 ) -dialkylamino group are -N (CH 3 ) 2 , -N (CH 2 CH 3 ) 2 .
Beispiele für (C1 bis C4)-Alkoxy-(C-ι bis C4)-alkylgruppen sind die Gruppen -CH2CH2-O-CH3, -(-/H2(_/H2(-/H2-O-(-/H3, -(_/H2(_/H2-O-(-/H2(-/H3, -(_/H2(_/H2(-/H2-O-(-/H2(-/H3, -(_/H2(_/H2-O-(-/H((-/H3)2, -CH2CH2CH2-O-CH(CH3)2.Examples of (C 1 to C 4) alkoxy (C-ι-C 4) -alkyl groups are the groups -CH 2 CH 2 -O-CH 3, - (- / H 2 (_ / H 2 (- / H 2 -O - (- / H 3 , - (H 2 / H 2 (- / H 2 -O - (- / H 2 (- / H 3 , - (_ / H 2 (_ / H 2 (- / H 2 -O - (- / H 2 (- / H 3 , - (H 2 / H 2 - / H 2 -O - (- / H ((- / H 3 ) 2 , -CH 2 CH 2 CH 2 -O-CH (CH 3 ) 2 .
Beispiele für (C1 bis C4)-Alkoxy-(C-ι bis C4)-alkoxygruppen sind die Gruppen -0-CH2CH2-O-CH3, -0-CH2CH2CH2-O-CH3, -0-CH2CH2-O-CH2CH3, -0-CH2CH2CH2-O-CH2CH3, -0-CH2CH2-O- CH(CH3)2,Examples of (C 1 to C 4 ) -alkoxy- (C 1 -C 4 ) -alkoxy groups are the groups -O-CH 2 CH 2 -O-CH 3 , -O-CH 2 CH 2 CH 2 -O- CH 3, -0-CH 2 CH 2 -O-CH 2 CH 3, -0-CH 2 CH 2 CH 2 -O-CH 2 CH 3, -0-CH 2 CH 2 -O- CH (CH 3) 2 ,
-O-CH2CH2CH2-O-CH(CH3)2.-O-CH 2 CH 2 CH 2 -O-CH (CH 3 ) 2 .
Beispiele für Hydroxy-(C-ι bis C4)-alkoxyreste sind -0-CH2OH, -0-CH2CH2OH, -0-CH2CH2CH2OH, -O-CH2CH(OH)CH3, -O-CH2CH2CH2CH2OH.Examples of hydroxy- (C-ι-C 4) alkoxy groups are -0-CH 2 OH, -0-CH 2 CH 2 OH, -0-CH 2 CH 2 CH 2 OH, -O-CH 2 CH (OH ) CH 3 , -O-CH 2 CH 2 CH 2 CH 2 OH.
Beispiele für (C1 bis C4)-Aminoalkylreste sind -CH2NH2, -CH2CH2NH2, -CH2CH2CH2NH2, -CH2CH(NH2)CH31 -CH2CH2CH2CH2NH2.Examples of (C 1 to C 4 ) -aminoalkyl radicals are -CH 2 NH 2 , -CH 2 CH 2 NH 2 , -CH 2 CH 2 CH 2 NH 2 , -CH 2 CH (NH 2 ) CH 31 -CH 2 CH 2 CH 2 CH 2 NH 2 .
Ein Beispiel für Arylgruppen ist die Phenylgruppe, die auch substituiert sein kann. Beispiele für Aryl-(d bis C4)-alkylgruppen sind die Benzylgruppe und die 2-Phenylethylgruppe.An example of aryl groups is the phenyl group, which may also be substituted. Examples of aryl (C 1 to C 4 ) alkyl groups are the benzyl group and the 2-phenylethyl group.
Als Oxofarbstoffvorprodukte kommt bevorzugt eine Kombination aus mindestens einer Verbindung, die mindestens eine reaktive Carbonylgruppe enthält (Komponente (Oxo 1 )) mit mindestens einer Verbindung (Komponente Oxo2) Verbindungen, ausgewählt aus (Oxo2a) CH-aciden Verbindungen und/oder ausPreferred oxo dye precursors are a combination of at least one compound containing at least one reactive carbonyl group (component (oxo 1)) with at least one compound (component oxo2) compounds selected from (oxo2a) CH-acidic compounds and / or
(Oxo2b) Verbindungen mit primärer oder sekundärer Aminogruppe oder Hydroxygruppe, ausgewählt aus mindestens einer Verbindung der Gruppe, die gebildet wird aus primären oder sekundären aromatischen Aminen, stickstoffhaltigen heterozyklischen Verbindungen und aromatischen Hydroxyverbindungen zum Einsatz.(Oxo2b) Compounds having primary or secondary amino group or hydroxy group selected from at least one compound of the group formed from primary or secondary aromatic amines, nitrogen-containing heterocyclic compounds and aromatic hydroxy compounds.
Reaktive Carbonylverbindungen als Komponente (Oxo1 ) besitzen im Sinne der Erfindung mindestens eine Carbonylgruppe als reaktive Gruppe, welche mit der Komponente (Oxo2) unter Ausbildung einer kovalenten Bindung reagiert. Bevorzugte reaktive Carbonylverbindungen sind ausgewählt aus Verbindungen die mindestens eine Formylgruppe und/oder mindestens eine Ketogruppe, insbesondere mindestens eine Formylgruppe, tragen. Ferner sind erfindungsgemäß auch solche Verbindungen als Komponente (Oxo1 ) verwendbar, in denen die reaktive Carbonylgruppe derart derivatisiert bzw. maskiert ist, dass die Reaktivität des Kohlenstoffatoms der derivatisierten Carbonylgruppe gegenüber der Komponente (Oxo2) stets vorhanden ist. Diese Derivate sind bevorzugt Additionsverbindungen a) von Aminen und deren Derivate unter Bildung von Iminen oder Oximen als Additionsverbindung b) von Alkoholen unter Bildung von Acetalen oder Ketalen als Additionsverbindung c) von Wasser unter Bildung von Hydraten als Additionsverbindung (Komponente (Oxo1 ) leitet sich in diesem Fall c) von einem Aldehyd ab) an das Kohlenstoffatom der Carbonylgruppe der reaktiven Carbonylverbindung.Reactive carbonyl compounds as component (oxo1) have in the context of the invention at least one carbonyl group as a reactive group which reacts with the component (oxo2) to form a covalent bond. Preferred reactive carbonyl compounds are selected from compounds which carry at least one formyl group and / or at least one keto group, in particular at least one formyl group. Furthermore, those compounds according to the invention are also suitable as component (Oxo1) in which the reactive carbonyl group is derivatized or masked such that the reactivity of the carbon atom of the derivatized carbonyl group with respect to the component (Oxo2) is always present. These derivatives are preferably addition compounds a) of amines and their derivatives to form imines or oximes as addition compound b) of alcohols to form acetals or ketals as addition compound c) of water to form hydrates as addition compound (component (Oxo1) is derived in in this case c) from an aldehyde) to the carbon atom of the carbonyl group of the reactive carbonyl compound.
Bevorzugte reaktive Carbonylverbindungen der Komponente (Oxo1 ) werden ausgewählt aus der Gruppe, bestehend aus Benzaldehyd und seinen Derivaten, Naphthaldehyd und seinen Derivaten, Zimtaldehyd und seinen Derivaten, 2-Formylmethylen-1 ,3,3-trimethylindolin (Fischers Aldehyd oder Tribasen Aldehyd), 2-lndolaldehyd, 3-lndolaldehyd, 1-Methylindol-3-aldehyd, 2- Methylindol-3-aldehyd, 2-(1',3',3'-Trimethyl-2-indolinyliden)-acetaldehyd, 1-Methylpyrrol-2- aldehyd, Pyridoxal, Antipyrin-4-aldehyd, Furfural, 5-Nitrofurfural, Chromon-3-aldehyd, 3-(5'-Nitro- 2'-furyl)-acrolein, 3-(2'-Furyl)-acrolein und lmidazol-2-aldehyd, 5-(4-Dimethylaminophenyl)penta- 2,4-dienal, 5-(4-Diethylaminophenyl)penta-2,4-dienal, 5-(4-Methoxyphenyl)penta-2,4-dienal, 5- (3,4-Dimethoxyphenyl)penta-2,4-dienal, 5-(2,4-Dimethoxyphenyl)penta-2,4-dienal, 5-(4- Piperidinophenyl)penta-2,4-dienal, 5-(4-Morpholinophenyl)penta-2,4-dienal, 5-(4-Preferred reactive carbonyl compounds of the component (oxo1) are selected from the group consisting of benzaldehyde and its derivatives, naphthaldehyde and its derivatives, cinnamaldehyde and its derivatives, 2-formylmethylene-1,3,3-trimethylindoline (Fischer's aldehyde or tribasic aldehyde), 2-indolaldehyde, 3-indolaldehyde, 1-methylindole-3-aldehyde, 2-methylindole-3-aldehyde, 2- (1 ', 3', 3'-trimethyl-2-indolinylidene) -acetaldehyde, 1-methylpyrrole-2 aldehyde, pyridoxal, antipyrin-4-aldehyde, furfural, 5-nitrofurfural, chromone-3-aldehyde, 3- (5'-nitro-2'-furyl) -acrolein, 3- (2'-furyl) -acrolein and imidazole-2-aldehyde, 5- (4-dimethylaminophenyl) penta-2,4-dienal, 5- (4-diethylaminophenyl) penta-2,4-dienal, 5- (4-methoxyphenyl) penta-2,4-dienal , 5- (3,4-dimethoxyphenyl) penta-2,4-dienal, 5- (2,4-dimethoxyphenyl) penta-2,4-dienal, 5- (4-piperidinophenyl) penta-2,4-dienal, 5- (4-morpholinophenyl) penta-2,4-dienal, 5- (4-
Pyrrolidinophenyl)penta-2,4-dienal, 5-(4-Dimethylamino-1-naphthyl)penta-3,5-dienal, Piperonal, 6- Nitropiperonal, 2-Nitropiperonal, 5-Nitrovanillin, 2,5-Dinitrosalicylaldehyd, 5-Brom-3- nitrosalicylaldehyd, 3-Nitro-4-formylbenzolsulfonsäure, 4-Formyl-1-methylpyridinium-, 2-Formyl-1- methylpyridinium-, 4-Formyl-1-ethylpyridinium-, 2-Formyl-1-ethylpyridinium-, 4-Formyl-1- benzylpyridinium-, 2-Formyl-1-benzylpyridinium-, 4-Formyl-1 ,2-dimethylpyridinium-, 4-Formyl-1 ,3- dimethylpyridinium-, 4-Formyl-1-methylchinolinium-, 2-Formyl-1-methylchinolinium-, 5-Formyl-1- methylchinolinium-, 6-Formyl-1-methylchinolinium-, 7-Formyl-1-methylchinolinium-, 8-Formyl-1- methylchinolinium, 5-Formyl-1-ethylchinolinium-, 6-Formyl-1-ethylchinolinium-, 7-Formyl-1- ethylchinolinium-, 8-Formyl-1-ethylchinolinium, 5-Formyl-1-benzylchinolinium-, 6-Formyl-1- benzylchinolinium-, 7-Formyl-1-benzylchinolinium-, 8-Formyl-1-benzylchinolinium, 5-Formyl-1- allylchinolinium-, 6-Formyl-1-allylchinolinium-, 7-Formyl-1-allylchinolinium- und 8-Formyl-1- allylchinolinium-benzolsulfonat, -p-toluolsulfonat, -methansulfonat, -Perchlorat, -sulfat, -chlorid, - bromid, -iodid, -tetrachlorozinkat, -methylsulfat-, -trifluormethansulfonat, -tetrafluoroborat, lsatin, 1-Methyl-isatin, 1-Allyl-isatin, 1-Hydroxymethyl-isatin, 5-Chlor-isatin, 5-Methoxy-isatin, 5- Nitroisatin, 6-Nitro-isatin, 5-Sulfo-isatin, 5-Carboxy-isatin, Chinisatin, 1-Methylchinisatin, sowie beliebigen Gemischen der voranstehenden Verbindungen. Ganz besonders bevorzugt werden als reaktive Carbonylkomponente im Rahmen der Oxofärbung Benzaldehyd und/oder Zimtaldehyd und/oder Naphthaldehyd und/oder mindestens ein Derivat dieser vorgenannten Aldehyde, die insbesondere einen oder mehrere Hydroxy-, Alkoxy- oder Aminosubstituenten tragen, verwendet. Bevorzugt wird dabei wiederum die reaktive Carbonylverbindung der Komponente (Oxo1 ) ausgewählt aus mindestens einer Verbindung gemäß Formel (AC-1 ),Pyrrolidinophenyl) penta-2,4-dienal, 5- (4-dimethylamino-1-naphthyl) penta-3,5-dienal, piperonal, 6-nitropiperonal, 2-nitropiperonal, 5-nitrovanillin, 2,5-dinitrosalicylaldehyde, 5 -Brom-3-nitrosalicylaldehyde, 3-nitro-4-formylbenzenesulfonic acid, 4-formyl-1-methylpyridinium, 2-formyl-1-methylpyridinium, 4-formyl-1-ethylpyridinium, 2-formyl-1-ethylpyridinium , 4-formyl-1-benzyl-pyridinium, 2-formyl-1-benzyl-pyridinium, 4-formyl-1,2-dimethyl-pyridinium, 4-formyl-1,3-dimethyl-pyridinium, 4-formyl-1-methyl-quinolinium, 2-formyl-1-methylquinolinium, 5-formyl-1-methylquinolinium, 6-formyl-1-methylquinolinium, 7-formyl-1-methylquinolinium, 8-formyl-1-methylquinolinium, 5-formyl-1 ethylquinolinium, 6-formyl-1-ethylquinolinium, 7-formyl-1-ethylquinolinium, 8-formyl-1-ethylquinolinium, 5-formyl-1-benzylquinolinium, 6-formyl-1-benzylquinolinium, 7-formyl 1-benzylquinolinium, 8-formyl-1-benzylquinolinium, 5-formyl-1-allylquinolinium, 6-formyl-1-allylquinolinium, 7-formyl-1-al ylquinolinium and 8-formyl-1-allylquinolinium benzenesulfonate, p-toluenesulfonate, methanesulfonate, perchlorate, sulfate, chloride, bromide, iodide, tetrachlorozincate, methylsulfate, trifluoromethanesulfonate, tetrafluoroborate, isatin , 1-methyl-isatin, 1-allyl-isatin, 1-hydroxymethyl-isatin, 5-chloro-isatin, 5-methoxy-isatin, 5-nitro-isatin, 6-nitro-isatin, 5-sulfo-isatin, 5-carboxy -isatin, quinisatin, 1-methylquinisatin, and any mixtures of the above compounds. Benzaldehyde and / or cinnamaldehyde and / or naphthaldehyde and / or at least one derivative of these abovementioned aldehydes, which in particular carry one or more hydroxyl, alkoxy or amino substituents, are very particularly preferably used as the reactive carbonyl component in the oxo dyeing. In this case, preference is again given to the reactive carbonyl compound of the component (oxo1) selected from at least one compound of the formula (AC-1),
Figure imgf000034_0001
worin
Figure imgf000034_0001
wherein
• R1, R2 und R3 stehen unabhängig voneinander für ein Wasserstoffatom, ein Halogenatom, eine (C1 bis C6)-Alkylgruppe, eine (C2 bis C6)-Alkenylgruppe, eine Formylgruppe, eine Hydroxygruppe, eine C-|-C6-Alkoxygruppe, eine (C1 bis C6)-Dialkylaminogruppe, eine Di(C2- C6-hydroxyalkyl)aminogruppe, eine Di(C1 bis C6)-alkoxy-(C-ι bis C6)-alkyl)aminoguppe, eine (C1 bis C6)-Hydroxyalkyloxygruppe, eine Sulfonylgruppe, eine Carboxylgruppe, eine Sulfonsäuregruppe, eine Sulfonamidgruppe, eine Carbamoylgruppe, eine (C2 bis C6)- Acylgruppe, eine Acetylgruppe oder eine Nitrogruppe,R 1 , R 2 and R 3 independently of one another represent a hydrogen atom, a halogen atom, a (C 1 to C 6 ) -alkyl group, a (C 2 to C 6 ) -alkenyl group, a formyl group, a hydroxy group, a C 1 to C 6 | -C 6 alkoxy group, a (C 1 to C 6) dialkylamino group, a di - amino group, a di (C 1 to C 6) alkoxy (C-ι-C 6 (C 2 C 6 hydroxyalkyl) ) -alkyl) amino group, a (C 1 to C 6 ) -hydroxyalkyloxy group, a sulfonyl group, a carboxyl group, a sulfonic acid group, a sulfonamide group, a carbamoyl group, a (C 2 to C 6 ) -acyl group, an acetyl group or a nitro group,
• Z' steht für eine direkte Bindung oder eine Vinylengruppe,Z 'is a direct bond or a vinylene group,
• R4 und R5 stehen für ein Wasserstoffatom oder bilden gemeinsam, zusammen mit dem Restmolekül einen 5- oder 6-gliederigen aromatischen oder aliphatischen Ring.R 4 and R 5 represent a hydrogen atom or together form, together with the remainder of the molecule, a 5- or 6-membered aromatic or aliphatic ring.
Die Derivate der Benzaldehyde, Naphthaldehyde bzw. Zimtaldehyde der reaktiven Carbonylverbindung gemäß Komponente (Oxo1 ) werden bevorzugt ausgewählt aus mindestens einer Verbindung der Gruppe, bestehend aus 4-Hydroxy-3-methoxybenzaldehyd, 3,5-Dimethoxy- 4-hydroxybenzaldehyd, 4-Hydroxy-1-naphthaldehyd, 4-Hydroxy-2-methoxybenzaldehyd, 3,4- Dihydroxy-5-methoxybenzaldehyd, 3,4,5-Trihydroxybenzaldehyd, 3,5-Dibrom-4- hydroxybenzaldehyd, 4-Hydroxy-3-nitrobenzaldehyd, 3-Brom-4-hydroxybenzaldehyd, 4-Hydroxy- 3-methylbenzaldehyd, 3,5-Dimethyl-4-hydroxy-benzaldehyd, 5-Brom-4-hydroxy-3- methoxybenzaldehyd, 4-Diethylamino-2-hydroxybenzaldehyd, 4-Dimethylamino-2- methoxybenzaldehyd, 2-Methoxybenzaldehyd, 3-Methoxybenzaldehyd, 4-Methoxybenzaldehyd, 2-Ethoxybenzaldehyd, 3-Ethoxybenzaldehyd, 4-Ethoxybenzaldehyd, 4-Hydroxy-2,3-dimethoxy- benzaldehyd, 4-Hydroxy-2,5-dimethoxy-benzaldehyd, 4-Hydroxy-2,6-dimethoxy-benzaldehyd, A- Hydroxy-2-methyl-benzaldehyd, 4-Hydroxy-2,3-dimethyl-benzaldehyd, 4-Hydroxy-2,5-dimethyl- benzaldehyd, 4-Hydroxy-2,6-dimethyl-benzaldehyd, 3,5-Diethoxy-4-hydroxy-benzaldehyd, 2,6- Diethoxy-4-hydroxy-benzaldehyd, 3-Hydroxy-4-methoxy-benzaldehyd, 2-Hydroxy-4-methoxy- benzaldehyd, 2-Ethoxy-4-hydroxy-benzaldehyd, 3-Ethoxy-4-hydroxy-benzaldehyd, 4-Ethoxy-2- hydroxy-benzaldehyd, 4-Ethoxy-3-hydroxy-benzaldehyd, 2,3-Dimethoxybenzaldehyd, 2,4- Dimethoxybenzaldehyd, 2,5-Dimethoxybenzaldehyd, 2,6-Dimethoxybenzaldehyd, 3,4- Dimethoxybenzaldehyd, 3,5-Dimethoxybenzaldehyd, 2,3,4-Trimethoxybenzaldehyd, 2,3,5- Trimethoxybenzaldehyd, 2,3,6-Trimethoxybenzaldehyd, 2,4,6-Trimethoxybenzaldehyd, 2,4,5- Trimethoxybenzaldehyd, 2,5,6-Trimethoxybenzaldehyd, 2-Hydroxybenzaldehyd, 3- Hydroxybenzaldehyd, 4-Hydroxybenzaldehyd, 2,3-Dihydroxybenzaldehyd, 2,4-The derivatives of benzaldehydes, naphthaldehydes or cinnamaldehydes of the reactive carbonyl compound according to component (Oxo1) are preferably selected from at least one compound of the group consisting of 4-hydroxy-3-methoxybenzaldehyde, 3,5-dimethoxy-4-hydroxybenzaldehyde, 4-hydroxy 1-naphthaldehyde, 4-hydroxy-2-methoxybenzaldehyde, 3,4-dihydroxy-5-methoxybenzaldehyde, 3,4,5-trihydroxybenzaldehyde, 3,5-dibromo-4-hydroxybenzaldehyde, 4-hydroxy-3-nitrobenzaldehyde, 3 Bromo-4-hydroxybenzaldehyde, 4-hydroxy-3-methylbenzaldehyde, 3,5-dimethyl-4-hydroxybenzaldehyde, 5-bromo-4-hydroxy-3-methoxybenzaldehyde, 4-diethylamino-2-hydroxybenzaldehyde, 4-dimethylamino -2-methoxybenzaldehyde, 2-methoxybenzaldehyde, 3-methoxybenzaldehyde, 4-methoxybenzaldehyde, 2-ethoxybenzaldehyde, 3-ethoxybenzaldehyde, 4-ethoxybenzaldehyde, 4-hydroxy-2,3-dimethoxbenzaldehyde, 4-hydroxy-2,5-dimethoxy benzaldehyde, 4-hydroxy-2,6-dimethoxybenzaldehyde, A-hydroxy-2-methylbenzaldehyde, 4-hydroxy-2,3-dimethylbenzaldehyde, 4-hydroxy y-2,5-dimethylbenzaldehyde, 4-hydroxy-2,6-dimethylbenzaldehyde, 3,5-diethoxy-4-hydroxybenzaldehyde, 2,6-diethoxy-4-hydroxybenzaldehyde, 3-hydroxybenzaldehyde 4-methoxybenzaldehyde, 2-hydroxy-4-methoxybenzaldehyde, 2-ethoxy-4-hydroxybenzaldehyde, 3-ethoxy-4-hydroxybenzaldehyde, 4-ethoxy-2-hydroxybenzaldehyde, 4-ethoxy- 3-hydroxybenzaldehyde, 2,3-dimethoxybenzaldehyde, 2,4- Dimethoxybenzaldehyde, 2,5-dimethoxybenzaldehyde, 2,6-dimethoxybenzaldehyde, 3,4-dimethoxybenzaldehyde, 3,5-dimethoxybenzaldehyde, 2,3,4-trimethoxybenzaldehyde, 2,3,5-trimethoxybenzaldehyde, 2,3,6-trimethoxybenzaldehyde, 2,4,6-trimethoxybenzaldehyde, 2,4,5-trimethoxybenzaldehyde, 2,5,6-trimethoxybenzaldehyde, 2-hydroxybenzaldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, 2,3-dihydroxybenzaldehyde, 2,4-
Dihydroxybenzaldehyd, 2,4-Dihydroxy-3-methyl-benzaldehyd, 2,4-Dihydroxy-5-methyl- benzaldehyd, 2,4-Dihydroxy-6-methyl-benzaldehyd, 2,4-Dihydroxy-3-methoxy-benzaldehyd, 2,4- Dihydroxy-5-methoxy-benzaldehyd, 2,4-Dihydroxy-6-methoxy-benzaldehyd, 2,5-Dihydroxybenzaldehyde, 2,4-dihydroxy-3-methylbenzaldehyde, 2,4-dihydroxy-5-methylbenzaldehyde, 2,4-dihydroxy-6-methylbenzaldehyde, 2,4-dihydroxy-3-methoxy-benzaldehyde, 2,4-dihydroxy-5-methoxy-benzaldehyde, 2,4-dihydroxy-6-methoxybenzaldehyde, 2,5-
Dihydroxybenzaldehyd, 2,6-Dihydroxybenzaldehyd, 3,4-Dihydroxybenzaldehyd, 3,4-Dihydroxy-2- methyl-benzaldehyd, 3,4-Dihydroxy-5-methyl-benzaldehyd, 3,4-Dihydroxy-6-methyl-benzaldehyd, 3,4-Dihydroxy-2-methoxy-benzaldehyd, 3,5-Dihydroxybenzaldehyd, 2,3,4-Trihydroxybenzaldehyd, 2,3,5-Trihydroxybenzaldehyd, 2,3,6-Trihydroxybenzaldehyd, 2,4,6-Trihydroxybenzaldehyd, 2,4,5- Trihydroxybenzaldehyd, 2,5,6-Trihydroxybenzaldehyd, 4-Dimethylaminobenzaldehyd, A- Diethylaminobenzaldehyd, 4-Dimethylamino-2-hydroxybenzaldehyd, 4-Pyrrolidinobenzaldehyd, A- Morpholinobenzaldehyd, 2-Morpholinobenzaldehyd, 4-Piperidinobenzaldehyd, 3,5-Dichlor-4- hydroxybenzaldehyd, 4-Hydroxy-3,5-diiod-benzaldehyd, 3-Chlor-4-hydroxybenzaldehyd, 5-Chlor- 3,4-dihydroxybenzaldehyd, 5-Brom-3,4-dihydroxybenzaldehyd, 3-Chlor-4-hydroxy-5- methoxybenzaldehyd, 4-Hydroxy-3-iod-5-methoxybenzaldehyd, 2-Methoxy-1-naphthaldehyd, A- Methoxy-1-naphthaldehyd, 2-Hydroxy-1-naphthaldehyd, 2,4-Dihydroxy-1-napthaldehyd, A- Hydroxy-3-methoxy-1-naphthaldehyd, 2-Hydroxy-4-methoxy-1-naphthaldehyd, 3-Hydroxy-4- methoxy-1-naphthaldehyd, 2,4-Dimethoxy-1-naphthaldehyd, 3,4-Dimethoxy-1-naphthaldehyd, A- Dimethylamino-1-naphthaldehyd, 3-Hydroxy-4-nitrobenzaldehyd, 2-Hydroxy-3-methoxy-5- nitrobenzaldehyd, 5-Nitrovanillin, 2,5-Dinitrosalicylaldehyd, 5-Brom-3-nitrosalicylaldehyd, 2- Dimethylaminobenzaldehyd, 2-Chlor-4-dimethylaminobenzaldehyd, 4-Dimethylamino-2- methylbenzaldehyd, 4-Diethylamino-zimtaldehyd, 4-Dibutylamino-benzaldehyd, 3-Carboxy-4- hydroxy-benzaldehyd, 5-Carboxyvanillin, 3-Carboxy-4-hydroxy-5-methylbenzaldehyd, 3-Carboxy- 5-ethoxy-4-hydroxybenzaldehyd, 3-Carboxy-4-hydroxybenzaldehyd, 5-Carboxyvanillin, 3- Carboxy-4-hydroxy-5-methylbenzaldehyd, 3-Carboxy-5-ethoxy-4-hydroxybenzaldehyd, 3-Allyl-4- hydroxybenzaldehyd, 3-Allyl-4-hydroxy-5-methoxybenzaldehyd, 3-Allyl-4-hydroxy-5- methylbenzaldehyd, 3-Allyl-5-brom-4-hydroxybenzaldehyd, 3,5-Diallyl-4-hydroxybenzaldehyd, 3- Allyl-5-carboxy-4-hydroxybenzaldehyd (3-Allyl-5-formyl-2-hydroxybenzoesäure) und 3-Allyl-4- hydroxy-5-formylbenzaldehyd (5-Allyl-4-hydroxyisophthalaldehyd).Dihydroxybenzaldehyde, 2,6-dihydroxybenzaldehyde, 3,4-dihydroxybenzaldehyde, 3,4-dihydroxy-2-methylbenzaldehyde, 3,4-dihydroxy-5-methylbenzaldehyde, 3,4-dihydroxy-6-methylbenzaldehyde, 3,4-dihydroxy-2-methoxybenzaldehyde, 3,5-dihydroxybenzaldehyde, 2,3,4-trihydroxybenzaldehyde, 2,3,5-trihydroxybenzaldehyde, 2,3,6-trihydroxybenzaldehyde, 2,4,6-trihydroxybenzaldehyde, 2,4,5-trihydroxybenzaldehyde, 2,5,6-trihydroxybenzaldehyde, 4-dimethylaminobenzaldehyde, A-diethylaminobenzaldehyde, 4-dimethylamino-2-hydroxybenzaldehyde, 4-pyrrolidinobenzaldehyde, A-morpholinobenzaldehyde, 2-morpholinobenzaldehyde, 4-piperidinobenzaldehyde, 3, 5-dichloro-4-hydroxybenzaldehyde, 4-hydroxy-3,5-diiodobenzaldehyde, 3-chloro-4-hydroxybenzaldehyde, 5-chloro-3,4-dihydroxybenzaldehyde, 5-bromo-3,4-dihydroxybenzaldehyde, 3 Chloro-4-hydroxy-5-methoxybenzaldehyde, 4-hydroxy-3-iodo-5-methoxybenzaldehyde, 2-methoxy-1-naphthaldehyde, A-methoxy-1-naphthaldehyde, 2-hydroxy-1-naphthaldehyde, 2,4- Dihydroxy-1-naphthaldehyde, A-hydroxy-3-methoxy-1-nap 3-hydroxy-4-methoxy-1-naphthaldehyde, 2,4-dimethoxy-1-naphthaldehyde, 3,4-dimethoxy-1-naphthaldehyde, A-dimethylamino 1-naphthaldehyde, 3-hydroxy-4-nitrobenzaldehyde, 2-hydroxy-3-methoxy-5-nitrobenzaldehyde, 5-nitrovanillin, 2,5-dinitrosalicylaldehyde, 5-bromo-3-nitrosalicylaldehyde, 2-dimethylaminobenzaldehyde, 2-chloro 4-dimethylaminobenzaldehyde, 4-dimethylamino-2-methylbenzaldehyde, 4-diethylamino-cinnamaldehyde, 4-dibutylaminobenzaldehyde, 3-carboxy-4-hydroxybenzaldehyde, 5-carboxyvanillin, 3-carboxy-4-hydroxy-5-methylbenzaldehyde, 3-carboxy-5-ethoxy-4-hydroxybenzaldehyde, 3-carboxy-4-hydroxybenzaldehyde, 5-carboxyvanillin, 3-carboxy-4-hydroxy-5-methylbenzaldehyde, 3-carboxy-5-ethoxy-4-hydroxybenzaldehyde, 3 Allyl-4-hydroxybenzaldehyde, 3-allyl-4-hydroxy-5-methoxybenzaldehyde, 3-allyl-4-hydroxy-5-methylbenzaldehyde, 3-allyl-5-bromo-4-hydroxybenzaldehyde, 3,5-diallyl-4 hydroxybenzaldehyde, 3-allyl-5-carboxy-4-hydroxybenzaldehyde (3-allyl-5-formyl-2-h ydroxybenzoic acid) and 3-allyl-4-hydroxy-5-formylbenzaldehyde (5-allyl-4-hydroxyisophthalaldehyde).
Als CH-acide Verbindungen werden im Allgemeinen solche Verbindungen angesehen, die ein an ein aliphatisches Kohlenstoffatom gebundenes Wasserstoffatom tragen, wobei aufgrund von Elektronen-ziehenden Substituenten eine Aktivierung der entsprechenden Kohlenstoff- Wasserstoff-Bindung bewirkt wird. Prinzipiell sind der Auswahl der CH-aciden Verbindungen keine Grenzen gesetzt, solange nach der Kondensation mit den reaktiven Carbonylverbindungen der Komponente (Oxo1 ) eine für das menschliche Auge sichtbar farbige Verbindung erhalten wird. Es handelt sich erfindungsgemäß bevorzugt um solche CH-aciden Verbindungen, welche einen aromatischen und/oder einen heterozyklischen Rest enthalten. Der heterozyklische Rest kann wiederum aliphatisch oder aromatisch sein. Besonders bevorzugt werden die CH-aciden Verbindungen ausgewählt aus heterozyklischen Verbindungen, insbesondere kationischen, heterozyklischen Verbindungen.As CH-acidic compounds are generally considered those compounds which carry a bound to an aliphatic carbon atom hydrogen atom, wherein due to electron-withdrawing substituents, activation of the corresponding carbon-hydrogen bond is effected. In principle, there are no limits to the choice of CH-acidic compounds as long as a compound which is visibly colored visibly to the human eye is obtained after condensation with the reactive carbonyl compounds of the component (oxo1). According to the invention, these are preferably those CH-acidic compounds which contain an aromatic and / or a heterocyclic radical. The heterocyclic residue may again be aliphatic or aromatic. The CH-acidic compounds are particularly preferably selected from heterocyclic compounds, in particular cationic, heterocyclic compounds.
Ganz besonders bevorzugt wird als Komponente (Oxo2a) mindestens eine CH-acide Verbindung mit einem aromatischen oder aliphatischen, heterozyklischen Grundkörper eingesetzt, die ausgewählt wird aus zyklischen Oniumverbindungen mit der Struktureinheit der Formel (CH-1 ) und/oder Verbindungen der Formel (CH-2),Very particular preference is given to using as component (oxo2a) at least one CH-acidic compound having an aromatic or aliphatic, heterocyclic basic body which is selected from cyclic onium compounds having the structural unit of the formula (CH-1) and / or compounds of the formula (CH-) 2)
Figure imgf000036_0001
worin
Figure imgf000036_0001
wherein
• R6 steht für eine lineare oder cyclische (C1 bis C6)-Alkylgruppe, eine (C2 bis C6)- Alkenylgruppe, eine gegebenenfalls substituierte Arylgruppe, eine gegebenenfalls substituierte Heteroarylgruppe, eine Aryl-(d bis C6)-alkylgruppe, eine (C1 bis C6)- Hydroxyalkylgruppe, eine (C2 bis C6)-Polyhydroxyalkylgruppe, eine (C1 bis C6)-Alkoxy-(C-ι bis C6)-alkylgruppe, eine Gruppe R'R"N-(CH2)m-, worin R1 und R11 stehen unabhängig voneinander für ein Wasserstoffatom, eine (C1 bis C4)-Alkylgruppe, eine (C1 bis C4)-Hydroxyalkylgruppe oder eine Aryl-(C-ι bis C6)- alkylgruppe, wobei R1 und R" gemeinsam mit dem Stickstoffatom einen 5-, 6- oder 7- gliedrigen Ring bilden können und m steht für eine Zahl 2, 3, 4, 5 oder 6,R 6 represents a linear or cyclic (C 1 to C 6 ) alkyl group, a (C 2 to C 6 ) alkenyl group, an optionally substituted aryl group, an optionally substituted heteroaryl group, an aryl (d to C 6 ) alkyl group, a (C 1 -C 6) - hydroxyalkyl group, a (C 2 -C 6) -polyhydroxyalkyl group, a (C 1 to C 6) alkoxy alkyl (C-ι to C 6), a group R ' R "N- (CH 2 ) m -, in which R 1 and R 11 independently of one another represent a hydrogen atom, a (C 1 to C 4 ) -alkyl group, a (C 1 to C 4 ) -hydroxyalkyl group or an aryl- ( C 1 -C 6 ) -alkyl group, where R 1 and R "together with the nitrogen atom can form a 5-, 6- or 7-membered ring and m is a number 2, 3, 4, 5 or 6,
• R7 steht für eine (C1 bis C6)-Alkylgruppe, insbesondere für eine Methylgruppe,R 7 is a (C 1 to C 6 ) -alkyl group, in particular a methyl group,
• X' steht für ein physiologisch verträgliches Anion,X ' is a physiologically acceptable anion,
• der Zyklus der Formel (CH-1 ) repräsentiert alle Ringstrukturen, die zusätzlich weitere Heteroatome wie Stickstoff, Sauerstoff oder Schwefel enthalten können und ferner ankondensierte Ringstrukturen tragen können, wobei alle diese Ringsstrukturen zusätzliche Substituenten tragen können,The cycle of the formula (CH-1) represents all ring structures which may additionally contain other heteroatoms such as nitrogen, oxygen or sulfur and may further carry fused ring structures, all of these ring structures being able to carry additional substituents,
• Het steht für einen gegebenenfalls substituierten Heteroaromaten,Het is an optionally substituted heteroaromatic,
• X1 steht für eine direkte Bindung oder eine Carbonylgruppe.• X 1 represents a direct bond or a carbonyl group.
Bevorzugte Ringstrukturen, die die Struktureinheit der Formel (CH-1 ) tragen, werden erfindungsgemäß bevorzugt ausgewählt aus 3H-lndolium, Benzothiazolium, Benzoxazolium, 1 ,2- Dihydro-2-oxopyrimidinium, Chinolinium, Chinoxalinium oder Pyridinium.Preferred ring structures which carry the structural unit of the formula (CH-1) are preferably selected according to the invention from 3H-indolium, benzothiazolium, benzoxazolium, 1, 2-dihydro-2-oxopyrimidinium, quinolinium, quinoxalinium or pyridinium.
Erfindungsgemäß eignen sich Verbindungen gemäß Formel (CH-2) besonders gut solche, in denen sich der Rest Het gemäß Formel (CH-2) ableitet von einem der Heteroaromaten Furan, Thiophen, Pyrrol, Isoxazol, Isothiazol, Imidazol, Oxazol, Thiazol, Pyridin, Pyridazin, Pyrimidin, Pyrazin, 1 ,2,3-Triazin, 1 ,2,4-Triazin, 1 ,3,5-Triazin, Benzopyrrol, Benzofuran, Benzothiophen, Benzimidazol, Benzothiazol, Benzoxazol, Indazol, Benzoisoxazol, Benzoisothiazol, Indol, Chinolin, Isochinolin, Cinnolin, Phthalazin, Chinazolin, Chinoxalin, Acridin, Benzochinolin, Benzoisochinolin, Phenazin, Benzocinnolin, Benzochinazolin, Benzochinoxalin, Phenoxazin, Phenothiazin, Nephthyridin, Phenanthrolin, Indolizin, Chinolizin, Carbolin, Purin, Pteridin oder Cumarin, wobei die vorgenannten Heteroaromaten mit mindestens einer Gruppe ausgewählt aus einem Halogenatom, einer Nitrogruppe, einer Thiogruppe, einer ThJo-(C1 bis C6)-alkylgruppe, einer Heteroarylgruppe, einer Arylgruppe, einer (C1 bis C6)-Alkylgruppe, einer (C1 bis C6)- Alkoxygruppe, einer Hydroxygruppe, einer (C2 bis C6)-Hydroxyalkylgruppe, einer (C2 bis C6)- Polyhydroxyalkylgruppe, einer (C1 bis C6)-Alkoxy-(C-ι bis C6)-alkylgruppe, einer Aryl-(d bis C6)- alkylgruppe, einer Aminogruppe, einer (C1 bis C6)-Monoalkylaminogruppe, einer (C1 bis C6)- Dialkylaminogruppe, eine Dialkylaminoalkylgruppe -(CH2)n-NR'R", worin n eine ganze Zahl von 2 und 6 ist und R' und R" unabhängig voneinander eine lineare oder verzweigte Alkylgruppe bedeuten, welche gegebenenfalls zusammen einen Ring bilden können, substituiert sein können.According to the invention, compounds of the formula (CH-2) are particularly suitable for those in which the radical Het according to formula (CH-2) is derived from one of the heteroaromatic compounds furan, thiophene, pyrrole, isoxazole, isothiazole, imidazole, oxazole, thiazole, pyridine , Pyridazine, pyrimidine, pyrazine, 1, 2,3-triazine, 1, 2,4-triazine, 1, 3,5-triazine, benzopyrrole, benzofuran, benzothiophene, benzimidazole, benzothiazole, benzoxazole, indazole, benzoisoxazole, benzoisothiazole, indole . Quinoline, isoquinoline, cinnoline, phthalazine, quinazoline, quinoxaline, acridine, benzoquinoline, benzoisoquinoline, phenazine, benzocinnoline, benzoquinazoline, benzoquinoxaline, phenoxazine, phenothiazine, nephthyridine, phenanthroline, indolizine, quinolizine, carboline, purine, pteridine or coumarin, the aforementioned heteroaromatics having at least one group selected from a halogen atom, a nitro group, a thio group, a ThJo (C 1 to C 6 ) alkyl group, a heteroaryl group, an aryl group, a (C 1 to C 6 ) alkyl group, a (C 1 to C 6) - alkoxy group, a hydroxy group, a (C 2 to C 6) hydroxyalkyl group, a (C 2 to C 6) - polyhydroxyalkyl group, a (C 1 to C 6) alkoxy (C-ι-C 6) alkyl group, an aryl (d-C 6) - alkyl group, an amino group, a (C 1 -C 6) monoalkylamino group, a (C 1 to C 6) - dialkylamino group, a dialkylaminoalkyl group - (CH 2) n -NR 'R', where n is an integer of 2 and 6, and R 'and R''are independently of each other is a linear or branched alkyl group, which may optionally together form a ring may be substituted.
Vorzugsweise werden die Verbindungen gemäß Formel (CH-2) ausgewählt aus mindestens einer Verbindung der Gruppe bestehend aus 2-(2-Furoyl)-acetonitril, 2-(5-Brom-2-furoyl)-acetonitril, 3- (2,5-Dimethyl-3-furyl)-3-oxopropanitril, 2-(2-Thenoyl)-acetonitril, 2-(3-Thenoyl)-acetonitril, 2-(5- Fluor-2-thenoyl)-acetonitril, 2-(5-Chlor-2-thenoyl)-acetonitril, 2-(5-Brom-2-thenoyl)-acetonitril, 2-(5- Methyl-2-thenoyl)-acetonitril, 2-(2,5-Dimethylpyrrol-3-oyl)-acetonitril, 2-(1 ,2,5-Trimethylpyrrol-3- oyl)-acetonitril, 1 /-/-Benzimidazol-2-ylacetonitril, 1 /-/-Benzothiazol-2-ylacetonitril, 2-(Pyrid-2-yl)- acetonitril, 2,6-Bis(cyanmethyl)-pyridin, 2-(lndol-3-oyl)-acetonitril, 2-(2-Methyl-indol-3-oyl)- acetonitril und 2-(6-Hydroxy-4,7-dimethoxy-1-benzofuran-5-oyl)-acetonitril.Preferably, the compounds of formula (CH-2) are selected from at least one compound of the group consisting of 2- (2-furoyl) -acetonitrile, 2- (5-bromo-2-furoyl) -acetonitrile, 3- (2.5 -Dimethyl-3-furyl) -3-oxopropanitrile, 2- (2-thenoyl) -acetonitrile, 2- (3-thenoyl) -acetonitrile, 2- (5-fluoro-2-thenoyl) -acetonitrile, 2- (5 -Chloro-2-thenoyl) -acetonitrile, 2- (5-bromo-2-thenoyl) -acetonitrile, 2- (5-methyl-2-thenoyl) -acetonitrile, 2- (2,5-dimethylpyrrol-3-oyl ) -acetonitrile, 2- (1, 2,5-trimethylpyrrol-3-oyl) -acetonitrile, 1 / - / - benzimidazol-2-ylacetonitrile, 1 / - / - benzothiazol-2-ylacetonitrile, 2- (pyrid-2 -yl) - acetonitrile, 2,6-bis (cyanomethyl) pyridine, 2- (indole-3-oyl) -acetonitrile, 2- (2-methyl-indol-3-oyl) -acetonitrile and 2- (6- hydroxy-4,7-dimethoxy-1-benzofuran-5-oyl) -acetonitrile.
Die CH-aciden Verbindungen der Oxofarbstoffvorprodukte der Komponente (Oxo2a) werden bevorzugt aus mindestens einer Verbindung der Formel (CH-3) ausgewählt,The CH-acidic compounds of the oxo dye precursors of the component (oxo2a) are preferably selected from at least one compound of the formula (CH-3),
Figure imgf000037_0001
worin
Figure imgf000037_0001
wherein
