WO2007096027A1

WO2007096027A1 - Bleaching agents

Info

Publication number: WO2007096027A1
Application number: PCT/EP2007/000239
Authority: WO
Inventors: Astrid Kleen; Hartmut Manneck; Sina Eickhoff
Original assignee: Henkel Ag & Co. Kgaa
Priority date: 2006-02-20
Filing date: 2007-01-12
Publication date: 2007-08-30
Also published as: DE102006008149A1

Abstract

The invention relates to bleaching agents with a pH value greater than 7, which contain a mixture of at least two constituents A and B as the alkalisation agent instead of ammonia, where A is selected from special imidazole derivatives and B is selected from at least one alkanolamine, in particular from the group containing monoethanolamine, monoisopropanolamine, 2-amino-2-methyl-propanol, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol and 2-amino-2-methylbutanol. Said bleaching agents have an improved bleaching action and increased stability. The agents permit excellent bleaching results to be achieved without an unpleasant odour of ammonia during the bleaching process.

Description

"Bleach"

The invention relates to agents for whitening or bleaching keratin-containing fibers which contain a special combination of alkalizing agents and are free of ammonia.

Keratin fibers mean furs, wool, feathers and in particular human hair. Although the bleaching agents according to the invention are primarily suitable for dyeing keratin fibers, in principle there is nothing to prevent their use in other fields as well.

Lightening procedures, the so-called Blondierverfahren are often used as part of a cosmetic color change of the hair by the consumer. The oxidizing agents contained in the bleaching agents oxidatively act on the natural hair dye melanin and, optionally, on synthetic fibers present in the fiber. The coloring melanin can be almost completely decolorized oxidatively in this way. The basics of the bleaching technique are known to those skilled in the art and described in relevant monographs, e.g. by K. Schrader, Basics and Formulations of Cosmetics, 2nd edition, 1989, Dr. med. Alfred Hüthig Verlag, Heidelberg, or W. Limbach (ed.), Cosmetics, 2nd edition, 1995, Georg Thieme Verlag, Stuttgart, New York, described in summary.

For lightening or bleaching of human hair - especially for the application of highlights - usually anhydrous, solid or paste-to-oil preparations containing solid oxidizing agents and at least one alkaline salt immediately before use with an aqueous, diluted Hydrogen peroxide solution mixed. This mixture is then applied to the hair and rinsed again after a certain exposure time.

The conventional bleach ready for use keratin fibers contain hydrogen peroxide usually peroxodisulfate to increase the Aufhellleistung. These bleaches are usually made alkaline to achieve optimum brightening results. Most commercial products therefore have pH values of 9.0 to 11. The lightening power is optimal at this basic pH.

To adjust the pH, ammonia has hitherto usually been used, since ammonia-alkaline bleaching agents have better leaching than other alkaline bleaching agents.

The published patent application DE-A1-27 04 905 describes bleaches with ammonia-free alkalizing agent which contain a special guanidine compound to improve the lightening result. The alkalization is carried out with monoethanolamine.

The document WO-A2-02 / 78662 relates to ammonia-free bleaches as three separately stored components (kit), wherein a component contains as an alkalizing agent in an aqueous carrier at least 10 to 25 wt .-% monoethanolamine.

Alkaline bleaching agents that are free of ammonia can thus be formulated using short chain alkanolamines, such as monoethanolamine. While this clearly reduces the problem of ammonia odor, these amines still do not appear to be the optimal alkalizing agent. In order to be able to adjust the pH exclusively by means of the alkanolamines, high concentrations of this alkalizing agent are required. In particular, with frequent use of alkanolamines in higher concentrations, it may lead to undesirable effects on the hair structure. In addition, higher concentrations of alkanolamines, especially in combination with hydrogen peroxide, can cause scalp irritation in very sensitive individuals in some cases. In addition, suffers through the replacement of the ammonia by the alkanolamine the lightening power of the bleach noticeably.

For this reason, in addition to the alkanolamines, there is often added either a reduced amount of ammonia as the alkalizing agent or alternative alkalizing agents in combination with additional bleach boosters.

It has now surprisingly been found that the abovementioned difficulties can be overcome and bleaches having excellent properties can be formulated if the basicity of the bleaching agent is adjusted to an alkaline pH, in particular a pH of 8.0 to 10, by a special combination of alkalizing agents 12.0, is set.