R8 und R9 stehen unabhängig voneinander für eine lineare oder cyclische (C1 bis C6)- Alkylgruppe, eine (C2 bis C6)-Alkenylgruppe, eine gegebenenfalls substituierte Arylgruppe, eine gegebenenfalls substituierte Heteroarylgruppe, eine Aryl-(d bis C6)-alkylgruppe, eine (C1 bis C6)-Hydroxyalkylgruppe, eine (C2 bis C6)-Polyhydroxyalkylgruppe, eine (C1 bis C6)- AIkOXy-(C1 bis C6)-alkylgruppe, eine Gruppe R'RMN-(CH2)m-, worin R1 und R" stehen unabhängig voneinander für ein Wasserstoffatom, eine (C1 bis C4)-Alkylgruppe, eine (C1 bis C4)-Hydroxyalkylgruppe oder eine Aryl-(d bis C4)-alkylgruppe, wobei R1 und R11 gemeinsam mit dem Stickstoffatom einen 5-, 6- oder 7-gliedrigen Ring bilden können und m steht für eine Zahl 2, 3, 4, 5 oder 6, • R10 und R12 stehen unabhängig voneinander für ein Wasserstoffatom oder eine C1-C6- Alkylgruppe, wobei mindestens einer der Reste R10 und R12 eine (Ci bis C6)-Alkylgruppe bedeutet,R 8 and R 9 are each independently a linear or cyclic (C 1 to C 6 ) alkyl group, a (C 2 to C 6 ) alkenyl group, an optionally substituted aryl group, an optionally substituted heteroaryl group, an aryl (d to C 6 ) alkyl group, a (C 1 to C 6 ) hydroxyalkyl group, a (C 2 to C 6 ) polyhydroxyalkyl group, a (C 1 to C 6 ) alkoxy (C 1 to C 6 ) alkyl group, a R 'R M is N- (CH 2 ) m -, wherein R 1 and R "are each independently hydrogen, (C 1 to C 4 ) alkyl, (C 1 to C 4 ) hydroxyalkyl or a Aryl- (C 1 -C 4 ) -alkyl group, wherein R 1 and R 11 together with the nitrogen atom can form a 5-, 6- or 7-membered ring and m is a number 2, 3, 4, 5 or 6, R 10 and R 12 independently of one another represent a hydrogen atom or a C 1 -C 6 -alkyl group, where at least one of the radicals R 10 and R 12 denotes a (C 1 to C 6 ) -alkyl group,
• R11 steht für ein Wasserstoffatom, eine (C1 bis C6)-Alkylgruppe, eine (C1 bis C6)- Hydroxyalkylgruppe, eine (C2 bis C6)-Polyhydroxyalkylgruppe, eine (C1 bis C6)-Alkoxygruppe, eine (C1 bis C6)-Hydroxyalkoxygruppe, eine Gruppe R"'RlvN-(CH2)q-, worin R1" und Rιv stehen unabhängig voneinander für ein Wasserstoffatom, eine (C1 bis C6)-Alkylgruppe, eine (C1 bis C6)-Hydroxyalkylgruppe oder eine AIyI-(C1 bis C6)-alkylgruppe und q steht für eine Zahl 1 , 2, 3, 4, 5 oder 6, wobei der Rest R11 zusammen mit einem der Reste R10 oder R12 einen 5- oder 6-gliedrigen aromatischen Ring bilden kann, der gegebenenfalls mit einem Halogenatom, einer (C1 bis C6)-Alkylgruppe, einer (C1 bis C6)-Hydroxyalkylgruppe, einer (C2 bis C6)-Polyhydroxyalkylgruppe, einer (C1 bis C6)-Alkoxygruppe, einer (C1 bis C6)- Hydroxyalkoxygruppe, einer Nitrogruppe, einer Hydroxygruppe, einer Gruppe RVRVIN-(CH2)S-, worin Rv und Rvι stehen unabhängig voneinander für ein Wasserstoffatom, eine (C1 bis C6)-Alkylgruppe, eine (C1 bis C6)-Hydroxyalkylgruppe oder eine Aryl-(C-ι bis C6)- alkylgruppe und s steht für eine Zahl 0, 1 , 2, 3, 4, 5 oder 6 substituiert sein kann,• R 11 represents a hydrogen atom, a (C 1 to C 6) alkyl group, a (C 1 -C 6) - hydroxyalkyl group, a (C 2 -C 6) -polyhydroxyalkyl group, a (C 1 to C 6) - Alkoxy group, a (C 1 to C 6 ) -hydroxyalkoxy, a group R "'R lv N- (CH 2 ) q -, wherein R 1 " and R IV independently represent a hydrogen atom, a (C 1 to C 6 ) Alkyl group, a (C 1 to C 6 ) hydroxyalkyl group or an AIyI (C 1 to C 6 ) alkyl group and q is a number 1, 2, 3, 4, 5 or 6, wherein the radical R 11 together with one of the radicals R 10 or R 12 may form a 5- or 6-membered aromatic ring optionally substituted by a halogen atom, a (C 1 to C 6 ) -alkyl group, a (C 1 to C 6 ) -hydroxyalkyl group, a (C 2 to C 6 ) polyhydroxyalkyl group, a (C 1 to C 6 ) alkoxy group, a (C 1 to C 6 ) hydroxyalkoxy group, a nitro group, a hydroxy group, a group R V R VI N- (CH 2 ) S -, wherein R v and R vι are independently voneinande r is a hydrogen atom, a (C 1 to C 6 ) -alkyl group, a (C 1 to C 6 ) -hydroxyalkyl group or an aryl- (C 1 -C 6 ) -alkyl group and s is a number 0, 1, 2, 3, 4, 5 or 6 may be substituted,
• Y steht für ein Sauerstoffatom, ein Schwefelatom oder eine Gruppe NRV", worin Rv" steht für ein Wasserstoffatom, eine Arylgruppe, eine Heteroarylgruppe, eine (C1 bis C6)-Alkylgruppe oder eine Aryl-(d bis C6)-alkylgruppe,• Y represents an oxygen atom, a sulfur atom or a group NR V ", wherein R v" stands for a hydrogen atom, an aryl group, a heteroaryl group, a (C 1 to C 6) alkyl group or an aryl (d-C 6 ) alkyl,
• X" steht für ein physiologisch verträgliches Anion.• X " stands for a physiologically compatible anion.
Mindestens eine Gruppe R10 oder R12 gemäß Formel (CH-3) steht zwingend für eine (C1 bis C6)- Alkylgruppe. Diese Alkylgruppe trägt an deren α-Kohlenstoffatom bevorzugt mindestens zwei Wasserstoffatome. Besonders bevorzugte Alkylgruppen sind die Methyl-, Ethyl-, Propyl-, n-Butyl-, iso-Butyl, n-Pentyl-, neo-Pentyl-, n-Hexylgruppe. Ganz besonders bevorzugt stehen R10 und R12 unabhängig voneinander für Wasserstoff oder eine Methylgruppe, wobei mindestens eine Gruppe R10 oder R12 eine Methylgruppe bedeutet.At least one group R 10 or R 12 according to formula (CH-3) necessarily stands for a (C 1 to C 6 ) -alkyl group. This alkyl group preferably carries at least two hydrogen atoms on its α-carbon atom. Particularly preferred alkyl groups are the methyl, ethyl, propyl, n-butyl, iso-butyl, n-pentyl, neo-pentyl, n-hexyl group. Most preferably, R 10 and R 12 are each independently hydrogen or a methyl group, wherein at least one group R 10 or R 12 is a methyl group.
In einer bevorzugten Ausführungsform steht Y der Formel (CH-3) für ein Sauerstoff- oder ein Schwefelatom, besonders bevorzugt für ein Sauerstoffatom.In a preferred embodiment, Y of the formula (CH-3) is an oxygen or a sulfur atom, more preferably an oxygen atom.
Der Rest R8 der Formel (CH-3) wird bevorzugt ausgewählt aus einer (C1 bis C6)-Alkylgruppe (besonders bevorzugt einer Methylgruppe), einer (C2 bis C6)-Alkenylgruppe (insbesondere einer Allylgruppe), einer (C2 bis C6)-Hydroxyalkylgruppe (insbesondere eine 2-Hydroxyethylgruppe) oder einer gegebenenfalls substituierten Benzylgruppe.The radical R 8 of the formula (CH-3) is preferably selected from a (C 1 to C 6 ) -alkyl group (particularly preferably a methyl group), a (C 2 to C 6 ) -alkenyl group (in particular an allyl group), a ( C 2 to C 6 ) hydroxyalkyl group (especially a 2-hydroxyethyl group) or an optionally substituted benzyl group.
R11 der Formel (CH-3) steht bevorzugt für ein Wasserstoffatom.R 11 of the formula (CH-3) is preferably a hydrogen atom.
Besonders bevorzugt stehen in Formel (CH-3) die Reste R9, R10 und R12 für eine Methylgruppe, der Rest R11 für ein Wasserstoffatom, Y für ein Sauerstoff- oder ein Schwefelatom und der Rest R8 wird ausgewählt aus einer (C1 bis C6)-Alkylgruppe (besonders bevorzugt einer Methylgruppe), einer (C2 bis C6)-Alkenylgruppe (insbesondere einer Allylgruppe), einer (C2 bis C6)- Hydroxyalkylgruppe (insbesondere eine 2-Hydroxyethylgruppe) oder einer gegebenenfalls substituierten Benzylgruppe.Particularly preferred in formula (CH-3) are the radicals R 9 , R 10 and R 12 is a methyl group, the radical R 11 is a hydrogen atom, Y is an oxygen or sulfur atom and the radical R 8 is selected from a ( C 1 to C 6 ) -alkyl group (particularly preferably a methyl group), a (C 2 to C 6 ) alkenyl group (especially an allyl group), a (C 2 to C 6 ) hydroxyalkyl group (especially a 2-hydroxyethyl group) or an optionally substituted benzyl group.
Vorzugsweise sind die Verbindungen gemäß Formel (CH-3) ausgewählt aus einer oder mehrererPreferably, the compounds of formula (CH-3) are selected from one or more
Verbindungen der Gruppe von Salzen mit physiologisch verträglichem Gegenion X", die gebildet wird aus Salzen desCompounds of the group of salts with physiologically acceptable counterion X " , which is formed from salts of the
1 ,2-Dihydro-1 ,3,4,6-tetramethyl-2-oxo-pyrimidiniums,1, 2-dihydro-1, 3,4,6-tetramethyl-2-oxo-pyrimidinium,
1 ,2-Dihydro-1 ,3-diethyl-4,6-dimethyl-2-oxo-pyrimidiniums,1, 2-dihydro-1,3-diethyl-4,6-dimethyl-2-oxo-pyrimidinium,
1 ,2-Dihydro-1 ,3-dipropyl-4,6-dimethyl-2-oxo-pyrimidiniums,1, 2-dihydro-1,3-dipropyl-4,6-dimethyl-2-oxo-pyrimidinium,
1 ,2-Dihydro-1 ,3-di(2-hydroxyethyl)-4,6-dimethyl-2-oxo-pyrimidiniums,1, 2-dihydro-1,3-di (2-hydroxyethyl) -4,6-dimethyl-2-oxo-pyrimidinium,
1 ,2-Dihydro-1 ,3-diphenyl-4,6-dimethyl-2-oxo-pyrimidiniums,1, 2-dihydro-1,3-diphenyl-4,6-dimethyl-2-oxo-pyrimidinium,
1 ,2-Dihydro-1 ,3,4-trimethyl-2-oxo-pyrimidiniums,1, 2-dihydro-1, 3,4-trimethyl-2-oxo-pyrimidinium,
1 ,2-Dihydro-1 ,3-diethyl-4-methyl-2-oxo-pyrimidiniums,1, 2-dihydro-1,3-diethyl-4-methyl-2-oxo-pyrimidinium,
1 ,2-Dihydro-1 ,3-dipropyl-4-methyl-2-oxo-pyrimidiniums,1, 2-dihydro-1,3-dipropyl-4-methyl-2-oxo-pyrimidinium,
1 ,2-Dihydro-1 ,3-di(2-hydroxyethyl)-4-methyl-2-oxo-pyrimidiniums,1, 2-dihydro-1,3-di (2-hydroxyethyl) -4-methyl-2-oxo-pyrimidinium,
1 ,2-Dihydro-1 ,3-diphenyl-4-methyl-2-oxo-pyrimidiniums,1, 2-dihydro-1,3-diphenyl-4-methyl-2-oxo-pyrimidinium,
1-Allyl-1 ,2-dihydro-3,4,6-trimethyl-2-oxo-pyrimidiniums,1-allyl-1,2-dihydro-3,4,6-trimethyl-2-oxopyrimidinium,
1 ,2-Dihydro-1-(2-hydroxyethyl)-3,4,6-trimethyl-2-oxo-pyrimidiniums,1,2-dihydro-1- (2-hydroxyethyl) -3,4,6-trimethyl-2-oxo-pyrimidinium,
1 ,2-Dihydro-1 ,3,4,6-tetramethyl-2-thioxo-pyrimidiniums,1, 2-dihydro-1, 3,4,6-tetramethyl-2-thioxo-pyrimidinium,
1 ,2-Dihydro-1 ,3-diethyl-4,6-dimethyl-2-thioxo-pyrimidiniums,1, 2-dihydro-1,3-diethyl-4,6-dimethyl-2-thioxo-pyrimidinium,
1 ,2-Dihydro-1 ,3-dipropyl-4,6-dimethyl-2-thioxo-pyrimidiniums,1, 2-dihydro-1,3-dipropyl-4,6-dimethyl-2-thioxopyrimidiniums,
1 ,2-Dihydro-1 ,3-di(2-hydroxyethyl)-4,6-dimethyl-2-thioxo-pyrimidiniums,1, 2-dihydro-1,3-di (2-hydroxyethyl) -4,6-dimethyl-2-thioxo-pyrimidinium,
1 ,2-Dihydro-1 ,3-diphenyl-4,6-dimethyl-2-thioxo-pyrimidiniums,1, 2-dihydro-1,3-diphenyl-4,6-dimethyl-2-thioxo-pyrimidinium,
1 ,2-Dihydro-1 ,3,4-trimethyl-2-thioxo-pyrimidiniums,1, 2-dihydro-1, 3,4-trimethyl-2-thioxo-pyrimidinium,
1 ,2-Dihydro-1 ,3-diethyl-4-methyl-2-thioxo-pyrimidiniums,1, 2-dihydro-1,3-diethyl-4-methyl-2-thioxo-pyrimidinium,
1 ,2-Dihydro-1 ,3-dipropyl-4-methyl-2-thioxo-pyrimidiniums,1, 2-dihydro-1,3-dipropyl-4-methyl-2-thioxo-pyrimidinium,
1 ,2-Dihydro-1 ,3-di(2-hydroxyethyl)-4-methyl-2-thioxo-pyrimidiniums,1, 2-dihydro-1,3-di (2-hydroxyethyl) -4-methyl-2-thioxo-pyrimidinium,
1 ,2-Dihydro-1 ,3-diphenyl-4-methyl-2-thioxo-pyrimidiniums,1, 2-dihydro-1, 3-diphenyl-4-methyl-2-thioxo-pyrimidinium,
1 ,2-Dihydro-3,4-dimethyl-2-oxo-chinazoliniums und1, 2-dihydro-3,4-dimethyl-2-oxo-quinazolinium and
1 ,2-Dihydro-3,4-dimethyl-2-thioxo-chinazoliniums.1, 2-dihydro-3,4-dimethyl-2-thioxo-quinazolinium.
Ganz besonders bevorzugte Verbindungen gemäß Formel (CH-3) werden ausgewählt aus einer oder mehrerer Verbindungen der Gruppe von Salzen mit physiologisch verträglichem Gegenion X" Very particularly preferred compounds according to formula (CH-3) are selected from one or more compounds of the group of salts with physiologically acceptable counterion X "
, die gebildet wird aus Salzen deswhich is formed from salts of the
1 ,2-Dihydro-1 ,3,4,6-tetramethyl-2-oxo-pyrimidiniums,1, 2-dihydro-1, 3,4,6-tetramethyl-2-oxo-pyrimidinium,
1 ,2-Dihydro-1 ,3,4-trimethyl-2-oxo-pyrimidiniums,1, 2-dihydro-1, 3,4-trimethyl-2-oxo-pyrimidinium,
1-Allyl-1 ,2-dihydro-3,4,6-trimethyl-2-oxo-pyrimidiniums,1-allyl-1,2-dihydro-3,4,6-trimethyl-2-oxopyrimidinium,
1 ,2-Dihydro-1-(2-hydroxyethyl)-3,4,6-trimethyl-2-oxo-pyrimidiniums und1, 2-dihydro-1- (2-hydroxyethyl) -3,4,6-trimethyl-2-oxo-pyrimidinium and
1 ,2-Dihydro-1 ,3,4,6-tetramethyl-2-thioxo-pyrimidiniums. X' steht in den Formeln (CH-1 ) und (CH-3) sowie in obigen Listen bevorzugt für Halogenid, Benzolsulfonat, p-Toluolsulfonat, (C1 bis C4)-Alkansulfonat, Trifluormethansulfonat, Perchlorat, 0.5 Sulfat, Hydrogensulfat, Tetrafluoroborat, Hexafluorophosphat oder Tetrachlorozinkat. Besonders bevorzugt werden die Anionen Chlorid, Bromid, lodid, Hydrogensulfat oder p-Toluolsulfonat als X' eingesetzt.1, 2-Dihydro-1, 3,4,6-tetramethyl-2-thioxo-pyrimidiniums. X ' in the formulas (CH-1) and (CH-3) and in the above lists is preferably halide, benzenesulfonate, p-toluenesulfonate, (C 1 to C 4 ) -alkanesulfonate, trifluoromethanesulfonate, perchlorate, 0.5 sulfate, hydrogensulfate, Tetrafluoroborate, hexafluorophosphate or tetrachlorozincate. Particularly preferably, the anions chloride, bromide, iodide, hydrogen sulfate or p-toluenesulfonate are used as X ' .
Verbindungen der Formel (CH-3) werden erfindungsgemäß besonders bevorzugt verwendet.Compounds of the formula (CH-3) are particularly preferably used according to the invention.
Die CH-aciden Verbindungen der Oxofarbstoffvorprodukte der Komponente (Oxo2a) werden ganz besonders bevorzugt ausgewählt aus mindestens einer Verbindung der Gruppe, bestehend aus 2-(2-Furoyl)-acetonitril, 2-(5-Brom-2-furoyl)-acetonitril, 3-(2,5-Dimethyl-3-furyl)-3-oxopropanitril, 2- (2-Thenoyl)-acetonitril, 2-(3-Thenoyl)-acetonitril, 2-(5-Fluor-2-thenoyl)-acetonitril, 2-(5-Chlor-2- thenoyl)-acetonitril, 2-(5-Brom-2-thenoyl)-acetonitril, 2-(5-Methyl-2-thenoyl)-acetonitril, 2-(2,5- Dimethylpyrrol-3-oyl)-acetonitril, 2-(1 ,2,5-Trimethylpyrrol-3-oyl)-acetonitril, 1/-/-Benzimidazol-2- ylacetonitril, 1 /-/-Benzothiazol-2-ylacetonitril, 2-(Pyrid-2-yl)-acetonitril, 2,6-Bis(cyanmethyl)-pyridin, 2-(lndol-3-oyl)-acetonitril, 2-(2-Methyl-indol-3-oyl)-acetonitril, 2-(6-Hydroxy-4,7-dimethoxy-1- benzofuran-5-oyl)-acetonitril, 1 ,2,3,3-Tetramethyl-3H-indoliumiodid, 1 ,2,3,3-Tetramethyl-3H- indolium-p-toluolsulfonat, 1 ,2,3,3-Tetramethyl-3H-indolium-methansulfonat, 2,3-Dimethyl- benzothiazoliumiodid, 2,3-Dimethyl-benzothiazolium-p-toluolsulfonat, 1 ,4-Dimethylchinolinium- iodid, 1 ,2-Dimethylchinolinium-iodid, 3-Ethyl-2-methyl-benzoxazoliumiodid, 3-Ethyl-2-methyl- benzothiazoliumiodid, 1-Ethyl-4-methyl-chinoliniumiodid, 1-Ethyl-2-methylchinoliniumiodid, 1 ,2,3- Trimethylchinoxaliniumiodid, 3-Ethyl-2-methyl-benzoxazolium-p-toluolsulfonat, 3-Ethyl-2-methyl- benzothiazolium-p-toluolsulfonat, 1-Ethyl-4-methyl-chinolinium-p-toluolsulfonat, 1-Ethyl-2- methylchinolinium-p-toluolsulfonat, 1 ,2,3-Trimethylchinoxalinium-p-toluolsulfonat, 1-Allyl-i ,2- dihydro-3,4,6-trimethyl-2-oxopyrimidinium-bromid, 1 ,2-Dihydro-1-(2-hydroxyethyl)-3,4,6-trimethyl- 2-oxopyrimidinium-p-toluolsulfonat, 1 ,2-Dihydro-1 ,3,4,6-tetramethyl-2-oxo-pyrimidinium-chlorid, 1 ,2-Dihydro-1 ,3-diethyl-4,6-dimethyl-2-oxo-pyrimidinium-chlorid, 1 ,2-Dihydro-1 ,3-dipropyl-4,6- dimethyl-2-oxo-pyrimidinium-chlorid, 1-Allyl-1 ,2-dihydro-3,4,6-trimethyl-2-oxopyrimidinium- hydrogensulfat, 1 ,2-Dihydro-1-(2-hydroxyethyl)-3,4,6-trimethyl-2-oxopyrimidinium-hydrogensulfat, 1 ,2-Dihydro-1 ,3,4,6-tetramethyl-2-oxo-pyrimidinium-hydrogensulfat, 1 ,2-Dihydro-1 ,3-diethyl-4,6- dimethyl-2-oxo-pyrimidinium-hydrogensulfat, 1 ,2-Dihydro-1 ,3-dipropyl-4,6-dimethyl-2-oxo- pyrimidinium-hydrogensulfat, 1 ,2-Dihydro-1 ,3,4-trimethyl-2-oxo-pyrimidinium-chlorid, 1 ,2-Dihydro- 1 ,3,4-trimethyl-2-oxo-pyrimidinium-hydrogensulfat, 1 ,2-Dihydro-1 ,3-diethyl-4-methyl-2-oxo- pyrimidinium-chlorid, 1 ,2-Dihydro-1 ,3-diethyl-4-methyl-2-oxo-pyrimidinium-hydrogensulfat, 1 ,2- Dihydro-1 ,3-dipropyl-4-methyl-2-oxo-pyrimidinium-chlorid, 1 ,2-Dihydro-1 ,3-dipropyl-4-methyl-2- oxo-pyrimidinium-hydrogensulfat, 1 ,2-Dihydro-1 ,3,4,6-tetramethyl-2-thioxo-pyrimidinium-chlorid, 1 ,2-Dihydro-1 ,3-diethyl-4,6-dimethyl-2-thioxo-pyrimidinium-chlorid, 1 ,2-Dihydro-1 ,3-dipropyl-4,6- dimethyl-2-thioxo-pyrimidinium-chlorid, 1 ,2-Dihydro-1 ,3,4,6-tetramethyl-2-thioxo-pyrimidinium- hydrogensulfat, 1 ,2-Dihydro-1 ,3-dipropyl-4,6-dimethyl-2-thioxo-pyrimidinium-hydrogensulfat, 1 ,2- Dihydro-1 ,3,4-trimethyl-2-thioxo-pyrimidinium-chlorid, 1 ,2-Dihydro-1 ,3,4-trimethyl-2-thioxo- pyrimidinium-hydrogensulfat, 1 ,2-Dihydro-1 ,3-diethyl-4-methyl-2-thioxo-pyrimidinium-chlorid, 1 ,2- Dihydro-1 ,3-diethyl-4-methyl-2-thioxo-pyrimidinium-hydrogensulfat, 1 ,2-Dihydro-1 ,3-dipropyl-4- methyl-2-thioxo-pyrimidinium-chlorid und 1 ,2-Dihydro-1 ,3-dipropyl-4-methyl-2-thioxo-pyrimidinium- hydrogensulfat.The CH-acidic compounds of the oxo dye precursors of the component (oxo2a) are most preferably selected from at least one compound of the group consisting of 2- (2-furoyl) -acetonitrile, 2- (5-bromo-2-furoyl) -acetonitrile, 3- (2,5-dimethyl-3-furyl) -3-oxopropanitrile, 2- (2-thenoyl) -acetonitrile, 2- (3-thenoyl) -acetonitrile, 2- (5-fluoro-2-thenoyl) - acetonitrile, 2- (5-chloro-2-thenoyl) -acetonitrile, 2- (5-bromo-2-thenoyl) -acetonitrile, 2- (5-methyl-2-thenoyl) -acetonitrile, 2- (2.5 Dimethylpyrrol-3-oyl) -acetonitrile, 2- (1, 2,5-trimethylpyrrol-3-oyl) -acetonitrile, 1 / - / - benzimidazol-2-ylacetonitrile, 1 / - / - benzothiazol-2-ylacetonitrile, 2- (pyrid-2-yl) -acetonitrile, 2,6-bis (cyanomethyl) -pyridine, 2- (indole-3-oyl) -acetonitrile, 2- (2-methyl-indol-3-oyl) -acetonitrile , 2- (6-Hydroxy-4,7-dimethoxy-1-benzofuran-5-oyl) -acetonitrile, 1,2,3,3-tetramethyl-3H-indolium iodide, 1,2,3,3-tetramethyl-3H indolium p-toluenesulfonate, 1, 2,3,3-tetramethyl-3H-indolium methanesulfonate, 2,3-dimethylbenzothiazolium iodide, 2,3-Dimethylbenzothiazolium p-toluenesulfonate, 1,4-dimethylquinolinium iodide, 1,2-dimethylquinolinium iodide, 3-ethyl-2-methylbenzoxazolium iodide, 3-ethyl-2-methylbenzothiazolium iodide, 1 Ethyl 4-methyl-quinolinium iodide, 1-ethyl-2-methylquinolinium iodide, 1,2,3-trimethylquinoxaluminum iodide, 3-ethyl-2-methylbenzoxazolium p-toluenesulfonate, 3-ethyl-2-methylbenzothiazolium-p- toluenesulfonate, 1-ethyl-4-methyl-quinolinium p-toluenesulfonate, 1-ethyl-2-methylquinolinium p-toluenesulfonate, 1,2,3-trimethylquinoxaluminum p-toluenesulfonate, 1-allyl-i, 2-dihydro- 3,4,6-trimethyl-2-oxopyrimidinium bromide, 1, 2-dihydro-1- (2-hydroxyethyl) -3,4,6-trimethyl-2-oxopyrimidinium p-toluenesulfonate, 1, 2-dihydro- 1, 3,4,6-tetramethyl-2-oxo-pyrimidinium chloride, 1, 2-dihydro-1, 3-diethyl-4,6-dimethyl-2-oxo-pyrimidinium chloride, 1, 2-dihydro- 1, 3-dipropyl-4,6-dimethyl-2-oxo-pyrimidinium chloride, 1-allyl-1,2-dihydro-3,4,6-trimethyl-2-oxopyrimidinium hydrogen sulfate, 1,2-dihydrochloride 1- (2-hydroxyethyl) -3,4,6-trime ethyl 2-oxopyrimidinium hydrogensulfate, 1,2-dihydro-1,3,4,6-tetramethyl-2-oxopyrimidinium hydrogensulfate, 1,2-dihydro-1,3-diethyl-4,6-dimethyl- 2-oxopyrimidinium hydrogensulfate, 1,2-dihydro-1,3-dipropyl-4,6-dimethyl-2-oxopyrimidinium hydrogensulfate, 1,2-dihydro-1,3,4-trimethyl-2- oxo-pyrimidinium chloride, 1,2-dihydro-1,3,4-trimethyl-2-oxopyrimidinium hydrogen sulfate, 1,2-dihydro-1,3-diethyl-4-methyl-2-oxopyrimidinium chloride chloride, 1, 2-dihydro-1,3-diethyl-4-methyl-2-oxopyrimidinium hydrogensulfate, 1, 2-dihydro-1,3-dipropyl-4-methyl-2-oxopyrimidinium chloride, 1, 2-Dihydro-1,3-dipropyl-4-methyl-2-oxopyrimidinium hydrogen sulfate, 1,2-dihydro-1,3,4,6-tetramethyl-2-thioxopyrimidinium chloride, 1, 2-Dihydro-1,3-diethyl-4,6-dimethyl-2-thioxopyrimidinium chloride, 1, 2-dihydro-1,3-dipropyl-4,6-dimethyl-2-thioxopyrimidinium chloride, 1, 2-dihydro-1, 3,4,6-tetramethyl-2-thioxo-pyrimidinium hydrogen sulfate, 1, 2-dihydro-1, 3-dipropyl-4,6-dimethyl-2-thioxo-pyrimidinium-hydr ogensulfate, 1, 2-dihydro-1, 3,4-trimethyl-2-thioxo-pyrimidinium chloride, 1, 2-dihydro-1, 3,4-trimethyl-2-thioxo-pyrimidinium hydrogen sulfate, 1, 2 Dihydro-1,3-diethyl-4-methyl-2-thioxo-pyrimidinium chloride, 1, 2 Dihydro-1,3-diethyl-4-methyl-2-thioxo-pyrimidinium hydrogensulfate, 1,2-dihydro-1,3-dipropyl-4-methyl-2-thioxo-pyrimidinium chloride and 1,2-dihydrochloride 1, 3-dipropyl-4-methyl-2-thioxo-pyrimidinium hydrogen sulfate.
Des Weiteren kann als Komponente (Oxo2b) mindestens ein Oxidationsfarbstoffvorprodukt mit mindestens einer primären oder sekundären Aminogruppe und/oder mindestens einer Hydroxygruppe verwendet werden. Bevorzugt geeignete Vertreter finden sich unter der Ausführung der Oxidationsfarbstoffvorprodukte. Es ist jedoch erfindungsgemäß bevorzugt, wenn die Verbindungen der Komponente (Oxo2) nur unter CH-aciden Verbindungen ausgewählt werden.Furthermore, as component (Oxo2b) at least one oxidation dye precursor having at least one primary or secondary amino group and / or at least one hydroxyl group can be used. Preferred suitable representatives are found under the execution of the oxidation dye precursors. However, it is preferred according to the invention if the compounds of the component (oxo2) are selected only among CH-acidic compounds.
Die voranstehend genannten Verbindungen der Komponente (Oxo1 ) sowie der Komponente (Oxo2) werden, wenn sie zum Einsatz kommen, jeweils vorzugsweise in einer Menge von 0,03 bis 65 mmol, insbesondere von 1 bis 40 mmol, bezogen auf 100 g des gesamten Mittels, verwendet.The above-mentioned compounds of the component (Oxo1) and the component (Oxo2) are, when used, each preferably in an amount of 0.03 to 65 mmol, in particular from 1 to 40 mmol, based on 100 g of the total composition , used.
Weiterhin können die erfindungsgemäßen Mittel mindestens einen direktziehenden Farbstoff enthalten. Dabei handelt sich um Farbstoffe, die direkt auf das Haar aufziehen und keinen oxidativen Prozess zur Ausbildung der Farbe benötigen. Direktziehende Farbstoffe sind üblicherweise Nitrophenylendiamine, Nitroaminophenole, Azofarbstoffe, Anthrachinone oder Indophenole.Furthermore, the agents according to the invention may contain at least one substantive dye. These are dyes that raise directly on the hair and do not require an oxidative process to form the color. Direct dyes are usually nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols.
Die direktziehenden Farbstoffe werden jeweils bevorzugt in einer Menge von 0,001 bis 20 Gew.- %, bezogen auf die gesamte Anwendungszubereitung, eingesetzt. Die Gesamtmenge an direktziehenden Farbstoffen beträgt vorzugsweise höchstens 20 Gew.-%.The substantive dyes are each preferably used in an amount of 0.001 to 20% by weight, based on the total application preparation. The total amount of substantive dyes is preferably at most 20% by weight.
Direktziehende Farbstoffe können in anionische, kationische und nichtionische direktziehende Farbstoffe unterteilt werden.Direct dyes can be subdivided into anionic, cationic and nonionic substantive dyes.
Anionische direktziehende Farbstoffe:Anionic substantive dyes:
Als anionische direktziehende Farbstoffe eignen sich insbesondere 6-Hydroxy-5-[(4- sulfophenyl)azo]-2-naphthalinsulfonsäuredinatriumsalz (Cl. 15,985; Food Yellow No. 3; FD&C Yellow No. 6), 2,4-Dinitro-1-naphthol-7-sulfonsäure-dinatriumsalz (Cl. 10,316; Acid Yellow 1 ; Food Yellow No. 1 ), 2-(lndan-1 ,3-dion-2-yl)chinolin-x,x-sulfonsäure (Gemisch aus Mono- und Disulfonsäure) (Cl. 47,005; D&C Yellow No. 10; Food Yellow No. 13; Acid Yellow 3, Yellow 10), 4-((4-Amino-3-sulfophenyl)azo)benzolsulfonsäure-dinatriumsalz (Cl. 13,015, Acid Yellow 9), 5- Hydroxy-1-(4-sulfophenyl)-4-[(4-sulfophenyl)azo]pyrazol-3-carbonsäure-trinatriumsalz (Cl.Particularly suitable anionic direct dyes are 6-hydroxy-5 - [(4-sulfophenyl) azo] -2-naphthalenesulfonic acid disodium salt (CI 15.985, Food Yellow No. 3, FD & C Yellow No. 6), 2,4-dinitro-1 -naphthol-7-sulfonic acid disodium salt (Cl.10.316; Acid Yellow 1, Food Yellow No. 1), 2- (indan-1, 3-dion-2-yl) quinoline-x, x-sulfonic acid (mixture of mono and disulfonic acid) (CI 47,005, D & C Yellow No. 10, Food Yellow No. 13, Acid Yellow 3, Yellow 10), 4 - ((4-amino-3-sulfophenyl) azo) benzenesulfonic acid disodium salt (CI 13,015 , Acid Yellow 9), 5-hydroxy-1- (4-sulfophenyl) -4 - [(4-sulfophenyl) azo] pyrazole-3-carboxylic acid trisodium salt (Cl.
19,140; Food Yellow No. 4; Acid Yellow 23), 3-[(4-Phenylamino)phenyl]azobezolsulfon- säuresäure-natriumsalz (Cl. 13,065; Ki406; Acid Yellow 36), 9-(2-Carboxyphenyl)-6-hydroxy-3H- xanthen-3-on (Cl. 45,350; Acid Yellow 73; D&C Yellow No. 8), 5-[(2,4-Dinitrophenyl)amino]-2- phenylaminobenzolsulfonsäure-natriumsalz (Cl. 10,385; Acid Orange 3), 4-[(2,4- Dihydroxyphenyl)azo]-benzolsulfonsäure-natriumsalz (Cl. 14,270; Acid Orange 6), 4-[(2- Hydroxynaphth-1-yl)azo]-benzolsulfonsäure-natriumsalz (Cl. 15,510; Acid Orange 7), 4-[(2,4- Dihydroxy-3-[(2,4-dimethylphenyl)azo]-phenyl)azo]-benzolsulfonsäure-natriumsalz (Cl. 20,170; Acid Orange 24), 4-Hydroxy-3-[(2-methoxyphenyl)azo]-1-naphthalinsulfonsäure-natriumsalz (Cl. 14,710; Acid Red 4), 4-Hydroxy-3-[(4-sulfonaphth-1-yl)azo]-1-naphthalin-sulfonsäure- dinatriumsalz (Cl. 14,720; Acid Red No.14), 6- Hydroxy-5-[(4-sulfonaphth-1-yl)azo]-2,4- naphthalin-disulfonsäure-trinatriumsalz (Cl. 16,255; Ponceau 4R; Acid Red 18), 3-Hydroxy-4-[(4- sulfonaphth-1-yl)azo]-2,7-naphthalin-disulfonsäure-trinatriumsalz (Cl. 16,185; Acid Red 27), 8- Amino-1-hydroxy-2-(phenylazo)-3,6-naphthalin-disulfonsäure-dinatriumsalz (Cl. 17,200; Acid Red 33; Red 33), 5- (Acetylamino)-4-hydroxy-3-[(2-methylphenyl)azo]-2,7-naphthalin-disulfonsäure- dinatriumsalz (Cl. 18,065; Acid Red 35), 2-(3-Hydroxy-2,4,5,7-tetraiod-dibenzopyran-6-on-9-yl)- benzoesäure-dinatriumsalz (Cl. 45,430; Acid Red 51 ), N-[6-(Diethylamino)-9-(2,4-disulfophenyl)- 3H-xanthen-3-yliden]-N-ethylethanammonium-hydroxid, inneres Salz, Natriumsalz (Cl. 45,100; Acid Red 52), 8-[(4-(Phenylazo)phenyl)azo]-7-naphthol-1 ,3-disulfonsäure-dinatriumsalz (Cl. 27,290; Acid Red 73), 2',4',5',7'-Tetrabrom-3',6'- dihydroxyspiro[isobenzofuran-1(3H),9'- [9H]xanthen]-3-on-dinatriumsalz (Cl. 45,380; Acid Red 87), 2',4',5',7'-Tetrabrom-4,5,6,7- tetrachlor-3',6'- dihydroxyspiro[isobenzofuran-1(3H),9'[9H]xanthen]-3-on-dinatriumsalz (Cl. 45,410; Acid Red 92), 3',6'-Dihydroxy-4',5'-diiodospiro[isobenzofuran-1(3H),9'(9H)- xanthen]-3-on- dinatriumsalz (Cl. 45425; Acid Red 95), 2-Hydroxy-3-((2- hydroxynaphth-1-yl)azo)-5- nitrobenzolsulfonsäure-natriumsalz (Cl. 15,685; Acid Red 184), 3-Hydroxy-4-(3-methyl-5-oxo-1- phenyl-4,5-dihydro-1 H-pyrazol-4-ylazo)-naphthalin-1-sulfonsäure-natriumsalz, Chrom-Komplex (Acid Red 195), 3-Hydroxy-4-[(4-methyl-2-sulfonphenyl)azo]-2-naphthalincarbonsäure- calciumsalz (Cl. 15,850:1 ; Pigment Red 57:1 ), 3-[(2,4-Dimethyl-5-sulfophenyl)azo]-4-hydroxy-1- naphthalin-sulfonsäure-dinatriumsalz (Cl. 14,700; Food Red No. 1 ; Ponceau SX; FD&C Red No. 4), 1 ,4- Bis[(2-sulfo-4-methylphenyl)amino]-9,10-anthrachinon-dinatriumsalz (Cl. 61 ,570; Acid Green 25), Bis[4-(dimethylamino)phenyl]-(3,7-disulfo-2-hydroxynaphth-1-yl)carbenium-inneres Salz, Natriumsalz (Cl. 44,090; Food Green No. 4; Acid Green 50), Bis[4-(diethylamino)- phenyl](2,4-disulfophenyl)carbenium-inneres Salz, Natriumsalz (2:1 ) (Cl. 42,045; Food Blue No. 3; Acid Blue 1 ), Bis[4-(diethylamino)phenyl](5-hydroxy-2,4-disulfophenyl)-carbenium-inneres Salz, Calciumsalz (2:1 ) (Cl. 42,051 ; Acid Blue 3), N-[4-[(2,4-Disulfophenyl)[4- [ethyl(phenylmethyl)amino)phenyl]methylen]-2,5-cyclohexadien-1-yliden]-N- ethylbenzolmethanaminium-hydroxid, inneres Salz, Natriumsalz (Cl. 42,080; Acid Blue 7), (2- Sulfophenyl)di[4-(ethyl((4-sulfophenyl)methyl)amino)phenyl]-carbenium-dinatriumsalz Betain (Cl. 42,090; Acid Blue 9; FD&C Blue No. 1), 1-Amino-4-(phenylamino)-9,10-anthrachinon-2- sulfonsäure (Cl. 62,055; Acid Blue 25), 1-Amino-4-(cyclohexylamino)-9,10-anthrachinon-2- sulfonsäure-natriumsalz (Cl. 62045; Acid Blue 62), 2-(1 ,3-Dihydro-3-oxo-5-sulfo-2H-indol-2- yliden)-2,3-dihydro-3-oxo-1 H-indol-5- sulfonsäure-dinatriumsalz (Cl. 73,015; Acid Blue 74), 9-(2- Carboxyphenyl)-3-[(2-methylphenyl)amino]-6-[(2-methyl-4-sulfophenyl)amino]xanthylium-inneres Salz, Natriumsalz (Cl. 45,190; Acid Violet 9), 1-Hydroxy-4-[(4-methyl-2- sulfophenyl)amino]-9,10- anthrachinon-natriumsalz (Cl. 60,730; D&C Violett No. 2; Acid Violet 43), Bis[3-nitro-4-[(4- phenylamino)-3-sulfo-phenylamino]-phenyl]-sulfon (Cl. 10,410; Acid Brown 13), 5-Amino-4- hydroxy-6-[(4-nitrophenyl)-azo]-3-(phenylazo)-2,7-naphthalin-disulfonsäure-dinatriumsalz (Cl. 20,470; Acid Black 1 ), 3-Hydroxy-4-[(2-hydroxynaphth-1-yl)azo]-7-nitro-1-naphthalin-sulfonsäure- chromkomplex (3:2) (Cl. 15,71 1 ; Acid Black 52), 4-(Acetylamino)-5-hydroxy-6-[(7-sulfo-4-[(4- sulfophenyl)azo]naphth-1-yl)azo]-1 ,7-naphthalindisulfonsäure-tetranatriumsalz (Cl. 28,440; Food Black No. 1 ), 3',3",5',5"-Tetrabromphenolsulfonphthalein (Bromphenolblau).19,140; Food Yellow No. 4; Acid yellow 23), 3 - [(4-phenylamino) phenyl] azobenzenesulfonic acid sodium salt (CI 13.065, Ki406, Acid Yellow 36), 9- (2-carboxyphenyl) -6-hydroxy-3H-xanthene-3 on (Cl.45, 350; Acid Yellow 73; D & C Yellow No. 8), 5 - [(2,4-dinitrophenyl) amino] -2-phenylaminobenzenesulfonic acid, sodium salt (Cl.10, 385; Acid Orange 3), 4 - [(2 , 4- Dihydroxyphenyl) azo] -benzenesulfonic acid, sodium salt (CI 14,270, Acid Orange 6), 4 - [(2-hydroxynaphth-1-yl) azo] -benzenesulfonic acid, sodium salt (CI 15, 510, Acid Orange 7), 4 - [( 2,4-Dihydroxy-3 - [(2,4-dimethylphenyl) azo] -phenyl) azo] -benzenesulfonic acid, sodium salt (CI 20,170, Acid Orange 24), 4-hydroxy-3 - [(2-methoxyphenyl) azo ] -1-naphthalenesulfonic acid, sodium salt (Cl 14.710; Acid Red 4), 4-hydroxy-3 - [(4-sulfonaphth-1-yl) azo] -1-naphthalenesulfonic acid, dinatrium salt (Cl., 14, 720; Acid Red No. 14), 6-hydroxy-5 - [(4-sulfonaphth-1-yl) azo] -2,4-naphthalenedisulfonic acid trisodium salt (CI 16,255, Ponceau 4R, Acid Red 18), 3-hydroxy- 4 - [(4-sulfonaphth-1-yl) azo] -2,7-naphthalenedisulfonic acid trisodium salt (CI 16.185, Acid Red 27), 8-amino-1-hydroxy-2- (phenylazo) -3, 6-naphthalenedisulfonic acid disodium salt (CI 17,200, Acid Red 33, Red 33), 5- (2-methylphenyl) azo] -2,7-naphthalenedisulfonic acid disodium salt (Cl 18,065, Acid Red 35), 2- (3-hydroxy-2,4,5,7-tetraiodo-d ibenzopyran-6-on-9-yl) benzoic acid disodium salt (Cl. 45,430; Acid Red 51), N- [6- (diethylamino) -9- (2,4-disulfophenyl) -3H-xanthen-3-ylidene] -N-ethylethanammonium hydroxide, inner salt, sodium salt (CI 45, 100; Acid Red 52), 8 - [(4- (phenylazo) phenyl) azo] -7-naphthol-1,3-disulphonic acid disodium salt (CI 27,290, Acid Red 73), 2 ', 4', 5 ', 7'- Tetrabromo-3 ', 6'-dihydroxyspiro [isobenzofuran-1 (3H), 9'- [9H] xanthene] -3-one disodium salt (Cl.45, 380; Acid Red 87), 2', 4 ', 5', 7'-tetrabromo-4,5,6,7-tetrachloro-3 ', 6'-dihydroxyspiro [isobenzofuran-1 (3H), 9' [9H] xanthene] -3-one disodium salt (CI 45,410; Acid Red 92), 3 ', 6'-dihydroxy-4', 5'-diiodospiro [isobenzofuran-1 (3H), 9 '(9H) -xanthene] -3-one-disodium salt (CI 45425, Acid Red 95), 2-Hydroxy-3 - ((2-hydroxynaphth-1-yl) azo) -5-nitrobenzenesulfonic acid, sodium salt (Cl 15.655, Acid Red 184), 3-hydroxy-4- (3-methyl-5-oxo-1 - phenyl-4,5-dihydro-1H-pyrazol-4-ylazo) -naphthalene-1-sulfonic acid sodium salt, chromium complex (Acid Red 195), 3-hydroxy-4 - [(4-methyl-2-) sulfonphenyl) azo] -2-naphthalenecarboxylic acid calcium salt (Cl 15.850: 1; Pi Red. 57: 1), 3 - [(2,4-dimethyl-5-sulfophenyl) azo] -4-hydroxy-1-naphthalenesulfonic acid disodium salt (Cl. 14,700; Food Red No. 1 ; Ponceau SX; FD & C Red No. 4), 1, 4-bis [(2-sulfo-4-methylphenyl) amino] -9,10-anthraquinone disodium salt (Cl. 61, 570; Acid Green 25), bis [4- (dimethylamino) phenyl] - (3,7-disulfo-2-hydroxynaphth-1-yl) carbenium inner salt, sodium salt (CI 44,090, Food Green No. 4, Acid Green 50), bis [4- (diethylamino) -phenyl] (2, 4-disulfophenyl) carbenium inner salt, sodium salt (2: 1) (CI 42.045, Food Blue No. 3, Acid Blue 1), bis [4- (diethylamino) phenyl] (5-hydroxy-2,4-disulfophenyl ) carbenium inner salt, calcium salt (2: 1) (CI 42,051, Acid Blue 3), N- [4 - [(2,4-disulfophenyl) [4- [ethyl (phenylmethyl) amino) phenyl] methylene] -2,5-cyclohexadien-1-ylidene] -N-ethylbenzenemethanamine hydroxide, inner salt, sodium salt (CI 42.080, Acid Blue 7), (2-sulfophenyl) di [4- (ethyl (4-sulfophenyl) methyl ) amino) phenyl] -carbenium disodium salt betaine (CI 42,090, Acid Blue 9, FD & C Blue No. 1), 1-amino-4- (phenylamino) -9,10-anthraquinone-2-sulfonic acid (CI 62,055; Acid Blue 25), 1-amino-4- (cyclohexylamino) -9,10-anthraquinone-2-sulfonic acid natri umsalz (Cl. 62045; Acid Blue 62), 2- (1,3-dihydro-3-oxo-5-sulfo-2H-indol-2-ylidene) -2,3-dihydro-3-oxo-1H-indole-5-sulfonic acid disodium salt (CI 73.015, Acid Blue 74), 9- (2-carboxyphenyl) -3 - [(2-methylphenyl) amino] -6 - [(2-methyl-4-sulfophenyl) amino] xanthylium inner salt, sodium salt (Cl.45, 190; Acid Violet 9), 1-hydroxy-4 - [(4-methyl-2-sulfophenyl) amino] -9,10-anthraquinone, sodium salt (Cl.60,730; D & C Violet No. 2, Acid Violet 43 ), Bis [3-nitro-4 - [(4-phenylamino) -3-sulfophenylamino] phenyl] sulfone (Cl 10.410, Acid Brown 13), 5-amino-4- hydroxy-6 - [(4-nitrophenyl) -azo] -3- (phenylazo) -2,7-naphthalenedisulfonic acid disodium salt (Cl 20,470, Acid Black 1), 3-hydroxy-4 - [(2-hydroxynaphth 1-yl) azo] -7-nitro-1-naphthalenesulfonic acid chromium complex (3: 2) (Cl 15.71 1; Acid Black 52), 4- (acetylamino) -5-hydroxy-6- [ (7-sulfo-4 - [(4-sulfophenyl) azo] naphth-1-yl) azo] -1, 7-naphthalenedisulfonic acid tetrasodium salt (CI 28,440, Food Black No. 1), 3 ', 3 ", 5 ', 5 "-Tetrabromphenolsulfonphthalein (bromophenol blue).
Bevorzugte anionische direktziehende Farbstoffe sind die unter den internationalen Bezeichnungen bzw. Handelsnamen Acid Yellow 1 , Yellow 10, Acid Yellow 23, Acid Yellow 36, Acid Orange 7, Acid Red 33, Acid Red 52, Pigment Red 57:1 , Acid Blue 7, Acid Green 50, Acid Violet 43, Acid Black 1 und Acid Black 52 bekannten Verbindungen.Preferred anionic substantive dyes are those under the international designations or trade names Acid Yellow 1, Yellow 10, Acid Yellow 23, Acid Yellow 36, Acid Orange 7, Acid Red 33, Acid Red 52, Pigment Red 57: 1, Acid Blue 7, Acid Green 50, Acid Violet 43, Acid Black 1 and Acid Black 52 known compounds.
Kationische direktziehende Farbstoffe:Cationic direct dyes:
Als kationische direktziehende Farbstoffe eignen sich insbesondere 9-(Dimethylamino)- benzo[a]phenoxazin-7-ium-chlorid (Cl. 51 ,175; Basic Blue 6), Di[4-(diethylamino)phenyl][4- (ethylamino)naphthyl]carbenium-chlorid (Cl. 42,595; Basic Blue 7), Di-(4-(dimethylamino)phenyl)- (4-(methyl-phenylamino)-naphthalin-1-yl)carbenium-chlorid (Cl. 42,563; Basic Blue 8), 3,7- Di(dimethylamino)phenothiazin-5-ium-chlorid (Cl. 52,015 Basic Blue 9), Di[4- (dimethylamino)phenyl][4-(phenylamino)naphthyl] carbenium-chlorid (Cl. 44,045; Basic Blue 26), 2-[(4-(Ethyl(2-hydroxyethyl)amino)phenyl)azo]-6-methoxy-3-methyl-benzothiazolium-methylsulfat (Cl. 11 ,154; Basic Blue 41 ), 8-Amino-2-brom-5-hydroxy-4-imino-6-[(3-Particularly suitable cationic direct dyes are 9- (dimethylamino) benzo [a] phenoxazine-7-ium chloride (Cl 51, 175, Basic Blue 6), di [4- (diethylamino) phenyl] [4- (ethylamino ) naphthyl] carbenium chloride (Cl 42,595, Basic Blue 7), di- (4- (dimethylamino) phenyl) - (4- (methylphenylamino) naphthalen-1-yl) carbenium chloride (CI 42,563; Basic Blue 8), 3,7-di (dimethylamino) -phenothiazine-5-ium chloride (CI 52.015 Basic Blue 9), di [4- (dimethylamino) phenyl] [4- (phenylamino) naphthyl] carbenium chloride ( Cl.44,045; Basic Blue 26), 2 - [(4- (ethyl (2-hydroxyethyl) amino) phenyl) azo] -6-methoxy-3-methylbenzothiazolium methylsulfate (Cl.11, 154, Basic Blue 41 ), 8-amino-2-bromo-5-hydroxy-4-imino-6 - [(3
(trimethylammonio)phenyl)amino]-1(4H)-naphthalinon-chlorid (Cl. 56,059; Basic Blue No. 99), Bis[4- (dimethylamino)phenyl]-[4-(methylamino)phenyl]carbenium-chlorid (Cl. 42,535; Basic Violet 1 ), Tri(4-amino-3-methylphenyl)carbenium-chlorid (Cl. 42,520; Basic Violet 2), Tri[4- (dimethylamino)-phenyl]carbenium-chlorid (Cl. 42,555; Basic Violet 3), 2-[3,6- (Diethylamino)dibenzopyranium-9-yl]- benzoesäurechlorid (Cl. 45,170; Basic Violet 10), Di(4- aminophenyl)(4-amino-3- methylphenyl)carbeniumchlorid (Cl. 42,510 Basic Violet 14), 1 ,3- Bis[(2,4-diamino-5-methylphenyl)azo]-3-methylbenzol (Cl. 21 ,010; Basic Brown 4), 1-[(4- Aminophenyl)azo]-7-(trimethylammonio)- 2-naphthol-chlorid (Cl. 12,250; Basic Brown 16), 1-[(4- Amino-2-nitrophenyl)azo]-7-(trimethylammonio)-2-naphtholchlorid, 1-[(4-Amino-3- nitrophenyl)azo]-7-(trimethylammonio)-2-naphthol-chlorid (Cl. 12,251 ; Basic Brown 17), 3-[(4- Amino-2,5- dimethoxyphenyl)azo]-N,N,N-trimethylbenzolaminiumchlorid (Cl. 12,605, Basic Orange 69), 3,7-Diamino-2,8-dimethyl- 5-phenylphenazinium-chlorid (Cl. 50,240; Basic Red 2), 1 ,4-Dimethyl-5-[(4-(dimethylamino)phenyl)azo]-1 ,2,4-triazolium-chlorid (Cl. 11 ,055; Basic Red 22), 2-Hydroxy-1-[(2-methoxyphenyl)azo]-7-(trimethylammonio)-naphthalin-chlorid (Cl. 12,245; Basic Red 76), Di[4-(dimethylamino)phenyl]iminomethan-hydrochlorid (Cl. 41 ,000; Basic Yellow 2), 2-[2-((2,4- Dimethoxyphenyl)amino)ethenyl]-1 ,3,3-trimethyl-3H-indol-1-ium-chlorid (Cl. 48,055; Basic Yellow 11 ), 3-Methyl-1-phenyl-4-[(3-(trimethylammonio)phenyl)azo]-pyrazol-5-on-chlorid (Cl. 12,719; Basic Yellow 57), Bis[4-(diethylamino)phenyl]phenylcarbenium-hydrogensulfat (1 :1 ) (Cl. 42,040; Basic Green 1 ), Di(4- (dimethylamino)phenyl)-phenylmethanol (Cl. 42,000; Basic Green 4), 1-(2- Morpholiniumpropylamino)-4-hydroxy-9,10-anthrachinon-methylsulfat, 1-[(3- (Dimethyl-propylaminium)-propyl)amino]-4-(methylamino)-9,10-anthrachinon-chlorid und direktziehende Farbstoffe, die einen Heterocyclus enthalten, der mindestens ein quaternäres Stickstoffatom aufweist.(trimethylammonio) phenyl) amino] -1 (4H) -naphthalenone chloride (Cl 56.059, Basic Blue No. 99), bis [4- (dimethylamino) phenyl] - [4- (methylamino) phenyl] carbenium chloride ( Cl. 42,535; Basic Violet 1), tri (4-amino-3-methylphenyl) carbenium chloride (Cl 42,520, Basic Violet 2), tri [4- (dimethylamino) -phenyl] carbenium chloride (Cl 42,555; Basic Violet 3), 2- [3,6- (diethylamino) dibenzopyranium-9-yl] benzoic acid chloride (Cl.45, 170; Basic Violet 10), di (4-aminophenyl) (4-amino-3-methylphenyl) carbenium chloride ( Cl., 42, 510 Basic Violet 14), 1, 3-bis [(2,4-diamino-5-methylphenyl) azo] -3-methylbenzene (CI 21, 010, Basic Brown 4), 1 - [(4-aminophenyl ) azo] -7- (trimethylammonio) -2-naphthol chloride (Cl 12,250, Basic Brown 16), 1 - [(4-amino-2-nitrophenyl) azo] -7- (trimethylammonio) -2-naphthol chloride, 1 - [(4-Amino-3-nitrophenyl) azo] -7- (trimethylammonio) -2-naphthol chloride (CI 12,251, Basic Brown 17), 3 - [(4-amino-2,5-dimethoxyphenyl) azo] -N, N, N-trimethylbenzylaminium chloride (Cl 12.605, Basic Orange 69), 3.7 Diamino-2,8-dimethyl-5-phenylphenazinium chloride (Cl. 50.240; Basic Red 2), 1, 4-dimethyl-5 - [(4- (dimethylamino) phenyl) azo] -1,2,4-triazolium chloride (Cl 11, 055, Basic Red 22), 2-hydroxy- 1 - [(2-methoxyphenyl) azo] -7- (trimethylammonio) -naphthalene chloride (Cl 12,245, Basic Red 76), di [4- (dimethylamino) phenyl] iminomethane hydrochloride (CI 41, 000, Basic Yellow 2), 2- [2 - ((2,4-dimethoxyphenyl) amino) ethenyl] -1,3,3-trimethyl-3H-indol-1-ium chloride (Cl 48,055, Basic Yellow 11), 3 -Methyl-1-phenyl-4 - [(3- (trimethylammonio) phenyl) azo] pyrazol-5-one chloride (Cl 12.719; Basic Yellow 57), bis [4- (diethylamino) phenyl] phenylcarbenium hydrogensulfate (1: 1) (CI 42.040, Basic Green 1), di (4- (dimethylamino) phenyl) -phenylmethanol (CI 42,000, Basic Green 4), 1- (2-morpholiniumpropylamino) -4-hydroxy-9, 10-anthraquinone methylsulfate, 1 - [(3- (dimethylpropylaminium) -propyl) amino] -4- (methylamino) -9,10-anthraquinone chloride and substantive dyes containing a heterocycle having at least one quaternary nitrogen atom.
Bevorzugte kationische direktziehende Farbstoffe sind dabeiPreferred cationic substantive dyes are included
(a) kationische Triphenylmethanfarbstoffe, wie beispielsweise Basic Blue 7, Basic Blue 26, Basic Violet 2 und Basic Violet 14,(a) cationic triphenylmethane dyes such as Basic Blue 7, Basic Blue 26, Basic Violet 2 and Basic Violet 14,
(b) aromatischen Systeme, die mit einer quaternären Stickstoffgruppe substituiert sind, wie beispielsweise Basic Yellow 57, Basic Red 76, Basic Blue 99, Basic Brown 16 und Basic Brown 17, sowie(b) aromatic systems substituted with a quaternary nitrogen group, such as Basic Yellow 57, Basic Red 76, Basic Blue 99, Basic Brown 16 and Basic Brown 17, as well as
(c) direktziehende Farbstoffe, die einen Heterocyclus enthalten, der mindestens ein quaternäres Stickstoffatom aufweist, wie sie beispielsweise in der EP-A2-998 908, auf die an dieser Stelle explizit Bezug genommen wird, in den Ansprüchen 6 bis 1 1 genannt werden.(C) substantive dyes containing a heterocycle having at least one quaternary nitrogen atom, as mentioned for example in EP-A2-998 908, to which reference is explicitly made at this point in claims 6 to 1 1 are called.
Bevorzugte kationische direktziehende Farbstoffe der Gruppe (c) sind insbesondere die folgenden Verbindungen:Preferred cationic substantive dyes of group (c) are in particular the following compounds:
Figure imgf000044_0001
Figure imgf000044_0001
CH3SO4 " CH 3 SO 4 "
Figure imgf000044_0002
Figure imgf000044_0002
Cl" Cl "
(DZ3)
Figure imgf000044_0003
Figure imgf000045_0001
Die Verbindungen der Formeln (DZ1 ), (DZ3) und (DZ5), die auch unter den Bezeichnungen Basic Yellow 87, Basic Orange 31 und Basic Red 51 bekannt sind, sind ganz besonders bevorzugte kationische direktziehende Farbstoffe der Gruppe (c).(DZ3)
Figure imgf000044_0003
Figure imgf000045_0001
The compounds of the formulas (DZ1), (DZ3) and (DZ5), which are also known by the names Basic Yellow 87, Basic Orange 31 and Basic Red 51, are very particularly preferred cationic substantive dyes of group (c).
Die kationischen direktziehenden Farbstoffe, die unter dem Warenzeichen Arianor® vertrieben werden, sind erfindungsgemäß ebenfalls ganz besonders bevorzugte kationische direktziehende Farbstoffe.The cationic direct dyes, which are sold under the trademark Arianor ®, according to the invention are also very particularly preferred cationic direct dyes.
Nichtionische direktziehende Farbstoffe:Nonionic substantive dyes:
Als nichtionische direktziehende Farbstoffe eignen sich insbesondere nichtionische Nitro- undAs nonionic substantive dyes are in particular nonionic nitro and
Chinonfarbstoffe und neutrale Azofarbstoffe.Quinone dyes and neutral azo dyes.
Geeignete blaue Nitrofarbstoffe sind insbesondere:Suitable blue nitro dyes are in particular:
1 ,4-Bis[(2-hydroxyethyl)amino]-2-nitrobenzol, 1-(2-Hydroxyethyl)amino-2-nitro-4-[di(2- hydroxyethyl)amino]-benzol (HC Blue 2), 1-Methylamino-4- [methyl-(2,3-dihydroxypropyl)amino]- 2-nitrobenzol (HC Blue 6),1-[(2,3- Dihydroxypropyl)-amino]-4-[ethyl-(2-hydroxyethyl)amino]-2- nitrobenzol-hydrochlorid (HC Blue 9), 1-[(2,3-Dihydroxypropyl)amino]-4-[methyl-(2- hydroxyethyl)amino]-2-nitrobenzol (HC Blue 10), 4-[Di(2-hydroxyethyl)amino]-1-[(2- methoxyethyl)amino]-2-nitrobenzol (HC Blue 11 ), 4-[Ethyl-(2-hydroxyethyl)-amino]-1-[(2- hydroxyethyl)amino]-2-nitrobenzol-hydrochlorid (HC Blue 12), 2-((4-Amino-2-nitrophenyl)amino)- 5-dimethylamino-benzoesäure (HC Blue 13), 1-Amino-3-methyl-4-[(2-hydroxyethyl)amino]-6- nitrobenzol (HC Violet 1 ), 1-(3-Hydroxypropylamino)-4-[di(2-hydroxyethyl)amino]-2-nitrobenzol (HC Violet 2), 1-(2-Aminoethylamino)-4-[di(2-hydroxyethyl)amino]-2-nitrobenzol, 4-(Di(2- hydroxyethyl)amino)-2-nitro-1-phenylamino-benzol.1,4-bis [(2-hydroxyethyl) amino] -2-nitrobenzene, 1- (2-hydroxyethyl) amino-2-nitro-4- [di (2-hydroxyethyl) amino] benzene (HC Blue 2), 1-Methylamino-4- [methyl- (2,3-dihydroxypropyl) amino] -2-nitrobenzene (HC Blue 6), 1 - [(2,3-dihydroxypropyl) amino] -4- [ethyl- (2- hydroxyethyl) amino] -2-nitrobenzene hydrochloride (HC Blue 9), 1 - [(2,3-dihydroxypropyl) amino] -4- [methyl (2-hydroxyethyl) amino] -2-nitrobenzene (HC Blue 10) , 4- [di (2-hydroxyethyl) amino] -1 - [(2-methoxyethyl) amino] -2-nitrobenzene (HC Blue 11), 4- [ethyl- (2-hydroxyethyl) amino] -1- [ (2-hydroxyethyl) amino] -2-nitrobenzene hydrochloride (HC Blue 12), 2 - ((4-amino-2-nitrophenyl) amino) -5-dimethylaminobenzoic acid (HC Blue 13), 1-amino-3 Methyl 4 - [(2-hydroxyethyl) amino] -6-nitrobenzene (HC Violet 1), 1- (3-hydroxypropylamino) -4- [di (2-hydroxyethyl) amino] -2-nitrobenzene (HC Violet 2 ), 1- (2-aminoethylamino) -4- [di (2-hydroxyethyl) amino] -2-nitrobenzene, 4- (di (2-hydroxyethyl) amino) -2-nitro-1-phenylaminobenzene.
Geeignete rote Nitrofarbstoffe sind insbesondere:Suitable red nitro dyes are in particular:
1-Amino-4-[(2-hydroxyethyl)amino]-2-nitrobenzol (HC Red 7), 2-Amino-4,6-dinitrophenol (Pikraminsäure) und deren Salze, 1 ,4-Diamino-2-nitrobenzol (Cl. 76,070), 4-Amino-2-nitro- diphenylamin (HC Red 1 ), 1-Amino-4-[di(2-hydroxyethyl)amino]-2-nitrobenzol-hydrochlorid (HC Red 13), 1-Amino-4-[(2-hydroxyethyl)-amino]-5-chlor-2-nitrobenzol, 4-Amino-1-[(2- hydroxyethyl)amino]-2-nitrobenzol (HC Red 3), 4-[(2-Hydroxyethyl)methylamino]-1-(methylamino)- 2-nitrobenzol, 1-Amino-4-[(2,3-dihydroxypropyl)amino]-5-methyl-2-nitrobenzol, 1-Amino-4- (methylamino)-2-nitrobenzol, 4-Amino-2-nitro-1-[(prop-2-en-1-yl)-amino]-benzol, 4-Amino-3- nitrophenol, 4-[(2-Hydroxyethyl)-amino]-3-nitrophenol, 4-[(2-Nitrophenyl)amino]phenol (HC Orange 1 ), 1-[(2-Aminoethyl)amino]-4-(2-hydroxyethoxy)-2-nitrobenzol (HC Orange 2), 4-(2,3- Dihydroxypropoxy)-1-[(2-hydroxyethyl)amino]-2-nitrobenzol (HC Orange 3), 1-Amino-5-chlor-4- [(2,3-dihydroxypropyl)amino]-2-nitrobenzol (HC Red 10), 5-Chlor-1 ,4-[di(2,3- dihydroxypropyl)amino]-2-nitrobenzol (HC Red 11 ), 2-[(2- Hydroxyethyl)amino]-4,6-dinitrophenol, 4-Ethylamino-3-nitrobenzoesäure, 2-[(4-Amino-2-nitrophenyl)amino]-benzoesäure, 2-Chlor-6- ethylamino-4-nitrophenol, 2-Amino-6-chlor-4-nitrophenol, 4-[(3-Hydroxypropyl)amino]-3- nitrophenol (HC Red BN), 2,5-Diamino-6-nitropyridin, 6-Amino-3-[(2-hydroxyethyl)amino]-2- nitropyridin, 3-Amino-6-[(2-hydroxyethyl)amino]-2-nitropyridin, 3-Amino-6-(ethylamino)-2- nitropyridin, 3-[(2-Hydroxyethyl)amino]-6-(methylamino)-2-nitropyridin, 3- Amino-6-(methylamino)- 2-nitropyridin, 6-(Ethylamino)-3-[(2-hydroxyethyl)amino]-2-nitropyridin, 1 ,2,3,4-Tetrahydro-6- nitrochinoxalin, 7-Amino-3,4-dihydro-6-nitro-2H-1 ,4-benzoxazin (HC Red 14).1-Amino-4 - [(2-hydroxyethyl) amino] -2-nitrobenzene (HC Red 7), 2-amino-4,6-dinitrophenol (picramic acid) and its salts, 1, 4-diamino-2-nitrobenzene ( Cl., 76,070), 4-amino-2-nitro-diphenylamine (HC Red 1), 1-amino-4- [di (2-hydroxyethyl) amino] -2-nitrobenzene hydrochloride (HC Red 13), 1-amino 4 - [(2-hydroxyethyl) amino] -5-chloro-2-nitrobenzene, 4-amino-1 - [(2-hydroxyethyl) amino] -2-nitrobenzene (HC Red 3), 4 - [(2 -Hydroxyethyl) methylamino] -1- (methylamino) -2-nitrobenzene, 1-amino-4 - [(2,3-dihydroxypropyl) amino] -5-methyl-2-nitrobenzene, 1-amino-4- (methylamino) 2-nitrobenzene, 4-amino-2-nitro-1 - [(prop-2-en-1-yl) amino] benzene, 4-amino-3-nitrophenol, 4 - [(2-hydroxyethyl) - amino] -3-nitrophenol, 4 - [(2-nitrophenyl) amino] phenol (HC Orange 1), 1 - [(2-aminoethyl) amino] -4- (2-hydroxyethoxy) -2-nitrobenzene (HC Orange 2 ), 4- (2,3-dihydroxypropoxy) -1 - [(2-hydroxyethyl) amino] -2-nitrobenzene (HC Orange 3), 1-amino-5-chloro-4- [(2,3-dihydroxypropyl) amino] -2-nitrobenzene (HC Red 10), 5-chloro-1, 4- [di (2,3-dihydroxypropyl) ami no] -2-nitrobenzene (HC Red 11), 2 - [(2-hydroxyethyl) amino] -4,6-dinitrophenol, 4-ethylamino-3-nitrobenzoic acid, 2 - [(4-amino-2-nitrophenyl) amino ] benzoic acid, 2-chloro-6-ethylamino-4-nitrophenol, 2-amino-6-chloro-4-nitrophenol, 4 - [(3-hydroxypropyl) amino] -3-nitrophenol (HC Red BN), 2, 5-diamino-6-nitropyridine, 6-amino-3 - [(2-hydroxyethyl) amino] -2- nitropyridine, 3-amino-6 - [(2-hydroxyethyl) amino] -2-nitropyridine, 3-amino-6- (ethylamino) -2-nitropyridine, 3 - [(2-hydroxyethyl) amino] -6- (methylamino ) -2-nitropyridine, 3-amino-6- (methylamino) -2-nitropyridine, 6- (ethylamino) -3 - [(2-hydroxyethyl) amino] -2-nitropyridine, 1,2,3,4-tetrahydro 6-nitroquinoxaline, 7-amino-3,4-dihydro-6-nitro-2H-1,4-benzoxazine (HC Red 14).
Geeignete gelbe Nitrofarbstoffe sind insbesondere:Suitable yellow nitro dyes are in particular:
1 ,2-Diamino-4-nitrobenzol (Cl. 76,020), 1-[(2-Hydroxyethyl)amino]-2-nitrobenzol (HC Yellow 2), 1-(2-Hydroxyethoxy)-2-[(2-hydroxyethyl)amino]-5-nitrobenzol (HC Yellow 4), 1-Amino-2-[(2- hydroxyethyl)amino]-5-nitrobenzol (HC Yellow 5), 4-[(2,3-Dihydroxypropyl)-amino]-3-nitro-1- trifluormethyl-benzol (HC Yellow 6), 2-[Di(2-hydroxyethyl)amino]-5-nitrophenol, 2-[(2- Hydroxyethyl)amino]-1-methoxy-5-nitrobenzol, 2-Amino-3-nitrophenol, 2-Amino-4-nitrophenol, 1- Amino-2-methyl-6-nitrobenzol, 1-(2-Hydroxyethoxy)-3-methylamino-4-nitrobenzol, 2,3-(Dihydroxy- propoxy)-3-methylamino-4-nitrobenzol, 3-[(2-Aminoethyl)amino]-1-methoxy-4-nitrobenzol- hydrochlorid (HC Yellow 9), 1-Chlor-2,4-bis[(2-hydroxyethyl)amino]-5-nitrobenzol (HC Yellow 10), 2-[(2-Hydroxyethyl)amino]-5-nitrophenol (HC Yellow 11 ), 1-[(2'-Ureidoethyl)amino]-4-nitrobenzol, 1-Amino-4-[(2-aminoethyl)amino]-5-methyl-2-nitrobenzol, 4-[(2-Hydroxyethyl)amino]-3-nitro-1- methylbenzol, 1-Chlor-4-[(2-hydroxyethyl)amino]-3-nitrobenzol (HC Yellow 12), 4-[(2- Hydroxyethyl)amino]-3-nitro-1-trifluormethyl-benzol (HC Yellow 13), 4-[(2-Hydroxyethyl)-amino]-3- nitro-benzonitril (HC Yellow 14), 4-[(2-Hydroxyethyl)amino]-3-nitro-benzamid (HC Yellow 15) 3- [(2-Hydroxyethyl)amino]-4-methyl-1-nitrobenzol, 4-Chlor-3-[(2-hydroxyethyl)amino]-1-nitrobenzol.1,2-diamino-4-nitrobenzene (CI 76,020), 1 - [(2-hydroxyethyl) amino] -2-nitrobenzene (HC Yellow 2), 1- (2-hydroxyethoxy) -2 - [(2-hydroxyethyl ) amino] -5-nitrobenzene (HC Yellow 4), 1-amino-2 - [(2-hydroxyethyl) amino] -5-nitrobenzene (HC Yellow 5), 4 - [(2,3-dihydroxypropyl) amino] 3-nitro-1-trifluoromethylbenzene (HC Yellow 6), 2- [di (2-hydroxyethyl) amino] -5-nitrophenol, 2 - [(2-hydroxyethyl) amino] -1-methoxy-5-nitrobenzene , 2-amino-3-nitrophenol, 2-amino-4-nitrophenol, 1-amino-2-methyl-6-nitrobenzene, 1- (2-hydroxyethoxy) -3-methylamino-4-nitrobenzene, 2,3- ( Dihydroxypropoxy) -3-methylamino-4-nitrobenzene, 3 - [(2-aminoethyl) amino] -1-methoxy-4-nitrobenzene hydrochloride (HC Yellow 9), 1-chloro-2,4-bis [( 2-hydroxyethyl) amino] -5-nitrobenzene (HC Yellow 10), 2 - [(2-hydroxyethyl) amino] -5-nitrophenol (HC Yellow 11), 1 - [(2'-ureidoethyl) amino] -4- nitrobenzene, 1-amino-4 - [(2-aminoethyl) amino] -5-methyl-2-nitrobenzene, 4 - [(2-hydroxyethyl) amino] -3-nitro-1-methylbenzene, 1-chloro-4- [(2-hydroxyethyl) amino] -3-nitrobenzene (HC Yello w 12), 4 - [(2-hydroxyethyl) amino] -3-nitro-1-trifluoromethylbenzene (HC Yellow 13), 4 - [(2-hydroxyethyl) amino] -3-nitrobenzonitrile (HC Yellow 14), 4 - [(2-hydroxyethyl) amino] -3-nitrobenzamide (HC Yellow 15) 3- [(2-hydroxyethyl) amino] -4-methyl-1-nitrobenzene, 4-chloro-3- [ (2-hydroxyethyl) amino] -1-nitrobenzene.
Geeignete Chinonfarbstoffe sind insbesondere:Suitable quinone dyes are in particular:
1 ,4-Di[(2,3-dihydroxypropyl)amino]-9, 10-anthrachinon, 1 ,4-Di[(2-hydroxyethyl)amino]-9, 10- anthrachinon (Cl. 61 ,545, Disperse Blue 23), 1-[(2-Hydroxyethyl)amino]-4-methylamino-9,10- anthrachinon (Cl. 61 ,505, Disperse Blue 3), 2-[(2-Aminoethyl)amino]-9,10-anthrachinon (HC Orange 5), 1-Amino-4-hydroxy-9,10-anthrachinon (Cl. 60,710, Disperse Red 15), 1-Hydroxy-4- [(4-methyl-2-sulfophenyl)amino]-9,10-anthrachinon, 1-[(3-Aminopropyl)amino]-4-methylamino- 9,10-anthrachinon (HC Blue 8), 1-[(3-Aminopropyl)-amino]-9,10- anthrachinon (HC Red 8), 1 ,4- Diamino-2-methoxy-9,10-anthrachinon (Cl. 62,015, Disperse Red 11 , Solvent Violet No. 26), 1 ,4- Dihydroxy-5,8-bis[(2-hydroxyethyl)amino]-9,10-anthrachinon (Cl. 62,500, Disperse Blue 7, Solvent Blue No. 69), 1 ,4-Diamino-9,10-anthrachinon (Cl. 61 ,100, Disperse Violet 1 ), 1-Amino-4- (methylamino)-9,10-anthrachinon (Cl. 61 ,105, Disperse Violet 4, Solvent Violet No. 12), N-{6-[(3- Chlor-4-(methylamino)phenyl)imino]-4-methyl-3-oxo-1 ,4-cyclohexadien-1-yl}harnstoff (HC Red 9), 2-{{4-[Di(2-hydroxyethyl)amino]phenyl}amino}-5-[(2-hydroxyethyl)amino]-2,5-cyclohexadien-1 ,4- dion (HC Green 1 ), 1 ,2-Dihydro-2-(1 ,3-dihydro-3-oxo-2H-indol-2-yliden)-3H-indol-3-on (Cl. 73,000), 4-{{5-[(2-Hydroxyethyl) amino]-1-methyl-1 H- pyrazol-4-yl}imino}-4,5-dihydro-5-[(2- hydroxyethyl)-imino]-1-methyl-1 H-Pyrazol-sulfat(1 :1 ), Hydrat(1 :1 ).1,4-Di [(2,3-dihydroxypropyl) amino] -9,10-anthraquinone, 1,4-di [(2-hydroxyethyl) amino] -9,10-anthraquinone (CI 61,554, Disperse Blue 23), 1 - [(2-hydroxyethyl) amino] -4-methylamino-9,10-anthraquinone (CI 61, 505, Disperse Blue 3), 2 - [(2-aminoethyl) amino] -9,10- anthraquinone (HC Orange 5), 1-amino-4-hydroxy-9,10-anthraquinone (CI 60,710, Disperse Red 15), 1-hydroxy-4- [(4-methyl-2-sulfophenyl) amino] -9 , 10-anthraquinone, 1 - [(3-aminopropyl) amino] -4-methylamino-9,10-anthraquinone (HC Blue 8), 1 - [(3-aminopropyl) amino] -9,10-anthraquinone (HC Red 8), 1, 4-diamino-2-methoxy-9,10-anthraquinone (CI 62.015, Disperse Red 11, Solvent Violet No. 26), 1, 4-dihydroxy-5,8-bis [(2- hydroxyethyl) amino] -9,10-anthraquinone (CI 62,500, Disperse Blue 7, Solvent Blue No. 69), 1,4-diamino-9,10-anthraquinone (CI 61, 100, Disperse Violet 1), 1 -Amino-4- (methylamino) -9,10-anthraquinone (CI 61, 105, Disperse Violet 4, Solvent Violet No. 12), N- {6 - [(3-chloro-4- (methylamino) phenyl) imino] -4-methyl-3-oxo-1,4-cyclohex adien-1-yl} urea (HC Red 9), 2 - {{4- [di (2-hydroxyethyl) amino] phenyl} amino} -5 - [(2-hydroxyethyl) amino] -2,5-cyclohexadiene 1, 4-dione (HC Green 1), 1, 2-dihydro-2- (1,3-dihydro-3-oxo-2H-indol-2-ylidene) -3H-indol-3-one (Cl. 73,000), 4 - {{5 - [(2-hydroxyethyl) amino] -1-methyl-1H-pyrazol-4-yl} imino} -4,5-dihydro-5 - [(2-hydroxyethyl) -imino ] -1-methyl-1H-pyrazole sulfate (1: 1), hydrate (1: 1).
Geeignete neutrale Azofarbstoffe sind insbesondere:Suitable neutral azo dyes are in particular:
1-[Di(2-hydroxyethyl)amino]-3-methyl-4-[(4-nitrophenyl)azo]-benzol (Cl. 11 ,210, Disperse Red 17), 1-[Di(2-hydroxyethyl)amino]-4-[(4-nitrophenyl)azo]-benzol (Disperse Black 9), 4-[(4- Aminophenyl)azo]-1-[di(2-hydroxyethyl)amino]-3-methylbenzol (HC Yellow 7), 2,6-Diamino-3- [(pyridin-3-yl)azo]-pyridin, 2-{[4-(Acetylamino)phenyl]azo}-4-methylphenol (Cl. 11855; Disperse Yellow 3), 4-[(4-Nitrophenyl)azo]-anilin (Cl. 11 ,005; Disperse Orange 3).1- [di (2-hydroxyethyl) amino] -3-methyl-4 - [(4-nitrophenyl) azo] benzene (Cl. 11, 210, Disperse Red 17), 1- [di (2-hydroxyethyl) amino ] -4 - [(4-nitrophenyl) azo] benzene (Disperse Black 9), 4 - [(4- Aminophenyl) azo] -1- [di (2-hydroxyethyl) amino] -3-methylbenzene (HC Yellow 7), 2,6-diamino-3- [(pyridin-3-yl) azo] pyridine, 2- { [4- (acetylamino) phenyl] azo] -4-methylphenol (CI 11855, Disperse Yellow 3), 4 - [(4-nitrophenyl) azo] -aniline (CI 11, 005, Disperse Orange 3).
Bevorzugte nichtionische direktziehende Farbstoffe sind die unter den internationalen Bezeichnungen bzw. Handelsnamen HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, HC Orange 1 , Disperse Orange 3, HC Red 1 , HC Red 3, HC Red 10, HC Red 11 , HC Red 13, HC Red BN, HC Blue 2, HC Blue 11 , HC Blue 12, Disperse Blue 3, HC Violet 1 , Disperse Violet 1 , Disperse Violet 4, Disperse Black 9 bekannten Verbindungen, sowie 1 ,4-Diamino-2-nitrobenzol, 2-Amino-4-nitrophenol, 1 ,4-Bis-(2-hydroxyethyl)-amino-2-nitrobenzol, 3-Nitro-4-(2-hydroxyethyl)- aminophenol, 2-(2-Hydroxyethyl)amino-4,6-dinitrophenol, 4-[(2-Hydroxyethyl)amino]-3-nitro-1- methylbenzol, 1-Amino-4-(2-hydroxyethyl)-amino-5-chlor-2-nitrobenzol, 4-Amino-3-nitrophenol, 1- (2'-Ureidoethyl)amino-4-nitrobenzol, 2-[(4-Amino-2-nitrophenyl)amino]-benzoesäure, 6-Nitro- 1 ,2,3,4-tetrahydrochinoxalin, 2-Hydroxy-1 ,4-naphthochinon, Pikraminsäure und deren Salze, 2- Amino-6-chloro-4-nitrophenol, 4-Ethylamino-3-nitrobenzoesäure und 2-Chlor-6-ethylamino-4- nitrophenol.Preferred nonionic substantive dyes are those under the international designations or trade names HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, HC Orange 1, Disperse Orange 3, HC Red 1, HC Red 3, HC HC Red 11, HC Red 11, HC Red 11, HC Red 11, HC Blue 2, HC Blue 11, HC Blue 12, Disperse Blue 3, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Disperse Black 9 well-known compounds, as well 1, 4-diamino-2-nitrobenzene, 2-amino-4-nitrophenol, 1,4-bis (2-hydroxyethyl) amino-2-nitrobenzene, 3-nitro-4- (2-hydroxyethyl) aminophenol, 2- (2-hydroxyethyl) amino-4,6-dinitrophenol, 4 - [(2-hydroxyethyl) amino] -3-nitro-1-methylbenzene, 1-amino-4- (2-hydroxyethyl) amino-5- chloro-2-nitrobenzene, 4-amino-3-nitrophenol, 1- (2'-ureidoethyl) amino-4-nitrobenzene, 2 - [(4-amino-2-nitrophenyl) amino] benzoic acid, 6-nitro-1 , 2,3,4-tetrahydroquinoxaline, 2-hydroxy-1,4-naphthoquinone, picramic acid and its salts, 2-amino-6-chloro-4-nitrophenol, 4-ethylamino-3-nitrobenzoic acid and 2-chloro-6-ethylamino-4-nitrophenol.
Es ist nicht erforderlich, dass die direktziehenden Farbstoffe jeweils einheitliche Verbindungen darstellen. Vielmehr können, bedingt durch die Herstellungsverfahren für die einzelnen Farbstoffe, in untergeordneten Mengen noch weitere Komponenten enthalten sein, soweit diese nicht das Färbeergebnis nachteilig beeinflussen oder aus anderen Gründen, z.B. toxikologischen, ausgeschlossen werden müssen.It is not necessary that the substantive dyes each represent uniform compounds. Rather, due to the production process for the individual dyes, minor amounts of other components may be included, as far as these do not adversely affect the dyeing result or for other reasons, e.g. toxicological, must be excluded.
Die erfindungsgemäße Lehre lässt sich in Gegenwart mindestens eines zusätzlichen Oxidationsmittels durchführen, wenngleich es erfindungsgemäß bevorzugt ist, dass die erfindungsgemäßen Mittel frei von zusätzlichen Oxidationsmitteln sind.The teaching according to the invention can be carried out in the presence of at least one additional oxidizing agent, although it is preferred according to the invention that the agents according to the invention are free of additional oxidizing agents.
Im Sinne der Erfindung sind die zusätzlichen Oxidationsmittel von Luftsauerstoff verschieden und besitzen ein solches Oxidationspotenzial, das es ermöglicht, Disulfidbrücken innerhalb oder zwischen den Proteinen des Haarkeratins zu knüpfen und/oder das natürliche Farbpigment Melanin oxidativ aufzuhellen und/oder ein Oxidationsfarbstoffvorprodukt vom Entwicklertyp zu oxidieren.For the purposes of the invention, the additional oxidizing agents are different from atmospheric oxygen and have such an oxidation potential which makes it possible to bond disulfide bridges within or between the proteins of the hair keratin and / or oxidatively lighten the natural color pigment melanin and / or to oxidize a developer-type oxidation dye precursor.
Solche Oxidationsmittel sind beispielsweise Wasserstoffperoxid und seine Anlagerungsprodukte, organische Percarbonsäuren oder organische Peroxide.Such oxidizing agents are, for example, hydrogen peroxide and its addition products, organic percarboxylic acids or organic peroxides.
Als organische Percarbonsäuren eignen sich erfindungsgemäß besonders Monoperphthalsäure, Peressigsäure oder 6-(Phthalimidoperoxy)hexansäure (CAS-Nr.: 128275-31-0).Suitable organic percarboxylic acids according to the invention are in particular monoperphthalic acid, peracetic acid or 6- (phthalimidoperoxy) hexanoic acid (CAS No .: 128275-31-0).
Als Oxidationsmittel kommt bevorzugt Wasserstoffperoxid und/oder mindestens ein Anlagerungsprodukt davon, insbesondere an anorganische oder organische Verbindungen, in Frage. Die geeigneten Anlagerungsprodukte von Wasserstoffperoxid werden wiederum bevorzugt ausgewählt aus mindestens einer Verbindung der Gruppe, bestehend aus Natriumperborat,As the oxidizing agent is preferably hydrogen peroxide and / or at least one addition product thereof, in particular to inorganic or organic compounds in question. The appropriate addition products of hydrogen peroxide are again preferred selected from at least one compound of the group consisting of sodium perborate,
Natriumpercarbonat, Magnesiumpercarbonat, Natriumpercarbamid, Polyvinylpyrrolidon n H2O2 (n ist eine positive ganze Zahl größer 0), Harnstoffperoxid und Melaminperoxid.Sodium percarbonate, magnesium percarbonate, sodium percarbamide, polyvinylpyrrolidone nH 2 O 2 (n is a positive integer greater than 0), urea peroxide and melamine peroxide.
Erfindungsgemäß können die Oxidationsmittel auch zusammen mit einem Katalysator Anwendung finden. Der Katalysator aktiviert die Oxidation des Substrats, wie beispielsweise die Oxidation der Oxidationsfarbstoffvorprodukte oder des Melanins. Solche Katalysatoren sind z.B. Metallionen, lodide, Chinone oder bestimmte Enzyme.According to the invention, the oxidizing agents can also be used together with a catalyst. The catalyst activates the oxidation of the substrate, such as oxidation of the oxidation dye precursors or melanin. Such catalysts are e.g. Metal ions, iodides, quinones or certain enzymes.
Geeignete Metallionen sind beispielsweise Zn2+, Cu2+, Fe2+, Fe3+, Mn2+, Mn4+, Li+, Mg2+, Ca2+ und Al3+. Besonders geeignet sind dabei Zn2+, Cu2+ und Mn2+. Die Metallionen können prinzipiell in der Form eines beliebigen, physiologisch verträglichen Salzes oder in Form einer Komplexverbindung eingesetzt werden. Bevorzugte Salze sind die Acetate, Sulfate, Halogenide, Lactate und Tartrate. Durch Verwendung dieser Metallsalze kann die Oxidation beschleunigt als auch im Rahmen einer oxidativen Färbung die Farbnuance gezielt beeinflusst werden.Suitable metal ions are, for example, Zn 2+ , Cu 2+ , Fe 2+ , Fe 3+ , Mn 2+ , Mn 4+ , Li + , Mg 2+ , Ca 2+ and Al 3+ . Particularly suitable are Zn 2+ , Cu 2+ and Mn 2+ . The metal ions can in principle be used in the form of any physiologically acceptable salt or in the form of a complex compound. Preferred salts are the acetates, sulfates, halides, lactates and tartrates. By using these metal salts, the oxidation can be accelerated as well as the color shade can be specifically influenced in the context of an oxidative dyeing.
Geeignete Enzyme sind z.B. Peroxidasen, die die Wirkung geringer Mengen an Wasserstoffperoxid deutlich verstärken können. Weiterhin sind solche Enzyme erfindungsgemäß geeignet, die mit Hilfe von Luftsauerstoff in situ geringe Mengen Wasserstoffperoxid erzeugen und auf diese Weise die Oxidation der Farbstoffvorprodukte biokatalytisch aktivieren. Besonders geeignete Katalysatoren für die Oxidation von Farbstoffvorprodukten sind die sogenannten 2- Elektronen-Oxidoreduktasen in Kombination mit den dafür spezifischen Substraten, z.B.Suitable enzymes are e.g. Peroxidases that can significantly increase the effect of small amounts of hydrogen peroxide. Furthermore, such enzymes are suitable according to the invention, which generate with the aid of atmospheric oxygen in situ small amounts of hydrogen peroxide and biocatalytically activate the oxidation of the dye precursors in this way. Particularly suitable catalysts for the oxidation of dye precursors are the so-called 2-electron oxidoreductases in combination with the specific substrates, e.g.
Pyranose-Oxidase und z.B. D-Glucose oder Galactose,Pyranose oxidase and e.g. D-glucose or galactose,
Glucose-Oxidase und D-Glucose,Glucose oxidase and D-glucose,
Glycerin-Oxidase und Glycerin,Glycerol oxidase and glycerin,
Pyruvat-Oxidase und Benztraubensäure oder deren Salze, - Alkohol-Oxidase und Alkohol (MeOH, EtOH),Pyruvate oxidase and pyruvic acid or its salts, - alcohol oxidase and alcohol (MeOH, EtOH),
Lactat-Oxidase und Milchsäure und deren Salze,Lactate oxidase and lactic acid and their salts,
Tyrosinase-Oxidase und Tyrosin,Tyrosinase oxidase and tyrosine,
Uricase und Harnsäure oder deren Salze,Uricase and uric acid or their salts,
Cholinoxidase und Cholin,Choline oxidase and choline,
Aminosäure-Oxidase und Aminosäuren.Amino acid oxidase and amino acids.