The invention therefore relates to agents for lightening keratin-containing fibers, in particular human hair, which have a pH of greater than pH 7, in particular of pH 8.0 to 12.0, are free of ammonia and are present in a cosmetic carrier (a). at least one inorganic persalt, (b) at least one oxidizing agent and (c) as alkalizing agent a mixture of at least two constituents A and B, of which

A is selected from at least one imidazole derivative of the formula (I) and / or its physiologically tolerable salts,

wherein

R ¹ represents a hydrogen atom, an optionally substituted one

Aryl group or a (C _r C ₆ ) alkyl group, R ² is a hydrogen atom, a carboxaldehyde group, a (C

C ₆ ) alkyl group or a nitro group, R ³ represents a hydrogen atom, a carboxy (C ₁ -C ₆ ) alkyl group, a

Amino (C ₁ -C ₆ ) alkyl group, a carboxyl group, a

Carboxaldehyde group, a (CrCβJ-alkyl group, a nitro group, a 2-amino-3-hydroxypropyl group or a group -CH ₂ -CH (NH ₂ ) - COOH, R ⁴ represents a hydrogen atom, a carboxaldehyde group or a

Carboxyl group, and

B is selected from at least one alkanolamine.

The cosmetic agent according to the invention contains the components according to the invention in a cosmetic carrier. As cosmetic carriers are particularly suitable 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 cosmetic carriers may in particular be aqueous or aqueous-alcoholic.

An aqueous cosmetic carrier contains at least 50% by weight of water.

For the purposes of the present invention, aqueous-alcoholic cosmetic carriers are to be understood as meaning aqueous solutions containing from 3 to 70% by weight of a C ₁ -C ₄ -alkyl alcohol, in particular ethanol or isopropanol. Further alcoholic solvents are, for example, methoxybutanol, benzyl alcohol, 2-phenoxyethanol, ethyldiglycol or 1,2-propylene glycol.

The agents according to the invention are absolutely free of ammonia and preferably additionally free of ammonium ion-containing compounds, ie (NH ₄ ⁺ ) -containing compounds.

According to the invention, the inorganic persalts are inorganic peroxo compounds which are not addition products of hydrogen peroxide to other components represent. The selection of the inorganic persalts potentially contained in the agents according to the invention is subject in principle to no restrictions; customary inorganic persalts known to the person skilled in the art are, for example, ammonium peroxydisulfate, potassium peroxodisulfate, sodium peroxodisulfate,

Ammonium monopersulfate, potassium monopersulfate, sodium monopersulfate,

Potassium peroxide phosphate and peroxides such as magnesium and barium peroxide. Among these inorganic persalts, which may also be used in combination, those which do not contain ammonium ions (NH ₄ ⁺ ) are preferred according to the invention, since ammonia can be formed from the ammonium ions in a basic medium in an equilibrium reaction.

The inorganic persalts are preferably present in the bleaching agents according to the invention in amounts of 1-40% by weight, in particular in amounts of 2-30% by weight.

The agents according to the invention contain as an important component at least one oxidizing agent. The oxidizing agents according to the invention are different from the inorganic persalts. As the oxidizing agent of the present invention, hydrogen peroxide is preferably used. The hydrogen peroxide is added as a solution or in the form of a solid addition compound of hydrogen peroxide to inorganic or organic compounds, such as, for example, sodium perborate, sodium percarbonate,

Magnesium percarbonate, sodium percarbamide, polyvinylpyrrolidone n H ₂ O ₂ (n is a positive integer greater than 0), urea peroxide and melamine peroxide, used in the inventive compositions.

The concentration of a hydrogen peroxide solution is determined on the one hand by the legal requirements and on the other hand by the desired effect; As a rule, 6 to 12 percent solutions in water are used. The proportions of anhydrous composition and oxidizing agent-containing composition are usually in the range 1.5 to 1 to 1 to 2.

Preferably, the imidazole compounds according to formula I are selected from at least one member of a group which is formed from histamine, D-histidine, L-histidine, DL-histidine, D-histidinol, L-histidinol, DL-histidinol, imidazole, imidazole-4-acetic acid, imidazole-4-carboxylic acid, imidazole-4,5-dicarboxylic acid, imidazole-2-carboxaldehyde, imidazole-4-carboxaldehyde, imidazole-5-carboxaldehyde, 2-nitroimidazole, 4-nitroimidazole, 4-methylimidazole 5-carboxaldehyde, N-methylimidazole-2-carboxaldehyde, 4-methylimidazole, 2-methylimidazole, N-methylimidazole, N- (4-aminophenyl) -imidazole, and the physiologically acceptable salts of the aforementioned compounds. Imidazole is particularly preferably used as alkalizing agent A according to the invention.