Das Oxidationsmittel ist bevorzugt in einer Menge von 1 ,0 bis 10 Gew.-%, insbesondere von 3,0 bis 10,0 Gew.-%, jeweils bezogen auf das Gewicht des anwendungsbereiten Mittels, in einem erfindungsgemäß verwendbaren Mittel enthalten.The oxidizing agent is preferably contained in an amount of from 1.0 to 10% by weight, in particular from 3.0 to 10.0% by weight, in each case based on the weight of the ready-to-use agent, in an agent which can be used according to the invention.
In einer weiteren Ausführungsform können die erfindungsgemäß eingesetzten Mittel mindestens ein Tensid enthalten. Prinzipiell eignen sich sowohl weitere anionische als auch zwitterionische, ampholytische, nichtionische und kationische Tenside. In vielen Fällen hat es sich aber als vorteilhaft erwiesen, die Tenside aus anionischen, zwitterionischen oder nichtionischen Tensiden auszuwählen.In a further embodiment, the agents used according to the invention may contain at least one surfactant. In principle, both further anionic and zwitterionic, ampholytic, nonionic and cationic surfactants are suitable. In many cases, however, it has proved to be proven advantageous to select the surfactants from anionic, zwitterionic or nonionic surfactants.
Als weitere anionische Tenside eignen sich in erfindungsgemäßen Zubereitungen alle für die Verwendung am menschlichen Körper geeigneten anionischen oberflächenaktiven Stoffe. Diese sind gekennzeichnet durch eine wasserlöslichmachende, anionische Gruppe wie z. B. eine Carboxylat-, Sulfat-, Sulfonat- oder Phosphat-Gruppe und eine lipophile Alkylgruppe mit etwa 10 bis 22 C-Atomen. Zusätzlich können im Molekül Glykol- oder Polyglykolether-Gruppen, Ester-, Ether- und Amidgruppen sowie Hydroxylgruppen enthalten sein. Beispiele für geeignete anionische Tenside sind, jeweils in Form der Natrium-, Kalium- und Ammonium- sowie der Mono-, Di- und Trialkanolammoniumsalze mit 2 oder 3 C-Atomen in der Alkanolgruppe, lineare Fettsäuren mit 10 bis 22 C-Atomen (Seifen),Further anionic surfactants suitable in preparations according to the invention are all anionic surfactants suitable for use on the human body. These are characterized by a water-solubilizing, anionic group such. Example, a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group having about 10 to 22 carbon atoms. In addition, glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups may be present in the molecule. Examples of suitable anionic surfactants are, in each case in the form of the sodium, potassium and ammonium and the mono-, di- and Trialkanolammoniumsalze with 2 or 3 C atoms in the alkanol group, linear fatty acids having 10 to 22 carbon atoms (soaps )
Ethercarbonsäuren der Formel R-O-(CH2-CH2O)x -CH2-COOH, in der R eine lineare Alkylgruppe mit 10 bis 22 C-Atomen und x = 0 oder 1 bis 16 ist, anionische Alkyloligoglykoside bzw. anionische Alkenyloligoglykosid-Derivate, ausgewählt aus Alkyl- und/oder Alkenyl-Oligoglykosidcarboxylaten, -sulfaten, -phosphaten und/oder - isethionaten, die sich von Alkyl- und/oder Alkenyloligoglykosiden der allgemeinen Formel (II) ableiten,
Figure imgf000050_0001
mit der Bedeutung R C6.22-Alkyl oder C6.22-Alkenyl,Ethercarbonsäuren the formula RO- (CH 2 -CH 2 O) x -CH 2 -COOH, in which R is a linear alkyl group having 10 to 22 carbon atoms and x = 0 or 1 to 16, anionic alkyl oligoglycosides or anionic Alkenyloligoglykosid- Derivatives selected from alkyl and / or alkenyl oligoglycoside carboxylates, sulfates, phosphates and / or isethionates derived from alkyl and / or alkenyl oligoglycosides of general formula (II),
Figure imgf000050_0001
with the meaning RC 6 . 22 alkyl or C 6 . 22 alkenyl,
G Glykosideinheit, die sich von einem Zucker mit 5 oder 6 Kohlenstoffatomen ableitet, p Zahl von 1 bis 10, insbesondere das Laurylglucosidcarboxylat, wie es als Plantapon® LGC von Cognis Deutschland erhältlich ist,G glycoside unit which is derived from a sugar containing 5 or 6 carbon atoms, p number from 1 to 10, in particular the Laurylglucosidcarboxylat, such as is available as Plantapon ® LGC from Cognis Germany,
Acylisethionate mit 10 bis 18 C-Atomen in der Acylgruppe,Acyl isethionates having 10 to 18 C atoms in the acyl group,
Sulfobernsteinsäuremono- und -dialkylester mit 8 bis 18 C-Atomen in der Alkylgruppe und Sulfobernsteinsäuremono-alkylpolyoxyethylester mit 8 bis 18 C-Atomen in der Alkylgruppe und 1 bis 6 Oxyethylgruppen, lineare Alkansulfonate mit 12 bis 18 C-Atomen, lineare Alpha-Olefinsulfonate mit 12 bis 18 C-Atomen, Alpha-Sulfofettsäuremethylester von Fettsäuren mit 12 bis 18 C-Atomen, Alkylsulfate und Alkylpolyglykolethersulfate der Formel R-O(CH2-CH2O)x-SO3H, in der R eine bevorzugt lineare Alkylgruppe mit 10 bis 18 C-Atomen und x = 0 oder 1 bis 12 ist, Gemische oberflächenaktiver Hydroxysulfonate gemäß DE-A-37 25 030, sulfatierte Hydroxyalkylpolyethylen- und/oder Hydroxyalkylenpropylenglykolether gemäß DE-A-37 23 354,Sulfobernsteinsäuremono- and dialkyl esters having 8 to 18 carbon atoms in the alkyl group and sulfosuccinic monoalkylpolyoxyethylester having 8 to 18 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups, linear alkanesulfonates having 12 to 18 carbon atoms, linear alpha-olefinsulfonates with 12 to 18 carbon atoms, alpha-sulfofatty acid methyl esters of fatty acids having 12 to 18 carbon atoms, alkyl sulfates and Alkylpolyglykolethersulfate the formula RO (CH 2 -CH 2 O) x -SO 3 H, in the R is a preferably linear alkyl group with 10 bis 18 C-atoms and x = 0 or 1 to 12, mixtures of surface-active hydroxysulfonates according to DE-A-37 25 030, sulfated hydroxyalkylpolyethylene and / or hydroxyalkylene-propylene glycol ethers according to DE-A-37 23 354,
Sulfonate ungesättigter Fettsäuren mit 12 bis 24 C-Atomen und 1 bis 6 Doppelbindungen gemäß DE-A-39 26 344, Ester der Weinsäure und Zitronensäure mit Alkoholen, die Anlagerungsprodukte von etwa 2-15 Molekülen Ethylenoxid und/oder Propylenoxid an Fettalkohole mit 8 bis 22 C- Atomen darstellen.Sulfonates of unsaturated fatty acids having 12 to 24 carbon atoms and 1 to 6 double bonds according to DE-A-39 26 344, Esters of tartaric acid and citric acid with alcohols which are adducts of about 2-15 molecules of ethylene oxide and / or propylene oxide with fatty alcohols having 8 to 22 carbon atoms.
Bevorzugte zusätzliche anionische Tenside werden ausgewählt aus oben genannten anionischen Alkyloligoglykosid- bzw. anionischen Alkenyloligoglykosid-Derivaten, Ethercarbonsäuren mit 10 bis 18 C-Atomen in der Alkylgruppe und bis zu 12 Glykolethergruppen im Molekül sowie insbesondere Salzen von gesättigten und insbesondere ungesättigten C8-C22-Carbonsäuren, wie Ölsäure, Stearinsäure, Isostearinsäure und Palmitinsäure.Preferred additional anionic surfactants are selected from the abovementioned anionic alkyl oligoglycoside or anionic alkenyl oligoglycoside derivatives, ether carboxylic acids having 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule, and in particular salts of saturated and in particular unsaturated C 8 -C 22 Carboxylic acids such as oleic acid, stearic acid, isostearic acid and palmitic acid.
Nichtionogene Tenside enthalten als hydrophile Gruppe z. B. eine Polyolgruppe, eine Po- lyalkylenglykolethergruppe oder eine Kombination aus Polyol- und Polyglykolethergruppe. Solche Verbindungen sind beispielsweiseNonionic surfactants contain as hydrophilic group z. A polyol group, a polyalkylene glycol ether group or a combination of polyol and polyglycol ether groups. Such compounds are, for example
Anlagerungsprodukte von 2 bis 30 Mol Ethylenoxid und/oder 0 bis 5 Mol Propylenoxid an lineare Fettalkohole mit 8 bis 22 C-Atomen, an Fettsäuren mit 12 bis 22 C-Atomen und anAddition products of 2 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide to linear fatty alcohols having 8 to 22 carbon atoms, to fatty acids having 12 to 22 carbon atoms and on
Alkylphenole mit 8 bis 15 C-Atomen in der Alkylgruppe,Alkylphenols having 8 to 15 C atoms in the alkyl group,
C12-C22-Fettsäuremono- und -diester von Anlagerungsprodukten von 1 bis 30 MolC 12 -C 22 fatty acid mono- and diesters of addition products of 1 to 30 mol
Ethylenoxid an Glycerin,Ethylene oxide with glycerol,
C8-C22-Alkylmono- und -oligoglycoside und deren ethoxylierte Analoga sowieC 8 -C 22 alkyl mono- and oligoglycosides and their ethoxylated analogs and
Anlagerungsprodukte von 5 bis 60 Mol Ethylenoxid an Rizinusöl und gehärtetes Rizinusöl.Addition products of 5 to 60 moles of ethylene oxide with castor oil and hydrogenated castor oil.
Bevorzugte nichtionische Tenside sind Alkylpolyglykoside der allgemeinen Formel R1O-(Z)x. Diese Verbindungen sind durch die folgenden Parameter gekennzeichnet.Preferred nonionic surfactants are alkyl polyglycosides of the general formula R 1 O- (Z) x . These connections are identified by the following parameters.
Der Alkylrest R1 enthält 6 bis 22 Kohlenstoffatome und kann sowohl linear als auch verzweigt sein. Bevorzugt sind primäre lineare und in 2-Stellung methylverzweigte aliphatische Reste. Solche Alkylreste sind beispielsweise 1-Octyl, 1-Decyl, 1-Lauryl, 1-Myristyl, 1-Cetyl und 1-Stearyl. Besonders bevorzugt sind 1-Octyl, 1-Decyl, 1-Lauryl, 1-Myristyl. Bei Verwendung sogenannter "Oxo-Alkohole" als Ausgangsstoffe überwiegen Verbindungen mit einer ungeraden Anzahl von Kohlenstoffatomen in der Alkylkette.The alkyl radical R 1 contains 6 to 22 carbon atoms and may be both linear and branched. Preference is given to primary linear and methyl-branched in the 2-position aliphatic radicals. Such alkyl radicals are, for example, 1-octyl, 1-decyl, 1-lauryl, 1-myristyl, 1-cetyl and 1-stearyl. Particularly preferred are 1-octyl, 1-decyl, 1-lauryl, 1-myristyl. When using so-called "oxo-alcohols" as starting materials, compounds with an odd number of carbon atoms in the alkyl chain predominate.
Die erfindungsgemäß verwendbaren Alkylpolyglykoside können beispielsweise nur einen bestimmten Alkylrest R1 enthalten. Üblicherweise werden diese Verbindungen aber ausgehend von natürlichen Fetten und Ölen oder Mineralölen hergestellt. In diesem Fall liegen als Alkylreste R Mischungen entsprechend den Ausgangsverbindungen bzw. entsprechend der jeweiligen Aufarbeitung dieser Verbindungen vor.The alkyl polyglycosides which can be used according to the invention can contain, for example, only one particular alkyl radical R 1 . Usually, however, these compounds are prepared starting from natural fats and oils or mineral oils. In this case, the alkyl radicals R are mixtures corresponding to the starting compounds or corresponding to the particular work-up of these compounds.
Besonders bevorzugt sind solche Alkylpolyglykoside, bei denen R1 im wesentlichen aus C8- und C10-Alkylgruppen, im wesentlichen aus C12- und C14-Alkylgruppen, im wesentlichen aus C8- bis C16-Alkylgruppen oder im wesentlichen aus Ci2- bis C-|6-Alkylgruppen besteht.Particular preference is given to those alkyl polyglycosides in which R 1 consists essentially of C 8 and C 10 alkyl groups, essentially of C 12 and C 14 alkyl groups, essentially of C 8 to C 16 alkyl groups or essentially from Ci 2 - to C- | 6 alkyl groups.
Als Zuckerbaustein Z können beliebige Mono- oder Oligosaccharide eingesetzt werden. Üblicherweise werden Zucker mit 5 bzw. 6 Kohlenstoffatomen sowie die entsprechenden Oligosaccharide eingesetzt. Solche Zucker sind beispielsweise Glucose, Fructose, Galactose, Arabinose, Ribose, Xylose, Lyxose, Allose, Altrose, Mannose, Gulose, Idose, Talose und Sucrose. Bevorzugte Zuckerbausteine sind Glucose, Fructose, Galactose, Arabinose und Sucrose; Glucose ist besonders bevorzugt.As sugar building block Z it is possible to use any desired mono- or oligosaccharides. Usually, sugars with 5 or 6 carbon atoms and the corresponding oligosaccharides are used. Such sugars are, for example, glucose, fructose, galactose, arabinose, ribose, xylose, lyxose, allose, altrose, mannose, gulose, idose, talose and sucrose. Preferred sugar building blocks are glucose, fructose, galactose, arabinose and sucrose; Glucose is particularly preferred.
Die erfindungsgemäß verwendbaren Alkylpolyglykoside enthalten im Schnitt 1 ,1 bis 5 Zuckereinheiten. Alkylpolyglykoside mit x-Werten von 1 ,1 bis 1 ,6 sind bevorzugt. Ganz besonders bevorzugt sind Alkylglykoside, bei denen x 1 , 1 bis 1 ,4 beträgt.The alkyl polyglycosides which can be used according to the invention contain on average from 1.1 to 5 sugar units. Alkyl polyglycosides having x values of 1.1 to 1.6 are preferred. Very particular preference is given to alkyl glycosides in which x is 1: 1 to 1, 4.
Eine erfindungsgemäß besonders geeignete Verbindungsklasse aus dieser Substanzgruppe stellen die unter der Bezeichnung Plantacare® im Handel erhältlichen Glucoside dar.An inventively particularly suitable class of compounds from this group are the glucoside sold under the name Plantacare® ® commercially.
Die Alkylglykoside können neben ihrer Tensidwirkung auch dazu dienen, die Fixierung von Duftkomponenten auf dem Haar zu verbessern. Der Fachmann wird also für den Fall, dass eine über die Dauer der Haarbehandlung hinausgehende Wirkung des Parfümöles auf dem Haar gewünscht wird, bevorzugt erfindungsgemäß zu dieser Substanzklasse als weiterem Inhaltsstoff der Zubereitungen zurückgreifen.In addition to their surfactant action, the alkyl glycosides can also serve to improve the fixation of fragrance components on the hair. The person skilled in the art will therefore prefer to use this class of substance as further constituent of the preparations in the event that an effect of the perfume oil on the hair which exceeds the duration of the hair treatment is desired.
Auch die alkoxylierten Homologen der genannten Alkylpolyglykoside können erfindungsgemäß eingesetzt werden. Diese Homologen können durchschnittlich bis zu 10 Ethylenoxid- und/oder Propylenoxideinheiten pro Alkylglykosideinheit enthalten.The alkoxylated homologs of said alkyl polyglycosides can also be used according to the invention. These homologs may contain on average up to 10 ethylene oxide and / or propylene oxide units per alkyl glycoside unit.
Weiterhin können, insbesondere als Co-Tenside, zwitterionische Tenside verwendet werden. Als zwitterionische Tenside werden solche oberflächenaktive Verbindungen bezeichnet, die im Molekül mindestens eine quartäre Ammoniumgruppe und mindestens eine -COO( )- oder -SO3 ( )- Gruppe tragen. Besonders geeignete zwitterionische Tenside sind die sogenannten Betaine wie die N-Alkyl-N,N-dimethylammonium-glycinate, beispielsweise das Kokosalkyl-di- methylammonium-glycinat, N-Acyl-aminopropyl-N,N-dimethylammoniumglycinate, beispielsweise das Kokosacylaminopropyl-dimethylammoniumglycinat, und 2-Alkyl-3-carboxylmethyl-3-hydroxy- ethyl-imidazoline mit jeweils 8 bis 18 C-Atomen in der Alkyl- oder Acylgruppe sowie das Kokos- acylaminoethylhydroxyethylcarboxymethylglycinat. Ein bevorzugtes zwitterionisches Tensid ist das unter der INCI-Bezeichnung Cocamidopropyl Betaine bekannte Fettsäureamid-Derivat.Furthermore, zwitterionic surfactants can be used, in particular as cosurfactants. Zwitterionic surfactants are those surface-active compounds which carry at least one quaternary ammonium group and at least one -COO () or -SO 3 () group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines such as N-alkyl-N, N-dimethylammonium glycinates, for example cocoalkyldimethylammonium glycinate, N-acylaminopropyl-N, N-dimethylammonium glycinates, for example cocoacylaminopropyl-dimethylammonium glycinate, and 2-alkyl-3-carboxylmethyl-3-hydroxyethyl imidazolines having in each case 8 to 18 C atoms in the alkyl or acyl group and the coco acylaminoethylhydroxyethylcarboxymethylglycinate. A preferred zwitterionic surfactant is the fatty acid amide derivative known by the INCI name Cocamidopropyl Betaine.
Erfindungsgemäß werden als kationische Tenside insbesondere solche vom Typ der quartären Ammoniumverbindungen, der Esterquats und der Amidoamine eingesetzt.According to the invention, the cationic surfactants used are, in particular, those of the quaternary ammonium compound type, the esterquats and the amidoamines.
Bevorzugte quaternäre Ammoniumverbindungen sind Ammoniumhalogenide, insbesondere Chloride und Bromide, wie Alkyltrimethylammoniumchloride, Dialkyldimethylammoniumchloride und Trialkylmethylammoniumchloride, z. B. Cetyltrimethylammoniumchlorid, Stearyltri- methylammoniumchlorid, Distearyldimethylammoniumchlorid, Lauryldimethylammoniumchlorid, Lauryldimethylbenzylammoniumchlorid und Tricetylmethylammoniumchlorid, sowie die unter den INCI-Bezeichnungen Quaternium-27 und Quaternium-83 bekannten Imidazolium-Verbindungen. Die langen Alkylketten der oben genannten Tenside weisen bevorzugt 10 bis 18 Kohlenstoffatome auf.Preferred quaternary ammonium compounds are ammonium halides, in particular chlorides and bromides, such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, e.g. For example, cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride, as well as the imidazolium compounds known under the INCI names Quaternium-27 and Quaternium-83. The long alkyl chains of the above-mentioned surfactants preferably have 10 to 18 carbon atoms.
Bei Esterquats handelt es sich um bekannte Stoffe, die sowohl mindestens eine Esterfunktion als auch mindestens eine quartäre Ammoniumgruppe als Strukturelement enthalten. Bevorzugte Esterquats sind quaternierte Estersalze von Fettsäuren mit Triethanolamin, quaternierte Estersalze von Fettsäuren mit Diethanolalkylaminen und quaternierten Estersalze von Fettsäuren mit 1 ,2-Dihydroxypropyldialkylaminen. Solche Produkte werden beispielsweise unter den Warenzeichen Stepantex®, Dehyquart® und Armocare® vertrieben. Die Produkte Armocare® VGH-70, ein N,N-Bis(2-Palmitoyloxyethyl)dimethylammoniumchlorid, sowie Dehyquart® F-75 und Dehyquart® AU-35 sind Beispiele für solche Esterquats.Esterquats are known substances which contain both at least one ester function and at least one quaternary ammonium group as a structural element. Preferred ester quats are quaternized ester salts of fatty acids with triethanolamine, quaternized ester salts of fatty acids with diethanolalkylamines and quaternized ester salts of fatty acids with 1,2-dihydroxypropyldialkylamines. Such products are marketed under the trade names Stepantex® ®, ® and Dehyquart® Armocare® ®. The products Armocare ® VGH-70, a N, N-bis (2-palmitoyloxyethyl) dimethylammonium chloride, as well as Dehyquart ® F-75 and Dehyquart ® AU-35 are examples of such esterquats.
Die Alkylamidoamine werden üblicherweise durch Amidierung natürlicher oder synthetischer Fettsäuren und Fettsäureschnitte mit Dialkylaminoaminen hergestellt. Eine erfindungsgemäß besonders geeignete Verbindung aus dieser Substanzgruppe stellt das unter der Bezeichnung Tegoamid® S 18 im Handel erhältliche Stearamidopropyl-dimethylamin dar.The alkylamidoamines are usually prepared by amidation of natural or synthetic fatty acids and fatty acid cuts with dialkylaminoamines. An inventively particularly suitable compound from this group of substances under the name Tegoamid ® S 18 commercial stearamidopropyl dimethylamine is.
Weitere erfindungsgemäß verwendbare kationische Tenside stellen die quaternisierten Proteinhydrolysate dar.Further cationic surfactants which can be used according to the invention are the quaternized protein hydrolysates.
Ein Beispiel für ein als kationisches Tensid einsetzbares quaternäres Zuckerderivat stellt das Handelsprodukt Glucquat®100 dar, gemäß INCI-Nomenklatur ein "Lauryl Methyl Gluceth-10 Hydroxypropyl Dimonium Chloride".An example of a suitable cationic surfactant quaternary sugar derivative is the commercially available product Glucquat ® 100 is, according to INCI nomenclature a "lauryl methyl Gluceth-10 Hydroxypropyl Dimonium Chloride".
Bei den als Tensid eingesetzten Verbindungen mit Alkylgruppen kann es sich jeweils um einheitliche Substanzen handeln. Es ist jedoch in der Regel bevorzugt, bei der Herstellung dieser Stoffe von nativen pflanzlichen oder tierischen Rohstoffen auszugehen, so dass man Substanzgemische mit unterschiedlichen, vom jeweiligen Rohstoff abhängigen Alkylkettenlängen erhält.The compounds used as surfactant with alkyl groups may each be uniform substances. However, it is generally preferred to use native vegetable or animal raw materials in the production of these substances, so that substance mixtures having different alkyl chain lengths depending on the respective raw material are obtained.
Bei den Tensiden, die Anlagerungsprodukte von Ethylen- und/oder Propylenoxid an Fettalkohole oder Derivate dieser Anlagerungsprodukte darstellen, können sowohl Produkte mit einer "normalen" Homologenverteilung als auch solche mit einer eingeengten Homologenverteilung verwendet werden. Unter "normaler" Homologenverteilung werden dabei Mischungen von Homologen verstanden, die man bei der Umsetzung von Fettalkohol und Alkylenoxid unter Verwendung von Alkalimetallen, Alkalimetallhydroxiden oder Alkalimetallalkoholaten als Katalysatoren erhält. Eingeengte Homologenverteilungen werden dagegen erhalten, wenn beispielsweise Hydrotalcite, Erdalkalimetallsalze von Ethercarbonsäuren, Erdalkalimetalloxide, -hydroxide oder - alkoholate als Katalysatoren verwendet werden. Die Verwendung von Produkten mit eingeengter Homologenverteilung kann bevorzugt sein.In the case of the surfactants which are adducts of ethylene oxide and / or propylene oxide with fatty alcohols or derivatives of these addition products, both products with a "normal" homolog distribution and those with a narrow homolog distribution can be used. By "normal" homolog distribution are meant mixtures of homologs obtained in the reaction of fatty alcohol and alkylene oxide using alkali metals, alkali metal hydroxides or alkali metal alcoholates as catalysts. Narrowed homolog distributions are obtained when, for example Hydrotalcites, alkaline earth metal salts of ether carboxylic acids, alkaline earth metal oxides, hydroxides or - alkoxides can be used as catalysts. The use of products with narrow homolog distribution may be preferred.
Ferner können die erfindungsgemäß eingesetzten Mittel weitere Wirk-, Hilfs- und Zusatzstoffe, wie beispielsweise nichtionische, zwitterionische und amphotere, anioische oder kationische PolymereFurthermore, the agents used according to the invention may contain further active ingredients, auxiliaries and additives, such as, for example, nonionic, zwitterionic and amphoteric, anioic or cationic polymers
Strukturanten wie Maleinsäure und Milchsäure, haarkonditionierende Verbindungen wie Phospholipide, beispielsweise Sojalecithin, Ei-Lecitin und Kephaline,Structural agents such as maleic acid and lactic acid, hair conditioning compounds such as phospholipids, for example soya lecithin, egg lecithin and cephalins,
Proteinhydrolysate, insbesondere Elastin-, Kollagen-, Keratin-, Milcheiweiß-, Sojaprotein- undProtein hydrolysates, in particular elastin, collagen, keratin, milk protein, soy protein and
Weizenproteinhydrolysate, deren Kondensationsprodukte mit Fettsäuren sowie quaternisierteWheat protein hydrolysates, their condensation products with fatty acids and quaternized
Proteinhydrolysate,protein,
Parfümöle, Dimethylisosorbid und Cyclodextrine,Perfume oils, dimethylisosorbide and cyclodextrins,
Lösungsmittel und -vermittler wie Ethanol, Isopropanol, Ethylenglykol, Propylenglykol, Glyce- rin und Diethylenglykol, faserstrukturverbessernde Wirkstoffe, insbesondere Mono-, Di- und Oligosaccharide wie beispielsweise Glucose, Galactose, Fructose, Fruchtzucker und Lactose, quaternierte Amine wie Methyl-1-alkylamidoethyl-2-alkylimidazolinium-methosulfatSolvents and mediators such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol and diethylene glycol, fiber-structure-improving agents, especially mono-, di- and oligosaccharides such as glucose, galactose, fructose, fructose and lactose, quaternized amines such as methyl-1-alkylamidoethyl -2-alkylimidazolinium methosulfate
Entschäumer wie Silikone,Defoamers like silicones,
Farbstoffe zum Anfärben des Mittels,Dyes for staining the agent,
Antischuppenwirkstoffe wie Piroctone Olamine, Zink Omadine und Climbazol,Anti-dandruff agents such as Piroctone Olamine, Zinc Omadine and Climbazole,
Lichtschutzmittel, insbesondere derivatisierte Benzophenone, Zimtsäure-Derivate undLight stabilizers, in particular derivatized benzophenones, cinnamic acid derivatives and
Triazine,triazines,
Wirkstoffe wie Allantoin, Pyrrolidoncarbonsäuren und deren Salze sowie Bisabolol,Active ingredients such as allantoin, pyrrolidonecarboxylic acids and their salts, and bisabolol,
Vitamine, Provitamine und Vitaminvorstufen, insbesondere solche der Gruppen A, B3, B5, B6,Vitamins, provitamins and vitamin precursors, in particular those of groups A, B 3 , B 5 , B 6 ,
C, E, F und H,C, E, F and H,
Pflanzenextrakte wie die Extrakte aus Grünem Tee, Eichenrinde, Brennessel, Hamamelis,Plant extracts such as extracts of green tea, oak bark, stinging nettle, witch hazel,
Hopfen, Kamille, Klettenwurzel, Schachtelhalm, Weißdorn, Lindenblüten, Mandel, Aloe Vera,Hops, chamomile, burdock root, horsetail, hawthorn, lime blossom, almond, aloe vera,
Fichtennadel, Roßkastanie, Sandelholz, Wacholder, Kokosnuß, Mango, Aprikose, Limone,Spruce needle, horse chestnut, sandalwood, juniper, coconut, mango, apricot, lime,
Weizen, Kiwi, Melone, Orange, Grapefruit, Salbei, Rosmarin, Birke, Malve,Wheat, kiwi, melon, orange, grapefruit, sage, rosemary, birch, mallow,
Wiesenschaumkraut, Quendel, Schafgarbe, Thymian, Melisse, Hauhechel, Huflattich, Eibisch,Meadowfoam, Quendel, Yarrow, Thyme, Melissa, Hauhechel, Coltsfoot, Marshmallow,
Meristem, Ginseng und Ingwerwurzel,.Meristem, ginseng and ginger root ,.
Cholesterin,Cholesterol,
Konsistenzgeber wie Zuckerester, Polyolester oder Polyolalkylether,Bodying agents such as sugar esters, polyol esters or polyol alkyl ethers,
Fette und Wachse wie Walrat, Bienenwachs, Montanwachs und Paraffine,Fats and waxes such as spermaceti, beeswax, montan wax and paraffins,
Komplexbildner wie EDTA, NTA, ß-Alanindiessigsäure und Phosphonsäuren,Complexing agents such as EDTA, NTA, β-alaninediacetic acid and phosphonic acids,
Quell- und Penetrationsstoffe wie Glycerin, Propylenglykolmonoethylether, Carbonate,Swelling and penetration substances such as glycerol, propylene glycol monoethyl ether, carbonates,
Hydrogencarbonate, Guanidine, Harnstoffe sowie primäre, sekundäre und tertiäre Phosphate,Hydrogencarbonates, guanidines, ureas and primary, secondary and tertiary phosphates,
Trübungsmittel wie Latex, Styrol/PVP- und Styrol/Acrylamid-CopolymereOpacifiers such as latex, styrene / PVP and styrene / acrylamide copolymers
Perlglanzmittel wie Ethylenglykolmono- und -distearat sowie PEG-3-distearat, Pigmente,Pearlescing agents such as ethylene glycol mono- and distearate and PEG-3-distearate, pigments
Stabilisierungsmittel für Wasserstoffperoxid und andere Oxidationsmittel, Treibmittel wie Propan-Butan-Gemische, N2O, Dimethylether, CO2 und Luft, Antioxidantien, enthalten.Stabilizers for hydrogen peroxide and other oxidizing agents, propellants such as propane-butane mixtures, N 2 O, dimethyl ether, CO 2 and air, antioxidants.
In einer bevorzugten Ausführungsform der erfindungsgemäßen Lehre kann die Wirkung mit Polymeren weiter gesteigert werden. Unter Polymeren sind sowohl natürliche als auch synthetische Polymere, welche anionisch, kationisch, amphoter geladen oder nichtionisch sein können, zu verstehen.In a preferred embodiment of the teaching according to the invention, the effect can be further increased with polymers. By polymers are meant both natural and synthetic polymers which may be anionic, cationic, amphoteric or nonionic.
Unter kationischen Polymeren sind Polymere zu verstehen, welche in der Haupt- und/oder Seitenkette Gruppen aufweisen, welche „temporär" oder „permanent" kationisch sein kann. Als „permanent kationisch" werden erfindungsgemäß solche Polymere bezeichnet, die unabhängig vom pH-Wert des Mittels eine kationische Gruppe aufweisen. Dies sind in der Regel Polymere, die ein quartäres Stickstoffatom, beispielsweise in Form einer Ammoniumgruppe, enthalten. Bevorzugte kationische Gruppen sind quartäre Ammoniumgruppen. Insbesondere solche Polymere, bei denen die quartäre Ammoniumgruppe über eine Ci_4-Kohlenwasserstoffgruppe an eine aus Acrylsäure, Methacrylsäure oder deren Derivaten aufgebaute Polymerhauptkette gebunden sind, haben sich als besonders geeignet erwiesen. Homopolymere der allgemeinen Formel (III), R18 Cationic polymers are polymers which have groups in the main and / or side chain which may be "temporary" or "permanent" cationic. According to the invention, "permanently cationic" refers to those polymers which have a cationic group independently of the pH of the agent These are generally polymers which contain a quaternary nitrogen atom, for example in the form of an ammonium group Preferred cationic groups are quaternary ammonium groups . in particular, those polymers in which the quaternary ammonium group 4 hydrocarbon group bound to a synthesized from acrylic acid, methacrylic acid or derivatives thereof, polymer main chain via a CI_ have been found to be particularly suitable. homopolymers of the general formula (III), R 18
II
-[CH2-C-Jn X" (III)- [CH 2 -CJ n X " (III)
CO-O-(CH2)m-N+R19R20R21 CO-O- (CH 2 ) m -N + R 19 R 20 R 21
in der R18 = -H oder -CH3 ist, R19, R20 und R21 unabhängig voneinander ausgewählt sind aus C-ι-4-Alkyl-, -Alkenyl- oder -Hydroxyalkylgruppen, m = 1 , 2, 3 oder 4, n eine natürliche Zahl und X' ein physiologisch verträgliches organisches oder anorganisches Anion ist, sowie Copolymere, bestehend im wesentlichen aus den in Formel (III) aufgeführten Monomereinheiten sowie nichtionogenen Monomereinheiten, sind besonders bevorzugte kationische Polymere. Im Rahmen dieser Polymere sind diejenigen erfindungsgemäß bevorzugt, für die mindestens eine der folgenden Bedingungen gilt:in which R 18 = -H or -CH 3, R 19, R 20 and R 21 are independently selected from C-ι- 4 -alkyl, -alkenyl or -hydroxyalkyl groups, m = 1, 2, 3 or 4, n is a natural number and X 'is a physiologically acceptable organic or inorganic anion, and copolymers consisting essentially of the monomer units listed in formula (III) and nonionic monomer units are particularly preferred cationic polymers. In the context of these polymers, preference is given to those according to the invention for which at least one of the following conditions applies:
R18 steht für eine MethylgruppeR 18 is a methyl group
R19, R20 und R21 stehen für Methylgruppen m hat den Wert 2.R 19 , R 20 and R 21 are methyl groups m has the value 2.
Als physiologisch verträgliches Gegenionen X" kommen beispielsweise Halogenidionen, Sulfationen, Phosphationen, Methosulfationen sowie organische Ionen wie Lactat-, Citrat-, Tartrat- und Acetationen in Betracht. Bevorzugt sind Halogenidionen, insbesondere Chlorid. Ein besonders geeignetes Homopolymer ist das, gewünschtenfalls vernetzte, Po^methacryloyloxyethyltrimethylammoniumchlorid) mit der INCI-Bezeichnung Polyquaternium- 37. Die Vernetzung kann gewünschtenfalls mit Hilfe mehrfach olefinisch ungesättigter Verbindungen, beispielsweise Divinylbenzol, Tetraallyloxyethan, Methylenbisacrylamid, Diallylether, Polyallylpolyglycerylether, oder Allylethern von Zuckern oder Zuckerderivaten wie Erythritol, Pentaerythritol, Arabitol, Mannitol, Sorbitol, Sucrose oder Glucose erfolgen. Methylenbisacrylamid ist ein bevorzugtes Vernetzungsagens.Suitable physiologically tolerated counterions X " are, for example, halide ions, sulfate ions, phosphate ions, methosulfate ions and organic ions such as lactate, citrate, tartrate and acetate ions, preference being given to halide ions, in particular chloride. A particularly suitable homopolymer is, if desired cross-linked, Po ^ methacryloyloxyethyltrimethylammoniumchlorid) with the INCI name Polyquaternium- 37. The crosslinking can, if desired, using poly olefinically unsaturated compounds, for example divinylbenzene, tetraallyloxyethane, methylenebisacrylamide, diallyl ether, polyallylpolyglycerylether, or allyl ethers of sugars or Sugar derivatives such as erythritol, pentaerythritol, arabitol, mannitol, sorbitol, sucrose or glucose. Methylenebisacrylamide is a preferred crosslinking agent.