The alkalizing agent A is contained in the bleaching agents according to the invention preferably in amounts of 0.1 to 10 wt .-%, in particular from 0.5 to 6 wt .-%, based on the total agent.

According to the invention, the term alkanolamine is understood to mean organic amine compounds which carry at least one C ₂ - to C ₆ -hydroxyalkyl group. The C ₂ - to C ₆ - hydroxyalkyl group in turn carries at least one hydroxy group. The alkanolamines according to the invention are preferably primary amines.

For example, 2-hydroxyethyl, 1,3-dihydroxy-2-methyl-propan-2-yl, 2-ethyl-1,3-dihydroxy-propan-2-yl, 1-hydroxy function as the C ₂ - to C ₆ -hydroxyalkyl group 2-methylbutan-2-yl, 3-hydroxypropyl and 4-hydroxybutyl.

The alkalizing agent B is preferably selected from at least one member of the group consisting of 2-aminoethanol (monoethanolamine), monoisopropanolamine, 2-amino-2-methyl-propanol, 2-amino-2-methyl-1,3-propanediol, 2- Amino-2-ethyl-1, 3-propanediol and 2-amino-2-methylbutanol is formed, more preferably selected from at least one member of the group, the monoethanolamine, 2-amino-2-methyl-propanol and 2-amino 2-methyl-1,3-propanediol.

Monoethanolamine has proven to be a particularly suitable alkalizing agent B.

The alkalizing agent B is likewise preferably present in the bleaching agents according to the invention in amounts of from 0.1 to 10% by weight, in particular from 0.5 to 6% by weight, based on the total agent. Particularly advantageous properties have been found in bleaching agents in which the alkalizing agents A and B were present in a molar ratio of 1 to 10 to 10 to 1. Molar ratios of 1 to 5 to 5 to 1 have proven to be particularly suitable.

Furthermore, it has proved to be advantageous if the pH of the bleaching agent according to the invention was adjusted to a value of 9.0 to 11.0.

As an additional alkalizing agent C, the agents according to the invention may comprise at least one compound of amino acids and / or oligopeptides, these in each case having at least two amino groups and at least one -COOH- or -SO H-

Group have and their 2.5% solution in water each having a pH greater than 9.0.

Preferred alkalizing agents C are aminocarboxylic acids, in particular α-aminocarboxylic acids and omega-aminocarboxylic acids. Among the α-aminocarboxylic acids lysine and especially arginine are again particularly preferred.

Said amino acids can preferably be added to the agents according to the invention in free form. In a number of cases, however, it is also possible to use the amino acids in salt form. Preferred salts are then the compounds with hydrohalic acids, in particular the hydrochlorides and hydrobromides.

Furthermore, the amino acids can also be used in the form of oligopeptides and protein hydrolysates if it is ensured that the required amounts of the amino acids used according to the invention are contained therein. In this context, reference is made to the disclosure of DE-OS 22 15 303, to which reference is expressly made.

A particularly preferred alkalizing agent C is arginine, especially in free form, but also used as the hydrochloride. The anhydrous compositions of the present invention may additionally contain at least one other bleaching enhancer other than the inorganic persalts.

As bleach amplifiers, it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups. Preference is given to polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5- diacetoxy-2,5-dihydrofuran.

To further increase the lightening power, at least one optionally hydrated SiO ₂ compound may additionally be added to the anhydrous composition according to the invention as bleach booster. Although even small amounts of the optionally hydrated SiO ₂ compounds increase the lightening power, it may be preferred according to the invention, the optionally hydrated SiO ₂ compounds in amounts of 0.05 wt .-% to 15 wt .-%, particularly preferably in amounts of 0.15 wt .-% to 10 wt .-% and most preferably in amounts of 0.2 wt .-% to 5 wt .-%, each based on the anhydrous composition of the invention to use. The amounts given in each case the content of the SiO ₂ compounds (without their water content) in the funds again.

With regard to the optionally hydrated SiO ₂ compounds, the present invention is in principle subject to no restrictions. Preference is given to silicic acids, their oligomers and polymers and their salts. Preferred salts are Alkali salts, especially the potassium and sodium salts. The sodium salts are very particularly preferred.

The optionally hydrated SiO ₂ compounds can be present in various forms. According to the invention, the SiO ₂ compounds are preferably used in the form of silica gels (silica gel) or particularly preferably as water glass. These SiO ₂ compounds may be partially present in aqueous solution.