Das Homopolymer wird bevorzugt in Form einer nichtwäßrigen Polymerdispersion, die einen Polymeranteil nicht unter 30 Gew.-% aufweisen sollte, eingesetzt. Solche Polymerdispersionen sind unter den Bezeichnungen Salcare® SC 95 (ca. 50 % Polymeranteil, weitere Komponenten: Mineralöl (INCI-Bezeichnung: Mineral OiI) und Tridecyl-polyoxypropylen-polyoxyethylen-ether (INCI-Bezeichnung: PPG-1-Trideceth-6)) und Salcare® SC 96 (ca. 50 % Polymeranteil, weitere Komponenten: Mischung von Diestern des Propylenglykols mit einer Mischung aus Capryl- und Caprinsäure (INCI-Bezeichnung: Propylene Glycol Dicaprylate/Dicaprate) und Tridecyl- polyoxypropylen-polyoxyethylen-ether (INCI-Bezeichnung: PPG-1-Trideceth-6)) im Handel erhältlich.The homopolymer is preferably used in the form of a nonaqueous polymer dispersion which should not have a polymer content of less than 30% by weight. Such polymer dispersions are (under the names Salcare ® SC 95 about 50% polymer content, additional components: mineral oil (INCI name: Mineral Oil) and tridecyl-polyoxypropylene-polyoxyethylene-ether (INCI name: PPG-1 trideceth-6) ) and Salcare ® SC 96 (about 50% polymer content, additional components: mixture of diesters of propylene glycol with a mixture of caprylic and capric acid (INCI name: propylene glycol Dicaprylate / Dicaprate) and tridecyl polyoxypropylene-polyoxyethylene-ether (INCI Designation: PPG-1-trideceth-6)) are commercially available.
Copolymere mit Monomereinheiten gemäß Formel (IM) enthalten als nichtionogene Monomereinheiten bevorzugt Acrylamid, Methacrylamid, Acrylsäure-C-^-alkylester und Methacrylsäure-C-|.4-alkylester. Unter diesen nichtionogenen Monomeren ist das Acrylamid besonders bevorzugt. Auch diese Copolymere können, wie im Falle der Homopolymere oben beschrieben, vernetzt sein. Ein erfindungsgemäß bevorzugtes Copolymer ist das vernetzte Acrylamid-Methacryloyloxyethyltrimethylammoniumchlorid-Copolymer. Solche Copolymere, bei denen die Monomere in einem Gewichtsverhältnis von etwa 20:80 vorliegen, sind im Handel als ca. 50 %ige nichtwäßrige Polymerdispersion unter der Bezeichnung Salcare® SC 92 erhältlich.Copolymers with monomer units of the formula (III) contain, as nonionic monomer units, preferably acrylamide, methacrylamide, acrylic acid C 1 -4 -alkyl esters and methacrylic acid C 1. 4- alkyl esters. Among these nonionic monomers, the acrylamide is particularly preferred. These copolymers can also be crosslinked, as described above in the case of the homopolymers. A copolymer preferred according to the invention is the crosslinked acrylamide-methacryloyloxyethyltrimethylammonium chloride copolymer. Such copolymers in which the monomers are present in a weight ratio of about 20:80, are commercially available as approximately 50% non-aqueous polymer dispersion 92 under the name Salcare ® SC.
Weitere bevorzugte kationische Polymere sind beispielsweise: quaternisierte Cellulose-Derivate, wie sie unter den Bezeichnungen Celquat® und Polymer JR® im Handel erhältlich sind. Die Verbindungen Celquat® H 100, Celquat® L 200 und Polymer JR®400 sind bevorzugte quaternierte Cellulose-Derivate, kationische Alkylpolyglycoside gemäß der DE-PS 44 13 686, kationiserter Honig, beispielsweise das Handelsprodukt Honeyquat® 50, kationische Guar-Derivate, wie insbesondere die unter den Handelsnamen Cosmedia®Guar und Jaguar® vertriebenen Produkte,Other preferred cationic polymers are for example: quaternized cellulose derivatives, such as are available under the names of Celquat ® and Polymer JR ® commercially. The compounds Celquat ® H 100, Celquat ® L 200 and Polymer JR ® 400 are preferred quaternized cellulose derivatives, cationic alkyl polyglycosides according to DE-PS 44 13 686, cationized honey, for example the commercial product Honeyquat ® 50, cationic guar derivatives, such as in particular the products sold under the trade names Cosmedia® ® guar and Jaguar ® products,
- Polysiloxane mit quaternären Gruppen, wie beispielsweise die im Handel erhältlichen Produkte Q2-7224 (Hersteller: Dow Corning; ein stabilisiertes Trimethylsilylamodimethicon), Dow Corning® 929 Emulsion (enthaltend ein hydroxyl-amino-modifiziertes Silicon, das auch als Amodimethicone bezeichnet wird), SM-2059 (Hersteller: General Electric), SLM-55067 (Hersteller: Wacker) sowie Abil®-Quat 3270 und 3272 (Hersteller: Th. Goldschmidt; di- quaternäre Polydimethylsiloxane, Quaternium-80),Quaternary group polysiloxanes, such as the commercially available products Q2-7224 (manufactured by Dow Corning, a stabilized trimethylsilylamodimethicone), Dow Corning® 929 emulsion (containing a hydroxylamino-modified silicone, also referred to as amodimethicones), SM-2059 (manufacturer: General Electric), SLM-55067 (Manufacturer: Wacker) and Abil ® -Quat 3270 and 3272 (manufacturer: Th Goldschmidt; di- quaternary polydimethylsiloxanes, quaternium-80).,
- polymere Dimethyldiallylammoniumsalze und deren Copolymere mit Estern und Amiden von Acrylsäure und Methacrylsäure. Die unter den Bezeichnungen Merquat®100 (Poly(dimethyldiallylammoniumchlorid)) und Merquat®550 (Dimethyldiallylammoniumchlorid- Acrylamid-Copolymer) im Handel erhältlichen Produkte sind Beispiele für solche kationischen Polymere,- Dimethyldiallylammoniumsalze polymeric and their copolymers with esters and amides of acrylic acid and methacrylic acid. Under the names Merquat ® 100 (Poly (dimethyldiallylammonium chloride)) and Merquat ® 550 (dimethyldiallylammonium chloride-acrylamide copolymer) are examples of such cationic polymers,
Copolymere des Vinylpyrrolidons mit quaternierten Derivaten des Dialkylaminoalkylacrylats und -methacrylats, wie beispielsweise mit Diethylsulfat quaternierte Vinylpyrrolidon- Dimethylaminoethylmethacrylat-Copolymere. Solche Verbindungen sind unter den Bezeichnungen Gafquat®734 und Gafquat®755 im Handel erhältlich,Copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoalkyl acrylate and methacrylate, such as diethyl sulfate quaternized vinylpyrrolidone-dimethylaminoethyl methacrylate copolymers. Such compounds are sold under the names Gafquat ® 734 and Gafquat ® 755 commercially,
Vinylpyrrolidon-Vinylimidazoliummethochlorid-Copolymere, wie sie unter den Bezeichnungen Luviquat® FC 370, FC 550, FC 905 und HM 552 angeboten werden, quaternierter Polyvinylalkohol, sowie die unter den Bezeichnungen Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 undVinylpyrrolidone-Vinylimidazoliummethochlorid copolymers, such as those available under the names Luviquat ® FC 370, FC 550, FC 905 and HM 552, quaternized polyvinyl alcohol, as well as those under the names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and
Polyquaternium 27 bekannten Polymeren mit quartären Stickstoffatomen in der Polymerhauptkette.Polyquaternium 27 known polymers with quaternary nitrogen atoms in the polymer main chain.
Gleichfalls als kationische Polymere eingesetzt werden können die unter den Bezeichnungen Polyquaternium-24 (Handelsprodukt z. B. Quatrisoft® LM 200), bekannten Polymere. Ebenfalls erfindungsgemäß verwendbar sind die Copolymere des Vinylpyrrolidons, wie sie als Handelsprodukte Copolymer 845 (Hersteller: ISP), Gaffix® VC 713 (Hersteller: ISP), Gafquat®ASCP 1011 , Gafquat®HS 110, Luviquat®8155 und Luviquat® MS 370 erhältlich sind.Can be used as cationic polymers are sold under the names Polyquaternium-24 (commercial product z. B. Quatrisoft ® LM 200), known polymers. , Gaffix ® VC 713 (manufactured by ISP): Also according to the invention can be used the copolymers of vinylpyrrolidone, such as the commercial products Copolymer 845 (ISP manufacturer) are Gafquat ® ASCP 1011, Gafquat ® HS 110, Luviquat ® 8155 and Luviquat ® MS 370 available are.
Weitere erfindungsgemäße kationische Polymere sind die sogenannten „temporär kationischen" Polymere. Diese Polymere enthalten üblicherweise eine Aminogruppe, die bei bestimmten pH- Werten als quartäre Ammoniumgruppe und somit kationisch vorliegt. Bevorzugt sind beispielsweise Chitosan und dessen Derivate, wie sie beispielsweise unter den Handelsbezeichnungen Hydagen® CMF, Hydagen® HCMF, Kytamer® PC und Chitolam® NB/101 im Handel frei verfügbar sind. Chitosane sind deacetylierte Chitine, die in unterschiedlichen Deacetylierungsgraden und unterschiedlichen Abbaugraden (Molekulargewichten) im Handel erhältlich sind. Ihre Herstellung ist z.B. in DE 44 40 625 A1 und in DE 1 95 03 465 A1 beschrieben.Other cationic polymers of the present invention, the "temporarily cationic" polymers. These polymers are usually contain an amino group present at certain pH values as a quaternary ammonium group and hence cationic. For example, chitosan and its derivatives are preferred, such as for example, under the trade designations Hydagen ® CMF, Hydagen® ® HCMF, Kytamer ® PC and Chitolam ® NB / 101 are freely available commercially. chitosans are deacetylated, in different degrees of deacetylation and varying degrees of degradation (molecular weights) are commercially available. Their preparation is, for example, in DE 44 40 625 A1 and described in DE 1 95 03 465 A1.
Besonders gut geeignete Chitosane weisen einen Deacetylierungsgrad von wenigstens 80 % und ein Molekulargewicht von 5 ' 105 bis 5 ' 106 (g/mol) auf. Zur Herstellung erfindungsgemäßer Zubereitungen muß das Chitosan in die Salzform überführt werden. Dies kann durch Auflösen in verdünnten wäßrigen Säuren erfolgen. Als Säuren sind sowohl Mineralsäuren wie z.B. Salzsäure, Schwefelsäure und Phosphorsäure als auch organische Säuren, z.B. niedermolekulare Carbonsäuren, Polycarbonsäuren und Hydroxycarbonsäuren geeignet. Weiterhin können auch höhermolekulare Alkylsulfonsäuren oder Alkylschwefelsäuren oder Organophosphorsäuren verwendet werden, soweit diese die erforderliche physiologische Verträglichkeit aufweisen. Geeignete Säuren zur Überführung des Chitosans in die Salzform sind z.B. Essigsäure, Glycolsäure, Weinsäure, Apfelsäure, Citronensäure, Milchsäure, 2-Pyrrolidinon-5-carbonsäure, Benzoesäure oder Salicylsäure. Bevorzugt werden niedermolekulare Hydroxycarbonsäuren wie z.B. Glycolsäure oder Milchsäure verwendet.Particularly useful chitosans have a degree of deacetylation of at least 80% and a molecular weight of 5 '10 5 to 5' 10 6 (g / mol). For the production of preparations according to the invention, the chitosan must be converted into the salt form. This can be done by dissolving in dilute aqueous acids. Suitable acids are both mineral acids such as hydrochloric acid, sulfuric acid and phosphoric acid and organic acids, for example low molecular weight carboxylic acids, polycarboxylic acids and hydroxycarboxylic acids. Furthermore, higher molecular weight alkyl sulfonic acids or alkyl sulfuric acids or organophosphoric acids can be used, provided that they have the required physiological compatibility. Suitable acids for converting the chitosan into the salt form are, for example, acetic acid, glycolic acid, tartaric acid, malic acid, citric acid, lactic acid, 2-pyrrolidinone-5-carboxylic acid, benzoic acid or salicylic acid. Preference is given to using low molecular weight hydroxycarboxylic acids, for example glycolic acid or lactic acid.
Bei den anionischen Polymeren, welche die Wirkung des erfindungsgemäßen Wirkstoffes unterstützen können, handelt es sich um ein anionische Polymere, welche Carboxylat- und/oder Sulfonatgruppen aufweisen. Beispiele für anionische Monomere, aus denen derartige Polymere bestehen können, sind Acrylsäure, Methacrylsäure, Crotonsäure, Maleinsäureanhydrid und 2- Acrylamido-2-methylpropansulfonsäure. Dabei können die sauren Gruppen ganz oder teilweise als Natrium-, Kalium-, Ammonium-, Mono- oder Triethanolammonium-Salz vorliegen. Bevorzugte Monomere sind 2-Acrylamido-2-methylpropansulfonsäure und Acrylsäure.The anionic polymers which can support the action of the active ingredient according to the invention are anionic polymers which have carboxylate and / or sulfonate groups. Examples of anionic monomers from which such polymers may consist are acrylic acid, methacrylic acid, crotonic acid, maleic anhydride and 2-acrylamido-2-methylpropanesulfonic acid. The acidic groups may be wholly or partly present as sodium, potassium, ammonium, mono- or triethanolammonium salt. Preferred monomers are 2-acrylamido-2-methylpropanesulfonic acid and acrylic acid.
Weiterhin können als anionische Polymere zur Unterstützung der Wirkung des erfindungsgemäßen Mittels bevorzugt Polysaccharide eingesetzt werden, die ihren anionischen Charakter entweder durch den Einbau von Carbonsäure-Gruppen tragenden Furanosen oder Pyranosen oder durch die anionische Funktionalisierung von Hydroxy-Gruppen einzelner Zuckerbausteine begründen.Furthermore, it is possible to use as anionic polymers to support the action of the agent according to the invention preferably polysaccharides which substantiate their anionic character either by the incorporation of carboxylic acid-bearing furanoses or pyranoses or by the anionic functionalization of hydroxyl groups of individual sugar building blocks.
Unter den Carbonsäure-Gruppen tragenden Pyranosen und Furanosen befinden sich insbesondere Uronsäuren, wie beispielsweise Guluronsäure, Glucuronsäure, Mannuronsäure, Iduronsäure oder Galacturonsäure. Solche anionischen Polymere können entweder direkt aus pflanzlichen Rohstoffen isoliert werden oder durch biochemische Umsetzung erhalten werden. Beispiele für Pflanzenextrakte sind die Glycosaminoglycane Hyaluronsäure, Chondroitinsulfat und Keratansulfat und die Gummen Gummi arabicum, Karaya Gummi, Ghatti Gummi und Gummi Tragacantha. Erfindungsgemäß besonders bevorzugt sind Algin, welches beispielsweise unter dem Warenzeichen Kelgin® oder Texamid® vertrieben wird, sowie Xanthan (gum), welches beispielsweise unter den Warenzeichen Kelzan® oder Keltrol® im Handel erhältlich ist, und Gellan (gum), welches durch Fermentation gewonnen wird und unter den Warenzeichen Gelrite® und Kelcogel® im Handel erhältlich ist.Among the carboxylic acid groups bearing pyranoses and furanoses are in particular uronic acids, such as guluronic acid, glucuronic acid, mannuronic acid, iduronic acid or galacturonic acid. Such anionic polymers can either be isolated directly from vegetable raw materials or obtained by biochemical reaction. Examples of plant extracts are the glycosaminoglycans hyaluronic acid, chondroitin sulfate and keratan sulfate, and the gums gum arabic, karaya gum, ghatti gum and gum tragacantha. According to the invention are particularly preferred algin, which is marketed for example under the tradename Kelgin ® or Texamid ®, and xanthan (gum), which is available for example under the trademarks Kelzan ® or Keltrol ® commercially, and gellan (gum) which obtained by fermentation will and available under the trademark Gelrite ® and Kelcogel ® is commercially.
In Polysacchariden eingesetzte, anionisch funktionalisierte Zuckerbausteine enthalten zumeist sulfatierte, phosphatierte oder carboxymethylierte Hydroxygruppen. Natürlich vorkommende Sulfate sind die Rotalgen-Extrakte Carrageenan (Genuvisco® )und Agar. Besonders geeignete anionische Polymere sind insbesondere die Carboxymethylether-Derivate von Polysacchariden. Dazu eingesetzte Polysaccharide umfassen unter anderem Cellulose (Cellogen ®, Denvercel® ), Kartoffelstärke, Maisstärke, Carob gum, Guar gum, Tamarind Seed gum, Chitin (Chitin liquid® 111 140), beta-Glucan (CM Glucan® ), Inulin und Amylose.In polysaccharides used, anionically functionalized sugar units contain mostly sulfated, phosphated or carboxymethylated hydroxy groups. Naturally occurring sulfates are the red algae extracts carrageenan (Genuvisco ®) and agar. Particularly suitable anionic polymers are in particular the carboxymethyl ether derivatives of polysaccharides. Polysaccharides by used include, inter alia cellulose (Cellogen ®, Denvercel ®), Potato starch, corn starch, carob gum, guar gum, tamarind seed gum, chitin (Chitin Liquid ® 111 140), beta-glucan (glucan CM ®), inulin and amylose.
Als wirkungsvoll haben sich auch anionische Polymere erwiesen, die als alleiniges oder Co- Monomer 2-Acrylamido-2-methylpropansulfonsäure enthalten, wobei die Sulfonsäuregruppe ganz oder teilweise als Natrium-, Kalium-, Ammonium-, Mono- oder Triethanolammonium-Salz vorliegen kann.Anionic polymers have also proved to be effective which comprise 2-acrylamido-2-methylpropanesulfonic acid as sole or co-monomer, it being possible for the sulfonic acid group to be wholly or partly present as sodium, potassium, ammonium, mono- or triethanolammonium salt.
Bevorzugt ist dabei das Homopolymer der 2-Acrylamido-2-methylpropansulfonsäure, das beispielsweise unter der Bezeichnung Rheothik®11-80 im Handel erhältlich ist.Preference is given to the homopolymer of 2-acrylamido-2-methyl propane sulfonic acid, which is available for example under the name Rheothik ® 11-80 commercially.
Innerhalb dieser Ausführungsform kann es bevorzugt sein, Copolymere aus mindestens einem anionischen Monomer und mindestens einem nichtionogenen Monomer einzusetzen. Bezüglich der anionischen Monomere wird auf die oben aufgeführten Substanzen verwiesen. Bevorzugte nichtionogene Monomere sind Acrylamid, Methacrylamid, Acrylsäureester, Methacrylsäureester, Vinylpyrrolidon, Vinylether und Vinylester.Within this embodiment, it may be preferable to use copolymers of at least one anionic monomer and at least one nonionic monomer. With regard to the anionic monomers, reference is made to the substances listed above. Preferred nonionic monomers are acrylamide, methacrylamide, acrylic esters, methacrylic esters, vinylpyrrolidone, vinyl ethers and vinyl esters.
Bevorzugte anionische Copolymere sind Acrylsäure-Acrylamid-Copolymere sowie insbesondere Polyacrylamidcopolymere mit Sulfonsäuregruppen-haltigen Monomeren. Ein besonders bevorzugtes anionisches Copolymer besteht aus 70 bis 55 Mol-% Acrylamid und 30 bis 45 Mol-% 2-Acrylamido-2-methylpropansulfonsäure, wobei die Sulfonsäuregruppe ganz oder teilweise als Natrium-, Kalium-, Ammonium-, Mono- oder Triethanolammonium-Salz vorliegt. Dieses Copolymer kann auch vernetzt vorliegen, wobei als Vernetzungsagentien bevorzugt polyolefinisch ungesättigte Verbindungen wie Tetraallyloxyethan, Allylsucrose, Allylpentaerythrit und Methylen- bisacrylamid zum Einsatz kommen. Ein solches Polymer ist in dem Handelsprodukt Sepigel®305 der Firma SEPPIC enthalten. Die Verwendung dieses Compounds, das neben der Polymerkomponente eine Kohlenwasserstoffmischung (C13-C-i4-lsoparaffin) und einen nichtionogenen Emulgator (Laureth-7) enthält, hat sich im Rahmen der erfindungsgemäßen Lehre als besonders vorteilhaft erwiesen.Preferred anionic copolymers are acrylic acid-acrylamide copolymers and in particular polyacrylamide copolymers with sulfonic acid-containing monomers. A particularly preferred anionic copolymer consists of 70 to 55 mol% of acrylamide and 30 to 45 mol% of 2-acrylamido-2-methylpropanesulfonic acid, wherein the sulfonic acid group is wholly or partly in the form of sodium, potassium, ammonium, mono- or triethanolammonium Salt is present. This copolymer may also be crosslinked, with crosslinking agents preferably polyolefinically unsaturated compounds such as tetraallyloxyethane, allylsucrose, allylpentaerythritol and methylenebisacrylamide are used. Such a polymer is contained in the commercial product Sepigel ® 305 from SEPPIC. The use of this compound, which in addition to the polymer component contains a hydrocarbon mixture (C 13 -C 4 -lsoparaffin) and a non-ionic emulsifier (laureth-7), has proved to be particularly advantageous within the scope of the teaching according to the invention.
Auch die unter der Bezeichnung Simulgel®600 als Compound mit Isohexadecan und Polysorbat- 80 vertriebenen Natriumacryloyldimethyltaurat-Copolymere haben sich als erfindungsgemäß besonders wirksam erwiesen.Also sold under the name Simulgel ® 600 as a compound with isohexadecane and polysorbate 80 Natriumacryloyldimethyltaurat copolymers have proven to be particularly effective according to the invention.
Ebenfalls bevorzugte anionische Homopolymere sind unvernetzte und vernetzte Polyacrylsäuren. Dabei können Allylether von Pentaerythrit, von Sucrose und von Propylen bevorzugte Vernetzungsagentien sein. Solche Verbindungen sind beispielsweise unter dem Warenzeichen Carbopol® im Handel erhältlich.Likewise preferred anionic homopolymers are uncrosslinked and crosslinked polyacrylic acids. Allyl ethers of pentaerythritol, sucrose and propylene may be preferred crosslinking agents. Such compounds are for example available under the trademark Carbopol ® commercially.
Copolymere aus Maleinsäureanhydrid und Methylvinylether, insbesondere solche mit Vernetzungen, sind ebenfalls farberhaltende Polymere. Ein mit 1 ,9-Decadiene vernetztes Malein- säure-Methylvinylether-Copolymer ist unter der Bezeichnungg Stabileze® QM im Handel erhältlich.Copolymers of maleic anhydride and methyl vinyl ether, especially those with crosslinks, are also color-retaining polymers. A male compound cross-linked with 1, 9-decadiene acid-methyl vinyl ether copolymer available under the name Stabileze® ® QM.
Weiterhin können als Polymere zur Steigerung der Wirkung des erfindungsgemäßen Wirkstoffes amphotere Polymere als Bestandteil eingesetzt. Unter dem Begriff amphotere Polymere werden sowohl solche Polymere, die im Molekül sowohl freie Aminogruppen als auch freie -COOH- oder SO3H-Gruppen enthalten und zur Ausbildung innerer Salze befähigt sind, als auch zwitterionische Polymere, die im Molekül quartäre Ammoniumgruppen und -COO'- oder -SO3 '-Gruppen enthalten, und solche Polymere zusammengefaßt, die -COOH- oder SO3H-Gruppen und quartäre Ammoniumgruppen enthalten.Furthermore, amphoteric polymers can be used as constituents as polymers for increasing the action of the active ingredient according to the invention. The term amphoteric polymers includes both those polymers which contain in the molecule both free amino groups and free -COOH or SO 3 H groups and are capable of forming internal salts, as well as zwitterionic polymers which in the molecule have quaternary ammonium groups and -COO ' or -SO 3 ' groups, and those polymers comprising -COOH or SO 3 H groups and quaternary ammonium groups.
Ein Beispiel für ein erfindungsgemäß einsetzbares Amphopolymer ist das unter der Bezeichnung Amphomer® erhältliche Acrylharz, das ein Copolymeres aus tert.-Butylaminoethylmethacrylat, N- (1 ,1 ,3,3-Tetramethylbutyl)acrylamid sowie zwei oder mehr Monomeren aus der Gruppe Acrylsäure, Methacrylsäure und deren einfachen Estern darstellt.An example of the present invention amphopolymer suitable is the acrylic resin commercially available as Amphomer ®, which is a copolymer of tert-butylaminoethyl methacrylate, N- (1, 1, 3,3-tetramethylbutyl) -acrylamide and two or more monomers from the group of acrylic acid, Represents methacrylic acid and its simple esters.
Weitere erfindungsgemäß einsetzbare amphotere Polymere sind die in der britischen Offenlegungsschrift 2 104 091 , der europäischen Offenlegungsschrift 47 714, der europäischen Offenlegungsschrift 217 274, der europäischen Offenlegungsschrift 283 817 und der deutschen Offenlegungsschrift 28 17 369 genannten Verbindungen.Further amphoteric polymers which can be used according to the invention are the compounds mentioned in British Patent Application 2,104,091, European Patent Application 47,714, European Offenlegungsschrift 217,274, European Offenlegungsschrift 283,817 and German Offenlegungsschrift 28 17 369.
Bevorzugt eingesetzte amphotere Polymere sind solche Polymerisate, die sich im wesentlichen zusammensetzen ausPreferably used amphoteric polymers are those polymers which are composed essentially
(a) Monomeren mit quartären Ammoniumgruppen der allgemeinen Formel (IV),(a) monomers having quaternary ammonium groups of the general formula (IV),
R22-CH=CR23-CO-Z-(CnH2n)-N(+)R24R25R26 A( ) (IV)R 22 -CH = CR 23 -CO-Z- (C n H 2n ) -N (+) R 24 R 25 R 26 A () (IV)
in der R22 und R23 unabhängig voneinander stehen für Wasserstoff oder eine Methylgruppe und R24, R25 und R26 unabhängig voneinander für Alkylgruppen mit 1 bis 4 Kohlenstoff- Atomen, Z eine NH-Gruppe oder ein Sauerstoffatom, n eine ganze Zahl von 2 bis 5 und A( ) das Anion einer organischen oder anorganischen Säure istin which R 22 and R 23 independently of one another are hydrogen or a methyl group and R 24 , R 25 and R 26 independently of one another are alkyl groups having 1 to 4 carbon atoms, Z is an NH group or an oxygen atom, n is an integer from 2 to 5 and A () is the anion of an organic or inorganic acid
undand
(b) monomeren Carbonsäuren der allgemeinen Formel (V),(b) monomeric carboxylic acids of the general formula (V),
R27-CH=CR28-COOH (V)R 27 -CH = CR 28 -COOH (V)
in denen R27 und R28 unabhängig voneinander Wasserstoff oder Methylgruppen sind. Diese Verbindungen können sowohl direkt als auch in Salzform, die durch Neutralisation der Polymerisate, beispielsweise mit einem Alkalihydroxid, erhalten wird, erfindungsgemäß eingesetzt werden. Bezüglich der Einzelheiten der Herstellung dieser Polymerisate wird ausdrücklich auf den Inhalt der deutschen Offenlegungsschrift 39 29 973 Bezug genommen. Ganz besonders bevorzugt sind solche Polymerisate, bei denen Monomere des Typs (a) eingesetzt werden, bei denen R24, R25 und R26 Methylgruppen sind, Z eine NH-Gruppe und A( ) ein Halogenid-, Methoxysulfat- oder Ethoxysulfat-Ion ist; Acrylamidopropyl-trimethyl-ammoniumchlorid ist ein besonders bevorzugtes Monomeres (a). Als Monomeres (b) für die genannten Polymerisate wird bevorzugt Acrylsäure verwendet.in which R 27 and R 28 are independently hydrogen or methyl groups. These compounds can be used both directly and in salt form, which is obtained by neutralization of the polymers, for example with an alkali metal hydroxide, according to the invention. With regard to the details of the preparation of these polymers is expressly made to the content of German Patent Application 39 29 973 reference. Very particular preference is given to those polymers in which monomers of the type (a) are used in which R 24 , R 25 and R 26 are methyl groups, Z is an NH group and A () is a halide, methoxysulfate or ethoxysulfate ion is; Acrylamidopropyl trimethyl ammonium chloride is a particularly preferred monomer (a). Acrylic acid is preferably used as monomer (b) for the stated polymers.
Die erfindungsgemäßen Mittel können in einer dritten Variante weiterhin nichtionogene Polymere enthalten.In a third variant, the agents according to the invention may furthermore contain nonionogenic polymers.
Geeignete nichtionogene Polymere sind beispielsweise:Suitable nonionic polymers are, for example:
Vinylpyrrolidon/Vinylester-Copolymere, wie sie beispielsweise unter dem Warenzeichen Luviskol® (BASF) vertrieben werden. Luviskol® VA 64 und Luviskol® VA 73, jeweils Vinylpyrrolidon/Vinylacetat-Copolymere, sind ebenfalls bevorzugte nichtionische Polymere. Celluloseether, wie Hydroxypropylcellulose, Hydroxyethylcellulose undVinylpyrrolidone / vinyl ester copolymers, as sold, for example, under the trademark Luviskol ® (BASF). Luviskol ® VA 64 and Luviskol ® VA 73, each vinylpyrrolidone / vinyl acetate copolymers, are also preferred nonionic polymers. Cellulose ethers, such as hydroxypropyl cellulose, hydroxyethyl cellulose and
Methylhydroxypropylcellulose, wie sie beispielsweise unter den Warenzeichen Culminal® und Benecel® (AQUALON) vertrieben werden. SchellackMethylhydroxypropylcellulose, as for example sold under the trademarks Culminal ® and Benecel ® (AQUALON). shellac
Polyvinylpyrrolidone, wie sie beispielsweise unter der Bezeichnung Luviskol® (BASF) vertrieben werden.Polyvinylpyrrolidones, as sold for example under the name Luviskol ® (BASF).
Siloxane. Diese Siloxane können sowohl wasserlöslich als auch wasserunlöslich sein. Geeignet sind sowohl flüchtige als auch nichtflüchtige Siloxane, wobei als nichtflüchtige Siloxane solche Verbindungen verstanden werden, deren Siedepunkt bei Normaldruck oberhalb von 200 0C liegt. Bevorzugte Siloxane sind Polydialkylsiloxane, wie beispielsweise Polydimethylsiloxan, Polyalkylarylsiloxane, wie beispielsweise Polyphenylmethylsiloxan, ethoxylierte Polydialkylsiloxane sowie Polydialkylsiloxane, die Amin- und/oder Hydroxy- Gruppen enthalten. Glycosidisch substituierte Silicone gemäß der EP 0612759 B1.Siloxanes. These siloxanes can be both water-soluble and water-insoluble. Both volatile and nonvolatile siloxanes are suitable, nonvolatile siloxanes being understood as meaning those compounds whose boiling point is above 200 ° C. under normal pressure. Preferred siloxanes are polydialkylsiloxanes, such as, for example, polydimethylsiloxane, polyalkylarylsiloxanes, such as, for example, polyphenylmethylsiloxane, ethoxylated polydialkylsiloxanes and polydialkylsiloxanes which contain amine and / or hydroxyl groups. Glycosidically substituted silicones according to EP 0612759 B1.
Es ist erfindungsgemäß auch möglich, daß die verwendeten Zubereitungen mehrere, insbesondere zwei verschiedene Polymere gleicher Ladung und/oder jeweils ein ionisches und ein amphoteres und/oder nicht ionisches Polymer enthalten.It is also possible according to the invention that the preparations used contain a plurality of, in particular two different polymers of the same charge and / or in each case an ionic and an amphoteric and / or nonionic polymer.
Unter dem Begriff Polymer sind erfindungsgemäß ebenfalls spezielle Zubereitungen von Polymeren wie sphärische Polymerpulver zu verstehen. Es sind verschiedene Verfahren bekannt, solche Mikrokugeln aus verschiedenen Monomeren herzustellen, z.B. durch spezielle Polymerisationsverfahren oder durch Auflösen des Polymeren in einem Lösungsmittel und Versprühen in ein Medium, in dem das Lösungsmittel verdunsten oder aus den Teilchen herausdiffundieren kann. Ein solches Verfahren ist z.B. aus EP 466 986 B1 bekannt. Geeignete Polymerisate sind z.B. Polycarbonate, Polyurethane, Polyacrylate, Polyolefine, Polyester oder Polyamide. Besonders geeignet sind solche sphärischen Polymerpulver, deren Primärpartikeldurchmesser unter 1 μm liegt. Solche Produkte auf Basis eines Polymethacrylat- Copolymers sind z.B. unter dem Warenzeichen Polytrap®Q5-6603 (Dow Corning) im Handel. Andere Polymerpulver, z.B. auf Basis von Polyamiden (Nylon 6, Nylon 12) sind mit einer Teilchengröße von 2 - 10 μm (90 %) und einer spezifischen Oberfläche von ca. 10 m2/g unter der Handelsbezeichnung Orgasol® 2002 DU Nat Cos (Atochem S.A., Paris) erhältlich. Weitere sphärische Polymerpulver, die für den erfindungsgemäßen Zweck geeignet sind, sind z.B. die Polymethacrylate (Micropearl M) von SEPPIC oder (Plastic Powder A) von NIKKOL, die Styrol- Divinylbenzol-Copolymeren (Plastic Powder FP) von NIKKOL, die Polyethylen- und Polypropylen- Pulver (ACCUREL EP 400) von AKZO, oder auch Silikonpolymere (Silicone Powder X2-1605) von Dow Corning oder auch sphärische Cellulosepulver.According to the invention, the term polymer also means special preparations of polymers, such as spherical polymer powders. Various methods are known for producing such microspheres from different monomers, for example by special polymerization processes or by dissolving the polymer in a solvent and spraying it into a medium in which the solvent evaporates or from the particles can diffuse out. Such a method is known, for example, from EP 466 986 B1. Suitable polymers are, for example, polycarbonates, polyurethanes, polyacrylates, polyolefins, polyesters or polyamides. Particularly suitable are those spherical polymer powders whose primary particle diameter is less than 1 micron. Such products based on a polymethacrylate copolymer are, for example, under the trademark Polytrap ® Q5-6603 (Dow Corning) in the trade. Other polymer powders, for example based on polyamides (nylon 6, nylon 12) having a particle size of 2 - (10 microns (90%) and a specific surface area of about 10 m 2 / g under the trade name Orgasol ® 2002 DU Nat Cos Atochem SA, Paris). Further spherical polymer powders which are suitable for the purpose according to the invention are, for example, the polymethacrylates (Micropearl M) from SEPPIC or (Plastic Powder A) from NIKKOL, the styrene-divinylbenzene copolymers (Plastic Powder FP) from NIKKOL, the polyethylene and polypropylene AKZO powder (ACCUREL EP 400) or silicone polymers (Silicone Powder X2-1605) from Dow Corning or spherical cellulose powders.
Die Polymere sind in den erfindungsgemäß verwendeten Mitteln bevorzugt in Mengen von 0,01 bis 10 Gew.-%, bezogen auf das gesamte Mittel, enthalten. Mengen von 0,1 bis 5, insbesondere von 0,1 bis 3 Gew.-%, sind besonders bevorzugt.The polymers are preferably contained in the agents used according to the invention in amounts of from 0.01 to 10% by weight, based on the total agent. Amounts of 0.1 to 5, in particular from 0.1 to 3 wt .-%, are particularly preferred.
Silikone etcSilicones etc
Die erfindungsgemäßen Effekte können in synergistischer Weise gesteigert werden, wenn die erfindungsgemäßen Mittel zusätzlich mindestens eine weitere Komponente enthalten, die ausgewählt wird, aus mindestens einem Vertreter der Gruppe, die gebildet wird, aus d ) Proteinhydrolysaten, c2) Silikonderivaten und c3) (Pseudo)Ceramide.The effects according to the invention can be increased in a synergistic manner if the agents according to the invention additionally comprise at least one further component which is selected from at least one member of the group which is formed from d) protein hydrolysates, c2) silicone derivatives and c3) (pseudo) ceramides.
Die Proteinhydrolysate d ) sind Produktgemische, die durch sauer, basisch oder enzymatisch katalysierten Abbau von Proteinen (Eiweißen) erhalten werden.The protein hydrolyzates d) are product mixtures which are obtained by acid, alkaline or enzymatically catalyzed degradation of proteins (proteins).
Erfindungsgemäß können Proteinhydrolysate sowohl pflanzlichen als auch tierischen Ursprungs eingesetzt werden.According to the invention, protein hydrolysates of both vegetable and animal origin can be used.
Tierische Proteinhydrolysate sind beispielsweise Elastin-, Kollagen-, Keratin-, Seiden- und Milch- eiweiß-Proteinhydrolysate, die auch in Form von Salzen vorliegen können. Solche Produkte werden beispielsweise unter den Warenzeichen Keratin DEC® (Vincience), Dehylan® (Cognis), Promois® (Interorgana), Collapuron® (Cognis), Nutrilan® (Cognis), Gelita-Sol® (Deutsche Gelatine Fabriken Stoess & Co), Lexein® (Inolex) und Kerasol® (Croda) vertrieben.Animal protein hydrolysates are, for example, elastin, collagen, keratin, silk and milk protein protein hydrolysates, which may also be present in the form of salts. Such products are, for example, under the trademarks keratin DEC ® (Vincience) Dehylan ® (Cognis), Promois® ® (Interorgana) Collapuron ® (Cognis), Nutrilan® ® (Cognis), Gelita-Sol ® (German Gelatinefabriken Stoess & Co) distributed Lexein ® (Inolex) and kerasol tm ® (Croda).
Erfindungsgemäß bevorzugt ist die Verwendung von Proteinhydrolysaten pflanzlichen Ursprungs, z. B. Soja-, Mandel-, Reis-, Erbsen-, Kartoffel- und Weizenproteinhydrolysate. Solche Produkte sind beispielsweise unter den Warenzeichen Gluadin® (Cognis), DiaMin® (Diamalt), Lexein® (Inolex) und Crotein® (Croda) erhältlich.Preferred according to the invention is the use of protein hydrolysates of plant origin, eg. Soybean, almond, rice, pea, potato and wheat protein hydrolysates. Such products are, for example, under the trademarks Gluadin ® (Cognis), diamine ® (Diamalt) ® (Inolex) and Crotein ® (Croda) available.
Wenngleich der Einsatz der Proteinhydrolysate als solche bevorzugt ist, können an deren Stelle gegebenenfalls auch anderweitig erhaltene Aminosäuregemische oder einzelne Aminosäuren wie beispielsweise Arginin, Lysin, Histidin oder Pyrroglutaminsäure eingesetzt werden. Ebenfalls möglich ist der Einsatz von Derivaten der Proteinhydrolysate, beispielsweise in Form ihrer Fettsäure-Kondensationsprodukte. Solche Produkte werden beispielsweise unter den Bezeichnungen Lamepon® (Cognis), Gluadin® (Cognis), Lexein® (Inolex), Crolastin® (Croda) oder Crotein® (Croda) vertrieben.Although the use of the protein hydrolysates is preferred as such, amino acid mixtures or individual amino acids obtained otherwise, such as, for example, arginine, lysine, histidine or pyrroglutamic acid, may also be used in their place. Also possible is the use of derivatives of protein hydrolysates, for example in the form of their fatty acid condensation products. Such products are marketed for example under the names Lamepon ® (Cognis), Gluadin ® (Cognis), Lexein ® (Inolex), Crolastin ® (Croda) or Crotein ® (Croda).
Bevorzugt sind die Proteinhydrolysate in einer Menge von 0,05 bis 5 Gew.-%, besonders bevorzugt von 0,5 bis 2,0 Gew.-%, jeweils bezogen auf das Gewicht des anwendungsbereiten Mittels, enthalten.Preferably, the protein hydrolysates in an amount of 0.05 to 5 wt .-%, particularly preferably from 0.5 to 2.0 wt .-%, each based on the weight of the ready-to-use agent included.
Die Silikonderivate c2) sind, wenn sie in den erfindungsgemäß eingesetzten Mitteln zugegen sind, vorzugsweise in Mengen von 0,05 bis 5 Gew.-%, vorzugsweise von 0,2 bis 5 Gew.-%, jeweils bezogen auf das anwendungsbereite Mittel, enthalten.The silicone derivatives c2), when present in the agents used according to the invention, are preferably present in amounts of from 0.05 to 5% by weight, preferably from 0.2 to 5% by weight, based in each case on the ready-to-use agent ,
Insbesondere bevorzugt werden die Silikone c2) ausgewählt, aus mindestens einem Vertreter aus der Liste, die gebildet wird aus:More preferably, the silicones c2) are selected from at least one member of the list formed from:
(i) Polyalkylsiloxanen, Polyarylsiloxanen, Polyalkylarylsiloxanen, die flüchtig oder nicht flüchtig, geradkettig, verzweigt oder cyclisch, vernetzt oder nicht vernetzt sind;(i) polyalkyl siloxanes, polyaryl siloxanes, polyalkylaryl siloxanes which are volatile or nonvolatile, straight chain, branched or cyclic, crosslinked or uncrosslinked;
(ii) Polysiloxanen, die in ihrer allgemeinen Struktur eine oder mehrere organofunktionelle Gruppen enthalten, die ausgewählt sind unter: a) substituierten oder unsubstituierten aminierten Gruppen; b) (per)fluorierten Gruppen; c) Thiolgruppen; d) Carboxylatgruppen; e) hydroxylierten Gruppen; f) alkoxylierten Gruppen; g) Acyloxyalkylgruppen; h) amphoteren Gruppen; i) Bisulfitgruppen; j) Hydroxyacylaminogruppen; k) Carboxygruppen;(ii) polysiloxanes containing in their general structure one or more organofunctional groups selected from: a) substituted or unsubstituted aminated groups; b) (per) fluorinated groups; c) thiol groups; d) carboxylate groups; e) hydroxylated groups; f) alkoxylated groups; g) acyloxyalkyl groups; h) amphoteric groups; i) bisulfite groups; j) hydroxyacylamino groups; k) carboxy groups;
I) Sulfonsäuregruppen; und m) Sulfat- oder Thiosulfatgruppen;I) sulfonic acid groups; and m) sulfate or thiosulfate groups;
(iii) linearen Polysiloxan(A)- Polyoxyalkylen(B)- Blockcopoylmeren vom Typ (A-B)n mit n > 3; (iv) gepfropften Silikonpolymeren mit nicht silikonhaltigem, organischen Grundgerüst, die aus einer organischen Hauptkette bestehen, welche aus organischen Monomeren gebildet wird, die kein Silikon enthalten, auf die in der Kette sowie gegebenenfalls an mindestens einem Kettenende mindestens ein Polysiloxanmakromer gepfropft wurde;(iii) linear polysiloxane (A) - polyoxyalkylene (B) - block copolymers of the type (AB) n with n>3; (iv) grafted silicone polymers having a non-silicone-containing organic backbone consisting of an organic backbone formed from organic monomers, which contain no silicone to which at least one polysiloxane macromer has been grafted in the chain and optionally on at least one chain end;
(v) gepfropften Silikonpolymeren mit Polysiloxan-Grundgerüst, auf das nicht silikonhaltige, organische Monomere gepfropft wurden, die eine Polysiloxan-Hauptkette aufweisen, auf die in der Kette sowie gegebenenfalls an mindestens einem ihrer Enden mindestens ein organisches Makromer gepfropft wurde, das kein Silikon enthält, wie beispielsweise das unter der INCI-Bezeichnung Bis-PEG/PPG-20/20 Dimethicone vertriebene Handelsprodukt Abil B 8832 der Firma Degussa;(v) grafted polysiloxane backbone silicone polymers having grafted thereto non-silicone-containing organic monomers having a polysiloxane backbone to which at least one organic macromer containing no silicone has been grafted in the chain, and optionally at least at one of its ends , such as the commercial product Abil B 8832 from Degussa marketed under the INCI name Bis-PEG / PPG-20/20 dimethicone;
(vi) oder deren Gemischen.(vi) or mixtures thereof.
Besonders bevorzugte erfindungsgemäße kosmetische oder dermatologische Zubereitungen sind dadurch gekennzeichnet, dass sie mindestens ein Silikon der Formel (Si-1 )Particularly preferred cosmetic or dermatological preparations according to the invention are characterized in that they contain at least one silicone of the formula (Si-1)
(CH3)3Si-[O-Si(CH3)2]χ-O-Si(CH3)3 (Si-1 ),(CH 3 ) 3 Si - [O-Si (CH 3 ) 2] χ-O-Si (CH 3 ) 3 (Si-1),
enthalten, in der x für eine Zahl von 0 bis 100, vorzugsweise von 0 bis 50, weiter bevorzugt von 0 bis 20 und insbesondere 0 bis 10, steht.in which x is a number from 0 to 100, preferably from 0 to 50, more preferably from 0 to 20 and in particular 0 to 10.
Die erfindungsgemäß eingesetzten, bevorzugten kosmetischen oder dermatologischen Zubereitungen enthalten ein Silikon der vorstehenden Formel (Si-1 ). Diese Silikone werden nach der INCI-Nomenklatur als Dimethicone bezeichnet. Es werden im Rahmen der vorliegenden Erfindung als Silikon der Formel (Si-1 ) vorzugsweise die Verbindungen:
Figure imgf000064_0001
The preferred cosmetic or dermatological preparations used according to the invention comprise a silicone of the above formula (Si-1). These silicones are referred to as dimethicones according to the INCI nomenclature. It is in the context of the present invention as the silicone of the formula (Si-1), preferably the compounds:
Figure imgf000064_0001
(CH3)3Si-O-(CH3)2Si-O-Si(CH3)3 (CH 3 ) 3 Si-O- (CH 3 ) 2 Si-O-Si (CH 3 ) 3
(CH3)3Si-[O-(CH3)2Si]2-O-Si(CH3)3 (CH 3 ) 3 Si [O- (CH 3 ) 2 Si] 2 -O-Si (CH 3 ) 3
(CH3)3Si-[O-(CH3)2Si]3-O-Si(CH3)3 (CH 3 ) 3 Si [O- (CH 3 ) 2 Si] 3 -O-Si (CH 3 ) 3
(CH3)3Si-[O-(CH3)2Si]4-O-Si(CH3)3 (CH 3 ) 3 Si [O- (CH 3 ) 2 Si] 4 -O-Si (CH 3 ) 3
(CH3)3Si-[O-(CH3)2Si]5-O-Si(CH3)3 (CH 3 ) 3 Si [O- (CH 3 ) 2 Si] 5 -O-Si (CH 3 ) 3
(CH3)3Si-[O-(CH3)2Si]6-O-Si(CH3)3 (CH 3 ) 3 Si [O- (CH 3 ) 2 Si] 6 -O-Si (CH 3 ) 3
(CH3)3Si-[O-(CH3)2Si]7-O-Si(CH3)3 (CH 3 ) 3 Si [O- (CH 3 ) 2 Si] 7 -O-Si (CH 3 ) 3
(CH3)3Si-[O-(CH3)2Si]8-O-Si(CH3)3 (CH 3 ) 3 Si [O- (CH 3 ) 2 Si] 8 -O-Si (CH 3 ) 3
(CH3)3Si-[O-(CH3)2Si]9-O-Si(CH3)3 (CH 3 ) 3 Si [O- (CH 3 ) 2 Si] 9 -O-Si (CH 3 ) 3
(CH3)3Si-[O-(CH3)2Si]10-O-Si(CH3)3 (CH 3 ) 3 Si [O- (CH 3 ) 2 Si] 10 -O-Si (CH 3 ) 3
(CH3)3Si-[O-(CH3)2Si]11-O-Si(CH3)3 (CH 3 ) 3 Si [O- (CH 3 ) 2 Si] 11 -O-Si (CH 3 ) 3
(CH3)3Si-[O-(CH3)2Si]12-O-Si(CH3)3 (CH 3 ) 3 Si [O- (CH 3 ) 2 Si] 12 -O-Si (CH 3 ) 3
(CH3)3Si-[O-(CH3)2Si]13-O-Si(CH3)3 (CH 3 ) 3 Si [O- (CH 3 ) 2 Si] 13 -O-Si (CH 3 ) 3
(CH3)3Si-[O-(CH3)2Si]14-O-Si(CH3)3 (CH 3 ) 3 Si [O- (CH 3 ) 2 Si] 14 -O-Si (CH 3 ) 3
(CH3)3Si-[O-(CH3)2Si]15-O-Si(CH3)3 (CH 3 ) 3 Si [O- (CH 3 ) 2 Si] 15 -O-Si (CH 3 ) 3
(CH3)3Si-[O-(CH3)2Si]16-O-Si(CH3)3 (CH 3 ) 3 Si [O- (CH 3 ) 2 Si] 16 -O-Si (CH 3 ) 3
(CH3)3Si-[O-(CH3)2Si]17-O-Si(CH3)3 (CH3)3Si-[O-(CH3)2Si]18-O-Si(CH3)3 (CH3)3Si-[O-(CH3)2Si]19-O-Si(CH3)3 (CH3)3Si-[0-(CH3)2Si]2o-0-Si(CH3)3(CH 3 ) 3 Si [O- (CH 3 ) 2 Si] 17 -O-Si (CH 3 ) 3 (CH 3 ) 3 Si - [O - (CH 3 ) 2 Si] 18 - O - Si (CH 3 ) 3 (CH 3 ) 3 Si - [O - (CH 3 ) 2 Si] 19 - O - Si (CH 3 ) 3 (CH 3 ) 3Si- [0- (CH 3 ) 2 Si] 2 o-O-Si (CH 3 ) 3
eingesetzt, wobei (CH3)3Si-O-Si(CH3)3, (CH3)3Si-O-(CH3)2Si-O-Si(CH3)3 und/oder (CH3)3Si-[O- (CH3)2Si]2-O-Si(CH3)3 besonders bevorzugt sind.where (CH 3 ) 3 Si-O-Si (CH 3 ) 3, (CH 3 ) 3 Si-O- (CH 3 ) 2 Si-O-Si (CH 3 ) 3 and / or (CH 3 ) 3 Si [ O- (CH 3 ) 2 Si] 2 -O-Si (CH 3 ) 3 are particularly preferred.
Selbstverständlich können auch Mischungen der o.g. Silikone in den bevorzugten erfindungsgemäßen Mitteln enthalten sein.Of course, mixtures of o.g. Silicones may be included in the preferred compositions of the invention.
Bevorzugte erfindungsgemäß einsetzbare Silikone weisen bei 200C Viskositäten von 0,2 bis 2 mmV1 auf, wobei Silikone mit Viskositäten von 0,5 bis 1 mmV1 besonders bevorzugt sind.Preferred according to the invention can be used silicones have viscosities at 20 0 C for from 0.2 to 2 mmV 1, wherein silicones having viscosities of 0.5 to 1 mmV 1 are particularly preferred.
Besonders bevorzugte erfindungsgemäße Mittel enthalten ein oder mehrere aminofunktionelle Silikone. Solche Silikone können z.B. durch die Formel (Si-2)Particularly preferred agents according to the invention contain one or more amino-functional silicones. Such silicones may e.g. by the formula (Si-2)
M(RaQbSi0(4-a-b),2)x(RcSi0(4-c)/2)yM (Si-2)M (R a Q b Si0 (4 - a - b) , 2 ) x (R c Si0 (4 - c) / 2 ) y M (Si-2)
Beschrieben werden, wobei in der obigen FormelBe described, taking in the above formula
R ein Kohlenwasserstoff oder ein Kohlenwasserstoffrest mit 1 bis etwa 6R is a hydrocarbon or a hydrocarbon radical having from 1 to about 6
Kohlenstoffatomen ist, Q ein polarer Rest der allgemeinen Formel -R1HZ ist, worinCarbon atoms, Q is a polar radical of the general formula -R 1 HZ, wherein
R1 eine zweiwertige, verbindende Gruppe ist, die an Wasserstoff und den Rest Z gebunden ist, zusammengesetzt aus Kohlenstoff- und Wasserstoffatomen, Kohlenstoff-, Wasserstoff- und Sauerstoffatomen oder Kohlenstoff-, Wasserstoff- und Stickstoffatomen, undR 1 is a divalent linking group bonded to hydrogen and the radical Z composed of carbon and hydrogen atoms, carbon, hydrogen and oxygen atoms or carbon, hydrogen and nitrogen atoms, and
Z ein organischer, aminofunktioneller Rest ist, der mindestens eine aminofunktionelle Gruppe enthält; a Werte im Bereich von etwa 0 bis etwa 2 annimmt, b Werte im Bereich von etwa 1 bis etwa 3 annimmt, a + b kleiner als oder gleich 3 ist, und c eine Zahl im Bereich von etwa 1 bis etwa 3 ist, und x eine Zahl im Bereich von 1 bis etwa 2.000, vorzugsweise von etwa 3 bis etwa 50 und am bevorzugtesten von etwa 3 bis etwa 25 ist, und y eine Zahl im Bereich von etwa 20 bis etwa 10.000, vorzugsweise von etwa 125 bis etwa 10.000 und am bevorzugtesten von etwa 150 bis etwa 1.000 ist, und M eine geeignete Silikon-Endgruppe ist, wie sie im Stande der Technik bekannt ist, vorzugsweise Trimethylsiloxy. Nicht einschränkende Beispiele der in Formel (Si-2) durch R repräsentierten Reste schließen Alkylreste, wie Methyl, Ethyl, Propyl, Isopropyl, Isopropyl, Butyl, Isobutyl, Amyl, Isoamyl, Hexyl, Isohexyl und ähnliche; Alkenylreste, wie Vinyl, Halogenvinyl, Alkylvinyl, AIIyI, Halogenallyl, Alkylallyl; Cycloalkylreste, wie Cyclobutyl, Cyclopentyl, Cyclohexyl und ähnliche; Phenylreste, Benzylreste, Halogenkohlenwasserstoffreste, wie 3- Chlorpropyl, 4-Brombutyl, 3,3,3-Trifluor- propyl, Chlorcyclohexyl, Bromphenyl, Chlorphenyl und ähnliche sowie schwefelhaltige Reste, wie Mercaptoethyl, Mercaptopropyl, Mercaptohexyl, Mercaptophenyl und ähnliche ein; vorzugsweise ist R ein Alkylrest, der 1 bis etwa 6 Kohlenstoffatomen enthält, und am bevorzugtesten ist R Methyl. Beispiele von R1 schließen Methylen, Ethylen, Propylen, Hexamethylen, Decamethylen, - CH2CH(CH3)CH2-, Phenylen, Naphthylen, -CH2CH2SCH2CH 2-, -CH2CH2OCH2-, -OCH2CH2-, - OCH2 CH2CH2-, -CH2CH(CH3)C(O)OCH2-, -(CHz)3 CC(O)OCH2CH2-, -C6H 4C6H4-, -C6H 4CH2C6H4-; und -(CH 2)3C(O)SCH2CH2- ein.Z is an organic, amino-functional group containing at least one amino-functional group; a assumes values in the range of about 0 to about 2, b takes values in the range of about 1 to about 3, a + b is less than or equal to 3, and c is a number in the range of about 1 to about 3, and x a number ranging from 1 to about 2,000, preferably from about 3 to about 50, and most preferably from about 3 to about 25; and y is a number ranging from about 20 to about 10,000, preferably from about 125 to about 10,000 and most preferably from about 150 to about 1000, and M is a suitable silicone end group as known in the art, preferably trimethylsiloxy. Non-limiting examples of the groups represented by R in formula (Si-2) include alkyl groups such as methyl, ethyl, propyl, isopropyl, isopropyl, butyl, isobutyl, amyl, isoamyl, hexyl, isohexyl and the like; Alkenyl radicals such as vinyl, halovinyl, alkylvinyl, allyl, haloallyl, alkylallyl; Cycloalkyl radicals such as cyclobutyl, cyclopentyl, cyclohexyl and the like; Phenyl radicals, benzyl radicals, halohydrocarbon radicals such as 3-chloropropyl, 4-bromobutyl, 3,3,3-trifluoropropyl, chlorocyclohexyl, bromophenyl, chlorophenyl and the like, and sulfur-containing radicals such as mercaptoethyl, mercaptopropyl, mercaptohexyl, mercaptophenyl and the like; preferably R is an alkyl radical containing from 1 to about 6 carbon atoms, and most preferably R is methyl. Examples of R 1 include methylene, ethylene, propylene, hexamethylene, decamethylene, - CH 2 CH (CH 3 ) CH 2 -, phenylene, naphthylene, -CH 2 CH 2 SCH 2 CH 2 -, -CH 2 CH 2 OCH 2 - , -OCH 2 CH 2 -, - OCH 2 CH 2 CH 2 -, -CH 2 CH (CH 3 ) C (O) OCH 2 -, - (CHz) 3 CC (O) OCH 2 CH 2 -, -C 6 H 4 C 6 H 4 -, -C 6 H 4 CH 2 C 6 H 4 -; and - (CH 2 ) 3 C (O) SCH 2 CH 2 -.
Z ist gemäß Formel (Si-2) ein organischer, aminofunktioneller Rest, enthaltend mindestens eine funktionelle Aminogruppe. Eine mögliche Formel für besagtes Z ist NH(CH2)ZNH2, worin z eine ganze Zahl von größer gleich 1 ist. Eine andere mögliche Formel für besagtes Z ist -NH(CH2)Z(CH 2)ZZNH, worin sowohl z als auch zz unabhängig voneinander eine ganze Zahl von größer gleich 1 sind, wobei diese Struktur Diamino-Ringstrukturen umfasst, wie Piperazinyl. Besagtes Z ist am bevorzugtesten ein -NHCH2CH 2NH2-Rest. Eine andere mögliche Formel für besagtes Z ist -N(CH2)Z(CH2)ZZNX2 oder -NX2, worin jedes X von X2 unabhängig ausgewählt ist aus der Gruppe bestehend aus Wasserstoff und Alkylgruppen mit 1 bis 12 Kohlenstoffatomen, und zz O ist.Z is according to formula (Si-2) an organic, amino-functional radical containing at least one functional amino group. A possible formula for said Z is NH (CH 2 ) Z NH 2 , where z is an integer greater than or equal to 1. Another possible formula for said Z is -NH (CH 2 ) Z (CH 2 ) ZZ NH, wherein both z and zz independently of one another are an integer greater than or equal to 1, this structure comprising diamino ring structures, such as piperazinyl. Said Z is most preferably an -NHCH 2 CH 2 NH 2 radical. Another possible formula for said Z is -N (CH 2 ) Z (CH 2 ) ZZ NX 2 or -NX 2 , wherein each X of X 2 is independently selected from the group consisting of hydrogen and alkyl groups of 1 to 12 carbon atoms, and zz is O
Q gemäß Formel (Si-2) ist am bevorzugtesten ein polarer aminofunktioneller Rest der Formel - CH2CH2CH2NHCH2CH2NH 2.Q according to formula (Si-2) is most preferably a polar amino-functional radical of formula - CH 2 CH 2 CH 2 NH 2 CH 2 CH 2 NH 2 .
In der Formel (Si-2) nimmt a Werte im Bereich von O bis 2 an, b nimmt Werte im Bereich von 2 bis 3 an, a + b ist kleiner als oder gleich 3, und c ist eine Zahl im Bereich von 1 bis 3. Das molare Verhältnis der RaQb SiO(4.a.b)/2-Einheiten zu den R0SiO (4.C)/2-Einheiten in Formel (Si-2) liegt im Bereich von etwa 1 : 2 bis 1 : 65, vorzugsweise von etwa 1 : 5 bis etwa 1 : 65 und am bevorzugtesten von etwa 1 : 15 bis etwa 1 : 20. Werden ein oder mehrere Silikone der obigen Formel (Si-2) eingesetzt, dann können die verschiedenen variablen Substituenten in der obigen Formel bei den verschiedenen Silikonkomponenten, die in der Silikonmischung vorhanden sind, verschieden sein.In the formula (Si-2), α takes values in the range of 0 to 2, b takes values in the range of 2 to 3, a + b is less than or equal to 3, and c is a number in the range of 1 to 3. The molar ratio of the R a Q b SiO (4 a a b) / 2 units to the R 0 SiO (4 C) / 2 units in formula (Si-2) is in the range of about 1: From 2 to 1: 65, preferably from about 1: 5 to about 1:65, and most preferably from about 1:15 to about 1: 20. If one or more of the above formula (Si-2) silicones are used then the various variable substituents in the above formula may be different for the various silicone components present in the silicone blend.
Bevorzugte erfindungsgemäß eingesetzte, kosmetische oder dermatologische Zubereitungen enthalten ein aminofunktionelles Silikon der Formel (Si-3)Preferred cosmetic or dermatological preparations used according to the invention comprise an amino-functional silicone of the formula (Si-3)
R'aG3_a-Si(OSiG 2)n-(OSiG bR'2_ b)m-O-SiG3_a-R'a (Si-3),R 'a G 3 _ a -Si (OSiG 2) n - (OSiG b R' 2 _ b) m -O-SiG 3 _ a -R 'a (Si-3),
worin bedeutet: G ist -H, eine Phenylgruppe, -OH, -0-CH3, -CH3, -0-CH2CH3, -CH2CH3, -0-CH2CH2CH3, -CH2CH2CH3, -O~CH(Cπ3)2, -CH (C H 3)2, -O-CH2CH2CH2CH3, -CH2CH2CH2CH3, -O-CH2CH(CH3)2, -CH2CH(CH3)2, -0-CH(CH3)CH2CH3, -CH(CH3)CH2CH3, -0-C(CH3)3, -C(CH3)3 ; a steht für eine Zahl zwischen O und 3, insbesondere O; b steht für eine Zahl zwischen O und 1 , insbesondere 1 , m und n sind Zahlen, deren Summe (m + n) zwischen 1 und 2000, vorzugsweise zwischen 50 und 150 beträgt, wobei n vorzugsweise Werte von 0 bis 1999 und insbesondere von 49 bis 149 und m vorzugsweise Werte von 1 bis 2000, insbesondere von 1 bis 10 annimmt,where: G is -H, a phenyl group, -OH, -O-CH 3 , -CH 3 , -O-CH 2 CH 3 , -CH 2 CH 3 , -O-CH 2 CH 2 CH 3 , -CH 2 CH 2 CH 3 , -O-CH (Cπ 3 ) 2 , -CH (CH 3 ) 2 , -O-CH 2 CH 2 CH 2 CH 3 , -CH 2 CH 2 CH 2 CH 3 , -O-CH 2 CH ( CH 3 ) 2 , -CH 2 CH (CH 3 ) 2 , -O-CH (CH 3 ) CH 2 CH 3 , -CH (CH 3 ) CH 2 CH 3 , -O-C (CH 3 ) 3 , - C (CH 3 ) 3 ; a is a number between O and 3, in particular O; b is a number between O and 1, in particular 1, m and n are numbers whose sum (m + n) is between 1 and 2000, preferably between 50 and 150, where n is preferably values from 0 to 1999 and in particular from 49 to 149 and m preferably assumes values from 1 to 2000, in particular from 1 to 10,
R' ist ein monovalenter Rest ausgewählt aus -Q-N(R")-CH2-CH2-N(R")2 -Q-N(FT)2 -Q-N+(R")3A- -Q-N+H(R")2 A" -Q-N+H2(R")A" -Q-N(R")-CH2-CH2-N+R"H2A" , wobei jedes Q für eine chemische Bindung, -CH2-, -CH2-CH2-, -CH2CH2CH2-, -C(CHs)2-, -CH2CH2CH2CH2-, -CH2C(CH3)2-, -CH(CHs)CH2CH2- steht, R" für gleiche oder verschiedene Reste aus der Gruppe -H, -Phenyl, -Benzyl, -CH2- CH(CH3)Ph, der C-|.20-Alkylreste, vorzugsweise -CH3, -CH2CH3, -CH2CH2CH3, - CH(CH3)2, -CH2CH2CH2H3, -CH2CH(CH3)2, -CH(CH3)CH2CH3, -C(CH3)3, steht und A ein Anion repräsentiert, welches vorzugsweise ausgewählt ist aus Chlorid, Bromid, lodid oder Methosulfat.R ' is a monovalent radical selected from -QN (R ") - CH 2 -CH 2 -N (R") 2 -QN (FT) 2 -QN + (R ") 3 A- -QN + H (R" ) 2 a "QN + H 2 (R") a "-QN (R") - CH 2 -CH 2 -N + R "H 2 a", each Q is a chemical bond, -CH 2 -, -CH 2 -CH 2 -, -CH 2 CH 2 CH 2 -, -C (CH 2 ) 2 -, -CH 2 CH 2 CH 2 CH 2 -, -CH 2 C (CH 3 ) 2 -, -CH ( CHs) CH 2 CH 2 -, R "represents identical or different radicals from the group -H, -phenyl, -benzyl, -CH 2 - (CH CH 3) Ph, the C- | 20 -alkyl, preferably -. CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , - CH (CH 3 ) 2 , -CH 2 CH 2 CH 2 H 3 , -CH 2 CH (CH 3 ) 2 , -CH (CH 3 ) CH 2 CH 3 , -C (CH 3 ) 3 , and A represents an anion, which is preferably selected from chloride, bromide, iodide or methosulfate.
Erfindungsgemäß geeignet sind kationische Silikonöle wie beispielsweise die im Handel erhältliche Dow Corning 929 Emulsion (enthaltend ein hydroxylamino-modifiziertes Silikon, das als Amodimethicone bezeichnet wird), DC 2-2078 (Hersteller Dow Corning, INCI-Bezeichung: Aminopropyl Phenyl Trimethicone), DC 5-7113 (Hersteller Dow Corning, INCI-Bezeichnung: Silicone Quaternium 16), SM-2059 (Hersteller: General Electric), SLM-55067 (Hersteller: Wacker) sowie Abil®-Quat 3270 und 3272 (Hersteller: Th. Goldschmidt; diquaternäre Polydimethylsiloxane, Quaternium-80).Cationic silicone oils, such as the commercially available Dow Corning 929 emulsion (containing a hydroxylamino-modified silicone referred to as amodimethicone), DC 2-2078 (manufactured by Dow Corning, INCI: aminopropyl phenyl trimethicone), DC 5, are suitable according to the invention -7113 (manufacturer Dow Corning, INCI name: Silicone Quaternium 16), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil ® quat 3270 and 3272 (manufacturer: Th Goldschmidt; diquaternary. Polydimethylsiloxanes, quaternium-80).
Besonders bevorzugte, erfindungsgemäße Mittel sind dadurch gekennzeichnet, dass sie mindestens es ein aminofunktionelles Silikon der Formel (Si3-a)Particularly preferred agents according to the invention are characterized in that they contain at least one amino-functional silicone of the formula (Si 3-a)
(CH3)3Si-[O-Si(CH3)2]n[O-Si(CH3)]m-OSi(CH3)3 (Si-3a),(CH 3 ) 3 Si [O-Si (CH 3 ) 2 ] n [O-Si (CH 3 )] m -OSi (CH 3 ) 3 (Si-3a),
II
CH2CH(CH3)CH2NH(CH2)2NH2 enthalten, worin m und n Zahlen sind, deren Summe (m + n) zwischen 1 und 2000, vorzugsweise zwischen 50 und 150 beträgt, wobei n vorzugsweise Werte von 0 bis 1999 und insbesondere von 49 bis 149 und m vorzugsweise Werte von 1 bis 2000, insbesondere von 1 bis 10 annimmt.CH 2 CH (CH 3 ) CH 2 NH (CH 2 ) 2 NH 2 in which m and n are numbers whose sum (m + n) is between 1 and 2000, preferably between 50 and 150, where n preferably values of 0 to 1999 and in particular of 49 to 149 and m preferably values of 1 to 2000 , in particular from 1 to 10 assumes.
Diese Silikone werden nach der INCI-Deklaration als Trimethylsilylamodimethicone bezeichnet und sind beispielsweise unter der Bezeichnung Q2-7224 (Hersteller: Dow Corning; ein stabilisiertes Trimethylsilylamodimethicon) erhältlich.These silicones are referred to as trimethylsilylamodimethicones according to the INCI declaration and are available, for example, under the name Q2-7224 (manufacturer: Dow Corning, a stabilized trimethylsilylamodimethicone).
Besonders bevorzugt sind auch erfindungsgemäße Mittel, die mindestens ein aminofunktionelles Silikon der Formel (Si-3b)Particular preference is also given to compositions according to the invention which contain at least one amino-functional silicone of the formula (Si-3b)
R-[Si(CH3)2-O]n1[Si(R')-O]m-[Si(CH3)2-O]n2-SiMe2R (Si-3b),R- [Si (CH 3) 2 -O] n1 [Si (R ') - O] m - [Si (CH 3) 2 -O] n2 SiMe 2 R (Si-3b),
I (CH2)3NH(CH2)2NH2 I (CH 2 ) 3 NH (CH 2 ) 2 NH 2
enthalten, worincontain, in which
R für -OH, eine (gegebenenfalls ethoxylierte und/oder propoxylierte) (C1 bis C20)-R is -OH, (optionally ethoxylated and / or propoxylated) (C 1 to C 20 ) -
Alkoxygruppe oder eine -CH3-Gruppe steht,Alkoxy group or a -CH 3 group,
R' für -OH, eine (C1 bis C20)-Alkoxygruppe oder eine -CH3-Gruppe und m, n1 und n2 Zahlen sind, deren Summe (m + n1 + n2) zwischen 1 und 2000, vorzugsweise zwischen 50 und 150 beträgt, wobei die Summe (n1 + n2) vorzugsweise Werte von 0 bis 1999 und insbesondere von 49 bis 149 und m vorzugsweise Werte von 1 bis 2000, insbesondere von 1 bis 10 annimmt.R 'is -OH, a (C 1 to C 20 ) alkoxy group or a -CH 3 group and m, n1 and n2 are numbers whose sum (m + n1 + n2) is between 1 and 2,000, preferably between 50 and Is 150, wherein the sum (n1 + n2) preferably takes values from 0 to 1999 and in particular from 49 to 149 and m preferably values from 1 to 2000, in particular from 1 to 10.
Diese Silikone werden nach der INCI-Deklaration als Amodimethicone, bzw. als funktionalisierte Amodimethicone, wie beispielsweise Bis(C13-15 Alkoxy) PG Amodimethicone (beispielsweise als Handelsprodukt: DC 8500 der Firma Dow Corning erhältlich), Trideceth-9 PG-Amodimethicone (beispielsweise als Handelsprodukt Silcare Silicone SEA der Firma Clariant erhältlich) bezeichnet.These silicones are according to the INCI declaration as Amodimethicone, or as functionalized Amodimethicone, such as bis (C13-15 alkoxy) PG Amodimethicone (for example, as a commercial product: DC 8500 from Dow Corning available), trideceth-9 PG-amodimethicones (for example as a commercial product Silcare Silicone SEA available from Clariant).
Unabhängig davon, welche aminofunktionellen Silikone eingesetzt werden, sind erfindungsgemäß der Einsatz solcher kosmetische oder dermatologische Zubereitungen bevorzugt, die ein aminofunktionelles Silikon enthalten dessen Aminzahl oberhalb von 0,25 meq/g, vorzugsweise oberhalb von 0,3 meq/g und insbesondere oberhalb von 0,4 meq/g liegt. Die Aminzahl steht dabei für die Milli-Äquivalente Amin pro Gramm des aminofunktionellen Silikons. Sie kann durch Titration ermittelt und auch in der Einheit mg KOH/g angegeben werden.Regardless of which amino-functional silicones are used, according to the invention the use of such cosmetic or dermatological preparations containing an amino-functional silicone whose amine number is above 0.25 meq / g, preferably above 0.3 meq / g and in particular above 0 , 4 meq / g. The amine number stands for the milliequivalents of amine per gram of the amino-functional silicone. It can be determined by titration and also expressed in mg KOH / g.
Erfindungsgemäß bevorzugte kosmetische oder dermatologische Zubereitungen sind dadurch gekennzeichnet, dass sie, bezogen auf ihr Gewicht, 0,01 bis 10 Gew.%, vorzugsweise 0,1 bis 8 Gew.%, besonders bevorzugt 0,25 bis 7,5 Gew.% und insbesondere 0,5 bis 5 Gew.% aminofunk- tionelle(s) Silikon(e) enthalten. Auch die nach INCI als Cyclomethicone bezeichneten cyclischen Dimethicone sind erfindungsgemäß mit Vorzug einsetzbar. Hier sind erfindungsgemäße kosmetische oder dermatologische Zubereitungen bevorzugt, die mindestens ein Silikon der Formel (Si-4)Cosmetic or dermatological preparations preferred according to the invention are characterized in that, based on their weight, they contain 0.01 to 10% by weight, preferably 0.1 to 8% by weight, particularly preferably 0.25 to 7.5% by weight and in particular from 0.5 to 5% by weight of amino-functional silicone (s). The cyclic dimethicones designated as cyclomethicones according to INCI are also preferably used according to the invention. Here, cosmetic or dermatological preparations according to the invention are preferred which contain at least one silicone of the formula (Si-4)
Figure imgf000069_0001
enthalten, in der x für eine Zahl von 0 bis 200, vorzugsweise von 0 bis 10, weiter bevorzugt von 0 bis 7 und insbesondere 0, 1 , 2, 3, 4, 5 oder 6, steht.
Figure imgf000069_0001
in which x is a number from 0 to 200, preferably from 0 to 10, more preferably from 0 to 7 and in particular 0, 1, 2, 3, 4, 5 or 6 stands.
Die vorstehend beschriebenen Silikone weisen ein Rückgrat auf, welches aus -Si-O-Si-Einheiten aufgebaut ist. Selbstverständlich können diese Si-O-Si-Einheiten auch durch Kohlenstoffketten unterbrochen sein. Entsprechende Moleküle sind durch Kettenverlängerungsreaktionen zugänglich und kommen vorzugsweise in Form von Silikon-in-Wasser-Emulsionen zum Einsatz.The silicones described above have a backbone composed of -Si-O-Si units. Of course, these Si-O-Si units may also be interrupted by carbon chains. Appropriate molecules are accessible by chain extension reactions and are preferably used in the form of silicone-in-water emulsions.
Die erfindungsgemäß einsetzbaren Silikon-in-Wasser Emulsionen können nach bekannten Verfahren hergestellt werden, wie sie beispielsweise in US 5,998,537 und EP 0 874 017 A1 offenbart sind.The silicone-in-water emulsions which can be used according to the invention can be prepared by known processes, as disclosed, for example, in US Pat. No. 5,998,537 and EP 0 874 017 A1.
Zusammenfassend umfasst dieses Herstellungsverfahren die emulgierende Mischung von Komponenten, deren eine mindestens ein Polysiloxane enthält, deren andere mindestens ein Organosilikonmaterial enthält, das mit dem Polysiloxane in einer Kettenverlängerungsreaktion reagiert, wobei mindestens ein Metallion-enthaltender Katalysator für die Kettenverlängerungsreaktion, mindestens ein Tensid und Wasser zugegen sind.In summary, this method of preparation comprises the emulsifying mixture of components, one of which contains at least one polysiloxane, the other of which contains at least one organosilicone material which reacts with the polysiloxane in a chain extension reaction, with at least one metal ion-containing catalyst for the chain extension reaction, at least one surfactant and water present are.
Kettenverlängerungsreaktionen mit Polysiloxanen sind bekannt und können beispielsweise die Hydrosilylierungsreaktion umfassen, in der eine Si-H Gruppe mit einer aliphatisch ungesättigten Gruppe in Gegenwart eines Platin/Rhodium-Katalysators unter Bildung von Polysiloxanes mit einigen Si-(C)P-Si Bindungen (p = 1-6) reagiert, wobei die Polysiloxane auch als Polysiloxane-Poly- silalkylene-Copolymere bezeichnet werden.Chain extension reactions with polysiloxanes are known and may include, for example, the hydrosilylation reaction in which an Si-H group having an aliphatically unsaturated group in the presence of a platinum / rhodium catalyst to form polysiloxanes having some Si (C) P- Si bonds (p = 1-6), the polysiloxanes also being referred to as polysiloxane-polysilalkylene copolymers.
Die Kettenverlängerungsreaktion kann auch die Reaktion einer Si-OH Gruppe (beispielsweise eines Hydroxy-terminierten Polysiloxans) mit einer Alkoxygruppe (beispielsweise Alkoxysilanen, Silikaten oder Alkoxysiloxanen) in Gegenwart eines metallhaltigen Katalysators unter Bildung von Polysiloxanen umfassen.The chain extension reaction may also include the reaction of an Si-OH group (e.g., a hydroxy-terminated polysiloxane) with an alkoxy group (e.g., alkoxysilanes, silicates, or alkoxysiloxanes) in the presence of a metal-containing catalyst to form polysiloxanes.
Die Polysiloxane, die in der Kettenverlängerungsreaktion eingesetzt werden, umfassen ein substantiell lineares Polymer der folgenden Struktur: R-Si(R2M-O-Si(R2Hn-O-SiR3 The polysiloxanes used in the chain extension reaction comprise a substantially linear polymer of the following structure: R-Si (R 2 MO-Si (R 2 Hn-O-SiR 3
In dieser Struktur steht jedes R unabhängig voneinander für einen Kohlenwasserstoffrest mit bis zu 20 Kohlenstoffatomen, vorzugsweise mit 1 bis 6 C-Atomen, wie beispielsweise einer Alkylgruppe (beispielsweise Methyl, Ethyl, Propyl oder Butyl), eine Arylgruppe (beispielsweise Phenyl), oder die für die Kettenverlängerungsreaktion benötigte Gruppe ("reaktive Gruppe", beispielsweise Si-gebundene H-Atome, aliphatisch ungesättigte Gruppen wie Vinyl, AIIyI oder Hexenyl, Hydroxy, Alkoxy wie Methoxy, Ethoxy oder Propoxy, Alkoxy-Alkoxy, Acetoxy, Amino usw.), mit der Maßgabe, dass durchschnittlich ein bis zwei reaktive Gruppen pro Polymer vorliegen, n ist eine positive Zahl > 1. Vorzugsweise ist eine Mehrzahl der reaktiven Gruppen, besonders bevorzugt > 90%, und insbesondere > 98% der reaktiven Gruppen, an den endständigen Si-Atomen im Siloxan gebunden. Vorzugsweise steht n für Zahlen, die Polysiloxane beschreiben, welche Viskositäten zwischen 1 und 1.000.000 mm2/s besitzen, besonders bevorzugt Viskositäten zwischen 1.000 und 100.000 mm2/s.In this structure, each R independently represents a hydrocarbon radical having up to 20 carbon atoms, preferably having 1 to 6 carbon atoms, such as an alkyl group (for example, methyl, ethyl, propyl or butyl), an aryl group (for example, phenyl), or group required for the chain extension reaction ("reactive group", for example Si-bonded H atoms, aliphatically unsaturated groups such as vinyl, allyl or hexenyl, hydroxy, alkoxy, such as methoxy, ethoxy or propoxy, alkoxy-alkoxy, acetoxy, amino, etc.), with the proviso that on average one to two reactive groups are present per polymer, n is a positive number> 1. Preferably, a plurality of the reactive groups, more preferably> 90%, and especially> 98% of the reactive groups, at the terminal Si -Atomen bound in siloxane. Preferably, n is numbers describing polysiloxanes having viscosities between 1 and 1,000,000 mm 2 / s, more preferably viscosities between 1,000 and 100,000 mm 2 / s.
Die Polysiloxane können zu einem geringen Grad verzweigt sein (beispielsweise < 2 Mol-% der Siloxaneinheiten), bzw. sind die Polymere aber substantiell linear, besonders bevorzugt vollständig linear. Zudem können die Substituenten R ihrerseits substituiert sein, beispielsweise mit N-haltigen Gruppen (beispielsweise Aminogruppen), Epoxygruppen, S-haltige Gruppen, Si- haltige Gruppen, O-haltige Gruppen usw.. Vorzugsweise sind mindestens 80% der Reste R Alkylreste, besonders bevorzugt Methylgruppen.The polysiloxanes may be branched to a low degree (for example, <2 mol% of the siloxane units), but the polymers are substantially linear, more preferably fully linear. In addition, the substituents R may in turn be substituted, for example with N-containing groups (for example amino groups), epoxy groups, S-containing groups, Si-containing groups, O-containing groups, etc. Preferably, at least 80% of the radicals R are alkyl radicals, especially preferably methyl groups.
Das Organosilikonmaterial, das mit dem Polysiloxan in der Kettenverlängerungsreaktion reagiert, kann entweder ein zweites Polysiloxan sein, oder ein Molekül, das als Kettenverlängerer agiert. Wenn das Organosilikonmaterial ein Polysiloxan ist, hat es die vorstehend erwähnte generelle Struktur. In diesen Fällen besitzt ein Polysiloxan in der Reaktion (mindestens) eine reaktive Gruppe, und ein zweites Polysiloxan besitzt (mindestens) eine zweite reaktive Gruppe, die mit der ersten reagiert.The organosilicone material that reacts with the polysiloxane in the chain extension reaction may be either a second polysiloxane or a molecule that acts as a chain extender. When the organosilicone material is a polysiloxane, it has the above-mentioned general structure. In these cases, one polysiloxane in the reaction has (at least) one reactive group, and a second polysiloxane has (at least) a second reactive group that reacts with the first.
Falls das Organosilikonmaterial ein Kettenverlängerungs-Agens umfasst, kann dies ein Material sein wie beispielsweise ein Silan, ein Siloxan (beispielsweise Disiloxane oder Trisiloxan) oder ein Silazan. So kann beispielsweise eine Zusammensetzung, die ein Polysiloxan gemäß der vorstehend beschriebenen generellen Struktur umfasst, welches mindestens eine Si-OH Gruppe aufweist, ketteverlängert werden, indem mit einem Alkoxysilan (beispielsweise einem Dialkoxysilan oder Trialkoxysilan) in Gegenwart von Zinn- oder Titan-haltigen Katalysatoren reagiert wird.If the organosilicone material comprises a chain-extending agent, it may be a material such as a silane, a siloxane (e.g. disiloxane or trisiloxane) or a silazane. For example, a composition comprising a polysiloxane according to the general structure described above having at least one Si-OH group can be chain extended by reacting with an alkoxysilane (for example, a dialkoxysilane or trialkoxysilane) in the presence of tin or titanium-containing catalysts is reacted.
Die metallhaltigen Katalysatoren in der Kettenverlängerungsreaktion sind meist spezifisch für eine bestimmte Reaktion. Solche Katalysatoren sind im Stand der Technik bekannt und enthalten beispielsweise Metalle wie Platin, Rhodium, Zinn, Titan, Kupfer, Blei, etc.. In einer bevorzugten Kettenverlängerungsreaktion wird ein Polysiloxan mit mindestens einer aliphatisch ungesättigten Gruppe, vorzugsweise einer Endgruppe, mit einem Organosilikonmaterial in Gegenwart eines Hydrosilylierungskatalysators zur Reaktion gebracht, das ein Siloxan oder Polysiloxan mit minde- stens einer (vorzugsweise endständigen) Si-H Gruppe ist. Das Polysiloxan besitzt mindestens eine aliphatisch ungesättigte Gruppe und genügt der allgemeinen oben angegeben Formel, in der R und n wie vorstehend definiert sind, wobei im Durchschnitt zwischen 1 und 2 Gruppen R eine aliphatisch ungesättigte Gruppe pro Polymer besitzen. Repräsentative aliphatisch ungesättigte Gruppen sind beispielsweise Vinyl, AIIyI, Hexenyl und Cyclohexenyl oder eine Gruppe R2CH=CHR3, in der R2 für eine divalente aliphatische an das Silicium gebundene Kette und R3 für ein Wasserstoffatom oder eine Alkylgruppe steht. Das Organosilikonmaterial mit mindestens einer Si-H Gruppe hat vorzugsweise die oben genannte Struktur, in der R und n wie vorstehend definiert sind und wobei im Durchschnitt zwischen 1 und 2 Gruppen R ein Wasserstoff bedeuten und n 0 oder eine positive ganze Zahl ist.The metal-containing catalysts in the chain extension reaction are usually specific for a particular reaction. Such catalysts are known in the art and include, for example, metals such as platinum, rhodium, tin, titanium, copper, lead, etc. In a preferred chain extension reaction, a polysiloxane having at least one aliphatically unsaturated group, preferably an end group, is reacted with an organosilicone material The presence of a hydrosilylation catalyst which reacts with a siloxane or polysiloxane is a (preferably terminal) Si-H group. The polysiloxane has at least one aliphatically unsaturated group and satisfies the general formula given above in which R and n are as defined above, with an average of between 1 and 2 groups R having one aliphatically unsaturated group per polymer. Representative aliphatic unsaturated groups are, for example, vinyl, allyl, hexenyl and cyclohexenyl or a group R 2 CH = CHR 3 in which R 2 is a divalent aliphatic silicon-bonded chain and R 3 is a hydrogen atom or an alkyl group. The organosilicone material having at least one Si-H group preferably has the above-mentioned structure, wherein R and n are as defined above and wherein, on average, between 1 and 2 groups R is hydrogen and n is 0 or a positive integer.
Dieses Material kann ein Polymer oder ein niedermolekulares Material wie ein Siloxan sein (beispielsweise ein Disiloxane oder ein Trisiloxan).This material may be a polymer or a low molecular weight material such as a siloxane (for example, a disiloxane or a trisiloxane).
Das Polysiloxan mit mindestens einer aliphatisch ungesättigten Gruppe und das Organosilikonmaterial mit mindestens einer Si-H Gruppe reagieren in Gegenwart eines Hydrosilylierungskataly- sators. Solche Katalysatoren sind aus dem Stand der Technik bekannt und umfassen beispielsweise Platin- und Rhodium-enthaltende Materialien. Die Katalysatoren können jede bekannte Form annehmen, beispielsweise auf Trägermaterialien (wie beispielsweise Silica Gel oder Aktivkohle) aufgebrachtes Platin oder Rhodium oder andere geeignete Compounds wie Platinchlorid, Salze von Platin- oder Chloroplatinsäuren. Ein wegen der guten Dispergierbarkeit in Organosilikonsystemen und der geringen Farbveränderung bevorzugter Katalysator ist Chloroplatinsäure entweder als kommerziell verfügbares Hexahydrat oder in wasserfreier Form.The polysiloxane having at least one aliphatically unsaturated group and the organosilicone material having at least one Si-H group react in the presence of a hydrosilylation catalyst. Such catalysts are known in the art and include, for example, platinum and rhodium-containing materials. The catalysts may take any known form, for example platinum or rhodium coated on support materials (such as silica gel or activated carbon) or other suitable compounds such as platinum chloride, salts of platinum or chloroplatinic acids. Chloroplatinic acid either as a commercially available hexahydrate or in anhydrous form is a preferred catalyst because of good dispersibility in organosilicone systems and low color change.
Bei einer weiteren bevorzugten Kettenerweiterungsreaktion wird ein Polysiloxan mit mindestens einer Si-OH Gruppe, vorzugsweise einer Endgruppe, mit einem Organosilikonmaterial zu Reaktion gebracht, das mindestens eine Alkoxygruppe besitzt, vorzugsweise ein Siloxan mit mindestens einer Si-OR Gruppe oder ein Alkoxysilan mit mindestens zwei Alkoxygruppen. Hierbei wird als Katalysator wieder ein metallhaltiger Katalysator eingesetzt.In a further preferred chain extension reaction, a polysiloxane having at least one Si-OH group, preferably an end group, is reacted with an organosilicone material having at least one alkoxy group, preferably a siloxane having at least one Si-OR group or an alkoxysilane having at least two alkoxy groups , In this case, the catalyst used is again a metal-containing catalyst.
Für die Reaktion einer Si-OH Gruppe mit einer Si-OR Gruppe existieren viele literaturbekannte Katalysatoren, beispielsweise Organometallverbindungen wie Organozinnsalze, Titanate oder Titanchelate bzw. -komplexe. Beispiele umfassen Zinn-octoat, Dibutylzinn-dilaurat, Dibutylzinn- diacetat, Dimethyltinn-dineodecanoat, Dibutylzinn-dimethoxid, Isobutylzinn-triceroat, Dimethylzinn-dibutyrat, Dimethylzinn-dineodecanoat, Triethylzinn-tartrat, Zinnoleat, Zinnnaphthenat, Zinnbutyrat, Zinnacetat, Zinnbenzoat, Zinnsebacat, Zinnsuccinat, Tetrabutyltitanat, Tetraisopropyltitante, Tetraphenyltitanat, Tetraoctadecyltitanat, Titan- naphthanat, Ethyltriethanolamin-Titanat, Titani-diisopropyl-diethyl-acetoacetat, Titan-diisopropoxy- diacetyl-acetonat und Titani-tetra-Alkoxide, bei denen das Alkoxid Butoxy oder Propoxy ist. Erfindungsgemäß ebenfalls bevorzugt eingesetzte Mittel sind dadurch gekennzeichnet, dass sie mindestens ein Silikon der Formel (Si-5)For the reaction of an Si-OH group with an Si-OR group, there are many catalysts known from the literature, for example organometallic compounds such as organotin salts, titanates or titanium chelates or complexes. Examples include stannous octoate, dibutyltin dilaurate, dibutyltin diacetate, dimethyltin dineodecanoate, dibutyltin dimethoxide, isobutyltin triceroate, dimethyltin dibutyrate, dimethyltin dineodecanoate, triethyltin tartrate, tin oleate, tin naphthenate, tin butyrate, tin acetate, tin benzoate, tin sebacate, Tin succinate, tetrabutyl titanate, tetraisopropyl titanate, tetraphenyl titanate, tetraoctadecyl titanate, titanium naphthanate, ethyl triethanolamine titanate, titanium diisopropyl diethyl acetoacetate, titanium diisopropoxy diacetyl acetonate and titanium tetra alkoxides in which the alkoxide is butoxy or propoxy. Agents likewise preferably used according to the invention are characterized in that they contain at least one silicone of the formula (Si-5)
R3Si-[O-SiR2]χ-(CH2)n-[O-SiR2]y-O-SiR3 (Si-5),R 3 Si [O-SiR 2] χ- (CH 2 ) n - [O-SiR 2 ] y -O-SiR 3 (Si-5),
enthalten, in der R für gleiche oder verschiedene Reste aus der Gruppe -H, -Phenyl, -Benzyl, -CH2-CH(CH3)Ph, der C-|.20-Alkylreste, vorzugsweise -CH3, -CH2CH3, -CH2CH2CH3, - CH(CH3)2, -CH2CH2CH2H3, -CH2CH(CH3)2, -CH(CH3)CH2CH3, -C(CH3)3, steht, x bzw. y für eine Zahl von 0 bis 200, vorzugsweise von 0 bis 10, weiter bevorzugt von 0 bis 7 und insbesondere 0, 1 , 2, 3, 4, 5 oder 6, stehen, und n für eine Zahl von 0 bis 10, bevorzugt von 1 bis 8 und insbesondere für 2, 3, 4, 5, 6 steht.in which R is identical or different radicals from the group -H, -phenyl, -benzyl, -CH 2 -CH (CH 3 ) Ph, the C- |. 20 -alkyl radicals, preferably -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , --CH (CH 3 ) 2 , -CH 2 CH 2 CH 2 H 3 , -CH 2 CH (CH 3 ) 2 , -CH (CH 3 ) CH 2 CH 3 , -C (CH 3 ) 3 , x or y is a number from 0 to 200, preferably from 0 to 10, more preferably from 0 to 7 and in particular 0, 1, 2, 3, 4, 5 or 6, and n is a number from 0 to 10, preferably from 1 to 8 and especially for 2, 3, 4, 5, 6.
Mit Vorzug sind die Silikone wasserlöslich. Erfindungsgemäß bevorzugt eingesetzte Mittel der Ausführungsform mit einem Silikon c2) sind dadurch gekennzeichnet, dass das Silikon c2) wasserlöslich ist.The silicones are preferably water-soluble. Agents of the embodiment with a silicone c2) preferably used according to the invention are characterized in that the silicone c2) is water-soluble.
Entsprechende hydrophile Silikone werden beispielsweise aus den Verbindungen der Formeln (Si-6) und/oder (Si-7) ausgewählt. Insbesondere bevorzugte wasserlösliche Tenside auf Silikonbasis sind ausgewählt aus der Gruppe der Dimethiconcopolyole die bevorzugt alkoxyliert, insbesondere polyethoxyliert oder polypropoxyliert sind.Corresponding hydrophilic silicones are selected, for example, from the compounds of the formulas (Si-6) and / or (Si-7). Particularly preferred water-soluble silicone-based surfactants are selected from the group of dimethicone copolyols which are preferably alkoxylated, in particular polyethoxylated or polypropoxylated.
Unter Dimethiconcopolyolen werden erfindungsgemäß bevorzugt Polyoxyalkylen-modifizierte Dimethylpolysiloxane der allgemeinen Formeln (Si-6) oder (Si-7) verstanden:Dimethicone copolyols are understood according to the invention as meaning preferably polyoxyalkylene-modified dimethylpolysiloxanes of the general formulas (Si-6) or (Si-7):
Me MeMe Me
(H3C)3SiO-I-Si-O -Si- O-|-SiMe3 Me O C3H6(H 3 C) 3 SiO-I-Si-O-Si-O- | -SiMe 3 Me O C3H6
( ?C2H4O)a(C3H6O)b-R (Si-6)(C 2 H 4 O) a (C 3 H 6 O) b -R (Si-6)
R'— Si- ■[OSi(CH3)2]x-(OC2H4)a-(OC3H6)b-OR"R'- Si ■ [OSi (CH 3) 2] x - (OC 2 H 4) a - (OC 3 H 6) b -OR "
(Si-7) worin der Rest R steht für ein Wasserstoffatom, eine Alkylgruppe mit 1 bis 12 C-Atomen, eine Alkoxygruppe mit 1 bis 12 C-Atomen oder eine Hydroxylgruppe, die Reste R' und R" bedeuten Alkylgruppen mit 1 bis 12 C-Atomen, x steht für eine ganze Zahl von 1 bis 100, bevorzugt von 20 bis 30, y steht für eine ganze Zahl von 1 bis 20, bevorzugt von 2 bis 10 und a und b stehen für ganze Zahlen von 0 bis 50, bevorzugt von 10 bis 30.(Si-7) in which the radical R is a hydrogen atom, an alkyl group having 1 to 12 C atoms, an alkoxy group having 1 to 12 C atoms or a hydroxyl group, the radicals R 'and R "denote alkyl groups having 1 to 12 C atoms, x is an integer from 1 to 100, preferably from 20 to 30, y is an integer from 1 to 20, preferably from 2 to 10 and a and b are integers from 0 to 50, preferably from 10 to 30.
Verbindungen die unter die oben genannten Formeln fallen, werden in den folgenden Patentanmeldungen, auf die explizit Bezug genommen wird, offenbart: US-A-4, 122,029; US-A- 4,265,878; US-A-4,421 ,769 und GB-A-2,066,659.Compounds falling within the above formulas are disclosed in the following patent applications, which are incorporated herein by reference: US-A-4,122,029; US-A-4,265,878; US-A-4,421,769 and GB-A-2,066,659.
Besonders bevorzugte Dimethiconcopolyole im Sinne der Erfindung sind beispielsweise die kommerziell unter dem Handelsnamen SILWET (Union Carbide Corporation) und DOW CORNING (Dow) vertriebenen Produkte.Particularly preferred dimethicone copolyols according to the invention are, for example, the products sold commercially under the trade name SILWET (Union Carbide Corporation) and DOW CORNING (Dow).
Erfindungsgemäß besonders bevorzugte Dimethiconcopolyole sind Dow Corning 190 und Dow Corning 193 (Dow).Dimethicone copolyols particularly preferred according to the invention are Dow Corning 190 and Dow Corning 193 (Dow).
Als Ceramide c3) finden bevorzugt die Sphingolipide der Formel (CE-I) Verwendung,As ceramides c3), the sphingolipids of the formula (CE-I) are preferably used,
worin R1 steht für eine lineare C12- bis C30-Alkylgruppe oder eine gesättigte oder ungesättigte ω-(C12- bis C2o)-Acyloxy-(C-i2-C3o)-alkylgruppe (wie bevorzugt Tricosanyl, Heptadecanyl oder ω- wherein R 1 is a linear C 12 - to C 30 alkyl group or a saturated or unsaturated ω- (C 12 - to C 2 o) acyloxy (Ci 2 -C 3 o) alkyl group (as preferred tricosanyl, heptadecanyl or ω-
(Octadeca-9,12-dien-oyloxy)-nonacosanyl) und R2 steht für eine gesättigte oder ungesättigte C15-Alkylgruppe oder eine gesättigte oder ungesättigte C15-Hydroxyalkylgruppe (wie beispielsweise Pentadeca-1-en-1-yl, 3-(Octadeca-9,12-dienyloxy) -nonacosanyl) and R 2 is a saturated or unsaturated C 15 alkyl group or a saturated or unsaturated C 15 hydroxyalkyl group (such as pentadeca-1-en-1-yl, 3 -
Hydroxypentadeca-1-en-1-yl, 1-Hydroxypentadecanyl).Hydroxypentadeca-1-en-1-yl, 1-hydroxypentadecanyl).
Als bevorzugte Verbindungen gemäß Formel VI werden erfindungsgemäß die unter den INCI- Bezeichnungen bekannten Verbindungen Ceramide I, Ceramide II, Ceramide 1 , Ceramide 2, Ceramide 3, Ceramide 5 und Ceramide 6 als Wirkstoff (W) verwendet. Besonders bevorzugt werden Gemische der Verbindungen mit der Formel (CE-I) verwendet, die beispielsweise unter dem Handelsnamen SK-Influx® und Ceramide IM jeweils von der Firma Degussa Care Specialties erhältlich sind, sowie das Handelsprodukt Ceramide TIC-001 , das von der Firma Takasago International Corporation vermarktet wird. Die Verbindungen der Formel (CE-I) werden bevorzugt in einer Menge von 0,01 bis 1 ,0 Gew.-% bezogen auf das Gewicht des anwendungsbereiten kosmetischen Mittels verwendet.Preferred compounds according to formula VI according to the invention are the compounds ceramides I, ceramides II, ceramides 1, ceramides 2, ceramides 3, ceramides 5 and ceramides 6 known under the INCI names as active ingredient (W). Mixtures of the compounds of formula are particularly preferably used (CE-I) which are obtainable for example under the trade name of SK-Influx ® and Ceramide IM respectively by Degussa Care Specialties, and the commercial product Ceramide TIC-001, sold by the company Takasago International Corporation is marketed. The compounds of the formula (CE-I) are preferably used in an amount of 0.01 to 1.0% by weight, based on the weight of the ready-to-use cosmetic product.
Außerdem sind Pseodoceramide, wie insbesondere das Pseudoceramid N-(C8-22-Acyl)-C8-22-acyl- hydroxyprolin (wie beispielsweise das Cetyl-hydroxyprolin Palmitamide gemäß Handelsprodukt Sym Repair 153884 der Firma Symrise) erfindungsgemäße Pseudoceramide c3). Das gebrauchsfertige erfindungsgemäße Mittel sollte bevorzugt einen pH-Wert im Bereich von pH 5 bis pH 12, insbesondere von pH 7 bis pH 11 , aufweisen. Besonders bevorzugt ist die Anwendung der Haarfärbemittel in einem schwach alkalischen Milieu in einem pH-Bereich zwischen pH 7 und pH 9.In addition, Pseodoceramide, such as in particular the pseudoceramide N- (C 8-22 acyl) C 8-22 acyl hydroxyproline (such as cetyl-hydroxyproline Palmitamide according commercial product Sym Repair 153884 of the company Symrise) according to the invention pseudoceramides c3). The ready-to-use agent according to the invention should preferably have a pH in the range from pH 5 to pH 12, in particular from pH 7 to pH 11. Particularly preferred is the use of the hair dye in a weakly alkaline medium in a pH range between pH 7 and pH 9.
Im erfindungsgemäßen Mittel sind die Inhaltsstoffe bevorzugt in einem Träger enthalten. Solche Träger sind beispielsweise Cremes, Emulsionen, Gele oder auch tensidhaltige schäumende Lösungen, wie beispielsweise Shampoos, Schaumaerosole oder andere Zubereitungen, die insbesondere für die Anwendung auf dem Haar geeignet sind. Es ist aber auch denkbar, die Inhaltsstoffe in eine pulverförmige oder auch tablettenförmige Formulierung zu integrieren, welche vor der Anwendung in Wasser gelöst wird. Die Träger können insbesondere wässrig oder wässrig-alkoholisch sein.In the agent according to the invention, the ingredients are preferably contained in a carrier. Such carriers are, for example, creams, emulsions, gels or surfactant-containing foaming solutions, such as shampoos, foam aerosols or other preparations which are particularly suitable for use on the hair. But it is also conceivable to integrate the ingredients in a powdered or tablet-like formulation, which is dissolved in water before use. The carriers may in particular be aqueous or aqueous-alcoholic.
Ein wässriger Träger enthält mindestens 50 Gew.-% Wasser.An aqueous carrier contains at least 50% by weight of water.
Unter wässrig-alkoholischen Trägern sind im Sinne der vorliegenden Erfindung wässrige Lösungen enthaltend 3 bis 70 Gew.-% mindestens eines bei Raumtemperatur und Normaldruck flüssigen, d-C^AIkohols mit mindestens einer Hydroxylgruppe (insbesondere Ethanol, 1 ,2- Propylenglycol, Glycerin, Isopropanol) zu verstehen.For the purposes of the present invention, aqueous-alcoholic carriers are aqueous solutions containing from 3 to 70% by weight of at least one C.sub.12 alcohol which is liquid at room temperature and atmospheric pressure and has at least one hydroxyl group (in particular ethanol, 1,2-propylene glycol, glycerol, isopropanol). to understand.
Die erfindungsgemäßen Mittel können zusätzlich weitere organische Lösemittel, wie beispielsweise Methoxybutanol, Benzylalkohol, oder Ethyldiglykol enthalten. Bevorzugt sind dabei alle wasserlöslichen organischen Lösemittel.The compositions of the invention may additionally contain other organic solvents, such as methoxybutanol, benzyl alcohol, or ethyl diglycol. Preference is given to all water-soluble organic solvents.
Im ersten Erfindungsgegenstand beschriebene Mittel eignen sich besonders gut zur erfindungsgemäßen Verwendung auf keratinhaltigen Fasern, insbesondere menschlichen Haaren.Agents described in the first subject of the invention are particularly well suited for use according to the invention on keratin-containing fibers, in particular human hair.
Unter keratinhaltigen Fasern sind Wolle, Pelze, Federn und insbesondere menschliche Haare zu verstehen. Die erfindungsgemäße Kombination kann prinzipiell aber auch auf anderen Naturfasern, wie z. B. Baumwolle, Jute, Sisal, Leinen oder Seide, modifizierter Naturfasern, wie z. B. Regeneratcellulose, Nitro-, Alkyl- oder Hydroxyalkyl- oder Acetylcellulose und synthetischer Fasern, wie z. B. Polyamid-, Polyacrylnitril-, Polyurethan- und Polyesterfasern verwendet werden.Keratin fibers are wool, furs, feathers and especially human hair to understand. The combination of the invention may in principle but also on other natural fibers such. As cotton, jute, sisal, linen or silk, modified natural fibers such. As regenerated cellulose, nitro, alkyl or hydroxyalkyl or acetyl cellulose and synthetic fibers, such as. As polyamide, polyacrylonitrile, polyurethane and polyester fibers are used.
Ein weiterer Gegenstand daher der vorliegenden Erfindung ist ein Verfahren zur Behandlung keratinhaltiger Fasern, insbesondere menschlicher Haare, bei dem ein Mittel des ersten Erfindungsgegenstandes auf die Fasern aufgetragen wird und nach einer Einwirkzeit wieder abgespült wird.A further subject of the present invention is therefore a method for treating keratin-containing fibers, in particular human hair, in which an agent of the first subject of the invention is applied to the fibers and rinsed off again after a contact time.
Die Anwendungstemperaturen können in einem Bereich zwischen 15 und 40 0C liegen. Nach einer Einwirkungszeit von in der Regel 5 bis 45 Minuten wird das Haarfärbemittel durch Aus- spülen von dem zu färbenden Haar entfernt. Das Nachwaschen mit einem Shampoo entfällt, wenn ein stark tensidhaltiger Träger, z.B. ein Färbeshampoo, verwendet wurde.The application temperatures can be in a range between 15 and 40 0 C. After an exposure time of usually 5 to 45 minutes, the hair dye is removed by Rinse away from the hair to be dyed. The washing with a shampoo is omitted if a strong surfactant-containing carrier, such as a dyeing shampoo was used.
Ein dritter Gegenstand der Erfindung ist daher die Verwendung eines Mittels des ersten Erfindungsgegenstandes zur Färbung keratinhaltiger Fasern, insbesondere menschlicher Haare, welches 1 ,3-Dihydroxyaceton und mindestens einen Naturfarbstoff enthalten. Für die bevorzugten Mittel gelten mutatis mutandis die entsprechenden Ausführungsformen des ersten Erfindungsgegenstandes.A third aspect of the invention is therefore the use of an agent of the first subject of the invention for coloring keratin-containing fibers, in particular human hair, which contain 1, 3-dihydroxyacetone and at least one natural dye. Mutatis mutandis, the corresponding embodiments of the first subject of the invention apply to the preferred means.
Bevorzugt werden die erfindungsgemäßen Mittel zur Färbung keratinhaltiger Fasern, insbesondere menschlicher Haare, verwendet. The agents according to the invention are preferably used for coloring keratin-containing fibers, in particular human hair.
B e i s p i e l eB e i s p e e l e
Es wurden folgende Zusammensetzungen der nachfolgenden Tabelle 1 bereitgestellt. Alle Mengenangaben sind - wenn nicht anders gekennzeichnet - Gewichtsprozent. Folgende Handelsprodukte wurden als Rohstoffe verwendet:The following compositions of Table 1 below were provided. All quantities are - unless otherwise indicated - weight percent. The following commercial products were used as raw materials:
Figure imgf000076_0001
Figure imgf000076_0001
Tabelle 1 - HaarfärbegeleTable 1 - hair coloring gels
Figure imgf000076_0002
Figure imgf000076_0002
2 Gewichtsteile der in der Tabelle 1 gelisteten Formulierungen A-1 bis A-3 wurden bei Raumtemperatur und für 30 min Einwirkzeit jeweils auf 1 Gewichtsteil Büffel bauch haar (Fa. Hohenschildt, Berlin) ausgefärbt. Anschließend wurde das Haar mit handwarmem Wasser abgespült und an der Luft getrocknet.2 parts by weight of the formulations A-1 to A-3 listed in Table 1 were dyed at room temperature and for 30 min exposure time each to 1 part by weight of buffalo hair (Fa. Hohenschildt, Berlin). The hair was then rinsed with lukewarm water and dried in air.
Es wurden mit den beschriebenen Verfahren sehr intensive und waschechte Färbungen der Haare im natürlichen Farbspektrum erzielt. Very intensive and true dyeing of the hair in the natural color spectrum was achieved with the described methods.

Claims

P a t e n t a n s p r ü c h e Patent claims
1. Mittel zum Färben keratinhaltiger Fasern, insbesondere menschlicher Haare, dadurch gekennzeichnet, dass es 1 ,3-Dihydroxyaceton und mindestens einen Naturfarbstoff enthält.1. A composition for dyeing keratin fibers, in particular human hair, characterized in that it contains 1, 3-dihydroxyacetone and at least one natural dye.
2. Mittel gemäß Anspruch 1 , dadurch gekennzeichnet, dass es 1 ,3-Dihydroxyaceton in einer Menge von 0,1 bis 10,0 Gew.-%, bezogen auf das Gewicht des Mittels, enthält.2. Composition according to claim 1, characterized in that it contains 1, 3-dihydroxyacetone in an amount of 0.1 to 10.0 wt .-%, based on the weight of the composition.
3. Mittel gemäß Anspruch 1 , dadurch gekennzeichnet, dass es 1 ,3-Dihydroxyaceton in einer Menge von 1 ,0 bis 5,0 Gew.-%, bezogen auf das Gewicht des Mittels, enthält.3. Composition according to claim 1, characterized in that it contains 1, 3-dihydroxyacetone in an amount of 1, 0 to 5.0 wt .-%, based on the weight of the composition.
4. Mittel gemäß einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass es mindestens einen Naturfarbstoff in einer Menge von 0,001 bis 20,0 Gew.-%, bezogen auf das Gewicht des Mittels, enthält.4. Composition according to one of claims 1 to 3, characterized in that it contains at least one natural dye in an amount of 0.001 to 20.0 wt .-%, based on the weight of the composition.
5. Mittel gemäß einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass der Naturfarbstoff ausgewählt wird aus mindestens einer Verbindung aus der Gruppe, die gebildet wird, aus Diaryloylmethanfarbstoffen, Naphthochinonfarbstoffen, Flavonoidfarbstoffen, Anthrachinonfarbstoffen, Betalainfarbstoffen, Gallotanninfarbstoffen und indigoiden Farbstoffen.5. Composition according to one of claims 1 to 4, characterized in that the natural dye is selected from at least one compound from the group formed, from Diaryloylmethanfarbstoffen, naphthoquinone dyes, flavonoid dyes, Anthrachinonfarbstoffen, Betalainfarbstoffen, Gallotanninfarbstoffen and indigoid dyes.
6. Mittel gemäß einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass der Naturfarbstoff aus einer Pflanze erhalten wurde, die aus der Gruppe ausgewählt wird, die gebildet wird aus Indigofera tinctoria, Curcuma longa, Lawsonia inermis, Chamomilla recutita, Quercus robur, Rosmarinus officinalis, Rheum undulatum und Beta vulgaris.A composition according to any one of claims 1 to 5, characterized in that the natural dye is obtained from a plant selected from the group consisting of Indigofera tinctoria, Curcuma longa, Lawsonia inermis, Chamomilla recutita, Quercus robur, Rosmarinus officinalis, Rheum undulatum and Beta vulgaris.
7. Mittel gemäß einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass der Naturfarbstoff aus einer Pflanze erhalten wurde, die aus der Gruppe ausgewählt wird, die gebildet wird aus Indigofera tinctoria, Curcuma longa und Lawsonia inermis.7. Composition according to one of claims 1 to 5, characterized in that the natural dye was obtained from a plant selected from the group consisting of Indigofera tinctoria, Curcuma longa and Lawsonia inermis.
8. Mittel gemäß einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass es zusätzlich mindestens ein Kohlenhydrat gemäß der Formel (I)8. Composition according to one of claims 1 to 7, characterized in that it additionally contains at least one carbohydrate according to formula (I)
OO
HOH2C- (CHOH)n-" R (]) worin n für 1 oder 2 steht undHOH 2 C- (CHOH) n - "R ()) where n is 1 or 2 and
R für ein Wasserstoffatom oder eine Hydroxymethylgruppe steht, enthält. R represents a hydrogen atom or a hydroxymethyl group.
9. Verfahren zum Färben keratinhaltiger Fasern, insbesondere menschlicher Haare, dadurch gekennzeichnet, dass ein Mittel gemäß Anspruch 1 bis 8 auf die Fasern aufgetragen wird und nach einer Einwirkzeit wieder abgespült wird.9. A process for dyeing keratin fibers, in particular human hair, characterized in that an agent according to claim 1 to 8 is applied to the fibers and rinsed again after a contact time.
10. Verwendung eines Mittels gemäß Ansprüchen 1 bis 8 zur Färbung keratinhaltiger Fasern, insbesondere menschlicher Haare. 10. Use of an agent according to claims 1 to 8 for coloring keratin fibers, in particular human hair.
PCT/EP2008/057592 2007-09-06 2008-06-17 Coloring agent having natural dyes and 1,3-dihydroxyacetone WO2009033833A2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP08761090A EP2182915A2 (en) 2007-09-06 2008-06-17 Coloring agent having natural dyes and 1,3-dihydroxyacetone

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102007042286A DE102007042286A1 (en) 2007-09-06 2007-09-06 Colorants with natural dyes and 1,3-dihydroxyacetone
DE102007042286.7 2007-09-06

Publications (2)

Publication Number Publication Date
WO2009033833A2 true WO2009033833A2 (en) 2009-03-19
WO2009033833A3 WO2009033833A3 (en) 2010-02-25

Family

ID=39811647

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2008/057592 WO2009033833A2 (en) 2007-09-06 2008-06-17 Coloring agent having natural dyes and 1,3-dihydroxyacetone

Country Status (3)

Country Link
EP (1) EP2182915A2 (en)
DE (1) DE102007042286A1 (en)
WO (1) WO2009033833A2 (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011157666A1 (en) * 2010-06-16 2011-12-22 L'oreal Cosmetic use of a natural extract derived from beetroot peel for dyeing hair composition comprising the extract, an oxidizing agent, a basifying agent an optional metallic derivative
US8551188B2 (en) 2009-09-02 2013-10-08 L'oreal Composition comprising a hydrophobic dye, a particular organic and/or mineral alkaline agent, a particular compound (I) and a particular organic compound (II), and dyeing use thereof
CN115012230A (en) * 2022-07-21 2022-09-06 浙江龙天服饰有限公司 Method for dyeing underwear knitted fiber by using sol
CN115120523A (en) * 2022-07-25 2022-09-30 南京斯拜科生物科技股份有限公司 Natural single-agent hair dyeing composition

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2949333B1 (en) * 2009-09-02 2013-01-04 Oreal COMPOSITION COMPRISING A HYDROPHOBIC COLOR, A MINERAL BASE AND A PARTICULAR COMPOUND (I), AND ITS USE IN COLORING
FR2949339B1 (en) * 2009-09-02 2013-04-19 Oreal COMPOSITION COMPRISING A HYDROPHOBIC COLOR, AN ORGANIC ALKALI AGENT AND A PARTICULAR COMPOUND (I), AND ITS USE IN COLORING
FR2952817A1 (en) * 2009-11-23 2011-05-27 Oreal Composition, useful for dyeing keratin fibers, preferably human keratin fibers such as hair, comprises one or more dye precursors comprising indole derivatives and liquid organic compounds in a medium
DE102010064054A1 (en) * 2010-12-23 2012-06-28 Henkel Ag & Co. Kgaa Process for reshaping keratin-containing fibers
DE102011017522A1 (en) * 2011-04-26 2012-10-31 Beiersdorf Ag Composition, useful to dye keratin fibers, comprises an amino component e.g. lysine-lysine, lysine, histidine, or lysine esters of aliphatic alcohols and a carbonyl component e.g. glutaraldehyde, pyruvic acid, methylglyoxal or glyoxal
DE102011017519A1 (en) * 2011-04-26 2012-10-31 Beiersdorf Ag Hair treatment composition, useful e.g. for dyeing keratinous fibers, preferably feathers or hair, comprises 1,3-dihydroxyacetone, other carbonyl compounds comprising e.g. glutaraldehyde or glyoxylic acid, and an amino component
FR3004941B1 (en) * 2013-04-26 2015-05-22 Oreal COMPOSITION BASED ON HENNE OR INDIGO POWDER WITH OIL PRE-DISPERSION, HAIR COLORING METHOD USING THE SAME
US20190240133A1 (en) 2018-02-02 2019-08-08 Kao Usa Inc. Hair coloring compositions and methods thereof

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0998908A2 (en) 1998-11-04 2000-05-10 L'oreal Dyeing composition containing a cattonic and an oxidativ dye based an pyrazolo-(1,5)-pyramidine and dyeing process
EP1237818A1 (en) 1999-11-23 2002-09-11 Universite Laval Mesoporous zeolitic material with microporous crystalline mesopore walls
EP1237817A1 (en) 1999-12-14 2002-09-11 Hercules Incorporated Metal silicates, cellulose products and processes thereof
EP1293192A2 (en) 2001-09-12 2003-03-19 KPSS-Kao Professional Salon Services GmbH Hair dye and process for dyeing human hair
EP1250912B1 (en) 2001-04-18 2004-09-15 KPSS-Kao Professional Salon Services GmbH Hair dye composition
US20050210606A1 (en) 2004-03-27 2005-09-29 Kpss-Kao Professional Salon Services Gmbh Pre-treatment composition for oxidative coloring keratin fibres and process therefore
WO2005094763A1 (en) 2004-03-26 2005-10-13 Wella Aktiengesellschaft Hair coloring agent containing indigoid vat dyes
WO2005094762A1 (en) 2004-03-26 2005-10-13 Wella Aktiengesellschaft Hair coloring agent containing vat dyes
EP1250908B1 (en) 2001-04-18 2007-03-14 KPSS-Kao Professional Salon Services GmbH Hair dye

Family Cites Families (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4237253A (en) 1977-04-21 1980-12-02 L'oreal Copolymers, their process of preparation, and cosmetic compounds containing them
US4122029A (en) 1977-07-27 1978-10-24 Dow Corning Corporation Emulsion compositions comprising a siloxane-oxyalkylene copolymer and an organic surfactant
US4265878A (en) 1979-06-07 1981-05-05 Dow Corning Corporation Antiperspirant stick compositions
JPS5699407A (en) 1980-01-09 1981-08-10 Kao Corp Hair rinse composition
EP0047714B1 (en) 1980-09-05 1985-10-30 Ciba-Geigy Ag Mixtures of polymeric high-molecular acrylic quaternary ammonium salts and detergents, their preparation and use in cosmetic formulations
JPS5813700A (en) 1981-07-17 1983-01-26 花王株式会社 Detergent composition
US4421769A (en) 1981-09-29 1983-12-20 The Procter & Gamble Company Skin conditioning composition
EP0217274A3 (en) 1985-09-30 1988-06-29 Kao Corporation Hair cosmetic composition
DE3708451A1 (en) 1987-03-16 1988-10-06 Henkel Kgaa ZWITTERIONIC POLYMERS AND THEIR USE IN HAIR TREATMENT AGENTS
DE3723354A1 (en) 1987-07-15 1989-01-26 Henkel Kgaa SULFATED HYDROXY MIXERS, METHOD FOR THEIR PRODUCTION AND THEIR USE
DE3725030A1 (en) 1987-07-29 1989-02-09 Henkel Kgaa SURFACE ACTIVE HYDROXYSULFONATE
DE3926344A1 (en) 1989-08-09 1991-02-28 Henkel Kgaa METHOD FOR THE PRODUCTION OF LIGHT-COLORED OELSAEURESULFONATES
DE3929973A1 (en) 1989-09-08 1991-03-14 Henkel Kgaa HAIR CARE
DE69008526T2 (en) 1990-07-02 1994-08-18 Bend Res Inc Asymmetric microporous beads for adjustable release.
DE4306041A1 (en) 1993-02-26 1994-09-01 Wacker Chemie Gmbh Organosilicon compounds containing glycoside residues and process for their preparation
DE4413686C2 (en) 1994-04-20 1996-10-24 Henkel Kgaa Cationic sugar surfactants, process for their preparation and their use
DE4440625A1 (en) 1994-11-14 1996-05-15 Henkel Kgaa Process for the production of light colored chitosans
FR2726761A1 (en) * 1994-11-15 1996-05-15 Shiseido International France NEW SELF-TANNING COSMETIC COMPOSITIONS
DE19503465A1 (en) 1995-02-03 1996-08-08 Henkel Kgaa Process for the production of low-viscosity cationic biopolymers
GB9708182D0 (en) 1997-04-23 1997-06-11 Dow Corning Sa A method of making silicone in water emulsions
US5998537A (en) 1998-09-21 1999-12-07 Dow Corning Corporation Emulsions containing ultrahigh viscosity silicone polymers
FR2795639B1 (en) * 1999-07-02 2001-09-21 Oreal ARTIFICIAL SKIN COLORING COMPOSITIONS AND USES
FR2835183B1 (en) * 2002-01-30 2006-03-10 Caster SELF-TANNING COMPOSITION BASED ON A TERNARY ASSOCIATION OF COLORING AGENTS
JP3720000B2 (en) * 2002-04-04 2005-11-24 株式会社ナイアード Hair dye and hair dyeing method
DE10221811A1 (en) * 2002-05-16 2003-11-27 Beiersdorf Ag Skin-tanning cosmetics contain a malt extract to stabilize 1,3-dihydroxyacetone self-tanning agents and to color the composition
KR20040059173A (en) * 2002-12-28 2004-07-05 (주)바이오버드 Composition for preventing cardiovascular diseases
EP1591099A3 (en) * 2004-04-28 2005-11-09 MERCK PATENT GmbH Methods for stabilizing ingredients within cosmetics, personal care and household products
US20080260664A1 (en) * 2004-06-08 2008-10-23 Thomas Walenzyk Particles Functionalized with Organic Compounds

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0998908A2 (en) 1998-11-04 2000-05-10 L'oreal Dyeing composition containing a cattonic and an oxidativ dye based an pyrazolo-(1,5)-pyramidine and dyeing process
EP1237818A1 (en) 1999-11-23 2002-09-11 Universite Laval Mesoporous zeolitic material with microporous crystalline mesopore walls
EP1237817A1 (en) 1999-12-14 2002-09-11 Hercules Incorporated Metal silicates, cellulose products and processes thereof
EP1250912B1 (en) 2001-04-18 2004-09-15 KPSS-Kao Professional Salon Services GmbH Hair dye composition
EP1250908B1 (en) 2001-04-18 2007-03-14 KPSS-Kao Professional Salon Services GmbH Hair dye
EP1293192A2 (en) 2001-09-12 2003-03-19 KPSS-Kao Professional Salon Services GmbH Hair dye and process for dyeing human hair
WO2005094763A1 (en) 2004-03-26 2005-10-13 Wella Aktiengesellschaft Hair coloring agent containing indigoid vat dyes
WO2005094762A1 (en) 2004-03-26 2005-10-13 Wella Aktiengesellschaft Hair coloring agent containing vat dyes
US20050210606A1 (en) 2004-03-27 2005-09-29 Kpss-Kao Professional Salon Services Gmbh Pre-treatment composition for oxidative coloring keratin fibres and process therefore

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8551188B2 (en) 2009-09-02 2013-10-08 L'oreal Composition comprising a hydrophobic dye, a particular organic and/or mineral alkaline agent, a particular compound (I) and a particular organic compound (II), and dyeing use thereof
WO2011157666A1 (en) * 2010-06-16 2011-12-22 L'oreal Cosmetic use of a natural extract derived from beetroot peel for dyeing hair composition comprising the extract, an oxidizing agent, a basifying agent an optional metallic derivative
FR2961398A1 (en) * 2010-06-16 2011-12-23 Oreal COSMETIC USE OF A NATURAL EXTRACT FROM RED BEET PEEL, COMPOSITION COMPRISING THE EXTRACT AND A METAL DERIVATIVE, AN OXIDIZING AGENT AND AN ALKALINIZING AGENT
CN115012230A (en) * 2022-07-21 2022-09-06 浙江龙天服饰有限公司 Method for dyeing underwear knitted fiber by using sol
CN115120523A (en) * 2022-07-25 2022-09-30 南京斯拜科生物科技股份有限公司 Natural single-agent hair dyeing composition

Also Published As

Publication number Publication date
DE102007042286A1 (en) 2009-03-12
WO2009033833A3 (en) 2010-02-25
EP2182915A2 (en) 2010-05-12

Similar Documents

Publication Publication Date Title
EP2182915A2 (en) Coloring agent having natural dyes and 1,3-dihydroxyacetone
DE102008024030A1 (en) Brightening agent with cationic 3,4-Dihydroisochinoliniumderivaten, special alkanolamines and hydrogen peroxide
DE102008062239A1 (en) Process for decolorizing keratin-containing fibers
DE102008044715A1 (en) Cationic acylpyridinium derivatives as bleach activators
WO2009043613A1 (en) Brightening agent comprising cationic 3,4-dihydroisoquinoline derivatives and hydrogen peroxide
EP2014275A2 (en) Kit for preparing storage-stable formulations
DE102008052618A1 (en) Tricyclic aldehydes and C, H-acidic compounds
EP1893165A1 (en) Multicomponent composition for dyeing keratin fibres
DE102008044714A1 (en) Cationic dihydroisoquinolinium derivatives as bleach activators
DE102008061046A1 (en) Hair dye with color indicator
DE102008036535A1 (en) Coloration with cationizable polymer
DE102008046883A1 (en) Hair treatment with spirulina extract
WO2009019048A2 (en) Hair dyes
DE102009001039A1 (en) Cationic direct drawers and agents for dyeing keratinous fibers
DE102008018132A1 (en) Cationic direct drawers and agents for dyeing keratinous fibers
EP2044977B1 (en) Hair dye with oxidative pre-treatment
WO2009027112A1 (en) Hair treatment agents
DE102008046882A1 (en) Hair treatment agent with chitosan succinamide
EP1944010B1 (en) Brightening and/or colouring agent with acrylic acid derivative(s)
WO2009040149A1 (en) Biotin and silica to counter ageing of hair
DE102008061863A1 (en) Process for lamination of gray hair
DE102008056811A1 (en) Agent, useful e.g. for oxidative coloring of keratin fibers e.g. human hair, wool and feathers, comprises substituted 4-aminophenyl compounds and/or their salt as oxidation dyestuff precursor of developer-type in a cosmetic carrier
WO2009010415A2 (en) Agents comprising an anti-irritant active substance
DE102007053950A1 (en) Agent with bioflavonoid
EP1972323A2 (en) Hair colorant

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 08761090

Country of ref document: EP

Kind code of ref document: A2

WWE Wipo information: entry into national phase

Ref document number: 2008761090

Country of ref document: EP

NENP Non-entry into the national phase

Ref country code: DE