Very particular preference according to the invention is given to water glasses formed from a silicate of the formula (SiO ₂ ) _n (Na ₂ O) _m (K ₂ θ) p, where n is a positive rational number and m and p are each independently one positive rational number or 0, with the provisos that at least one of the parameters m or p is different from 0 and the ratio between n and the sum of m and p is between 1: 4 and 4: 1.

In addition to the components described by the empirical formula, the water glasses in small amounts may contain other additives, such as phosphates or magnesium salts.

According to the invention particularly preferred water glasses are sold among others by Henkel under the names Ferrosil® ^® 119, soda water glass 40/42, Portil ^® A, Portil ^® AW and Portil ^® W and by Akzo under the name Britesil® ^® C20.

As bleach booster, carbonate salts or bicarbonate salts can preferably be used according to the invention. These are preferably selected from the group of ammonium, alkali (especially sodium and potassium), and alkaline earth (especially calcium), carbonate salts or bicarbonate salts. Particularly preferred carbonate or bicarbonate salts are ammonium bicarbonate, ammonium carbonate, sodium bicarbonate, disodium carbonate,

Potassium bicarbonate, dipotassium carbonate and calcium carbonate. These particularly preferred salts can be used alone or in their mixtures of at least two representatives as bleaching amplifiers. As bleach booster of the type of monoalkyl carbonates and their derivatives, at least one carbonic acid monoester and / or at least one carbonic acid monoamide are preferably used in the process according to the invention. Preferred carbonic acid monoesters are the carbonic acid monoesters of the formula (I)

R-O-C-O-H (I)

Il o

in which R is a saturated or unsaturated, straight-chain, branched, or cyclic, substituted or unsubstituted hydrocarbon radical, or a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocycle.

In formula (I), R preferably represents a substituted or unsubstituted, straight-chain or branched alkyl, alkenyl or alkynyl radical, preference being given to hydroxy, amino, nitro, sulfonic acid groups or halogens as substituents. Further preferred radicals R are phenyl and benzyl radicals and further substituted representatives. R is particularly preferably a d-β-alkyl group. Examples of CrC ₆ -alkyl groups according to the invention are the groups methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, isopentyl and hexyl.

Compositions particularly preferably used according to the invention are characterized in that the radical R in formula (I) is selected from methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, tert-butyl - As well as hydroxymethyl and hydroxyethyl radicals.

As an alternative to the carbonic acid monoester or in conjunction with it, carbonic acid monoamides can be used as bleach boosters in the anhydrous compositions. In this case, it is preferred according to the invention to use at least one carbonic acid monoamide of the formula (II) R-NH-COH (II)

Il o

In formula (II), R preferably represents a substituted or unsubstituted, straight-chain or branched alkyl, alkenyl or alkynyl radical, preference being given to hydroxy, amino, nitro, sulfonic acid groups or halogens as substituents. Further preferred radicals R are phenyl and benzyl radicals and further substituted representatives. R is particularly preferably a C 1-6 -alkyl group. Examples of CVCe-alkyl groups according to the invention are the groups methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, isopentyl and hexyl.

Bleach enhancers of the formula (II) which are particularly preferred according to the invention are characterized in that the radical R in formula (II) is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl , tert-butyl and hydroxymethyl and hydroxyethyl radicals.

The acidic H atom of the carbonic acid monoester or monoamide may also be in neutralized form, i. salts of carbonic acid monoesters or carbonic acid monoamides can also be used according to the invention. Carbonic acid monoesters or the carbonic acid monoamides which are present in completely or partially neutralized form, preferably in the form of the alkali metal, ammonium, alkaline earth metal or aluminum salt and in particular in the form of its sodium salt, are preferred according to the invention.

As a bleach booster of the type of silyl carbonates and their derivatives are preferably at least one silyl carbonate and / or at least one Silylcarbamat in the incorporated compositions of the invention. Preference is given to using silyl carbonates of the formula (III)

R ²

R ¹ -Si-OCOR ⁴ (III)

R ³ O

in which the radicals R ¹ , R ² and R ³ independently of one another represent a hydrogen atom, a saturated or unsaturated, straight-chain, branched or cyclic, substituted or unsubstituted hydrocarbon radical or a trialkylsilyl group, preferably a trimethylsilyl group or a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocycle or a halogen, a substituted or unsubstituted hydroxy, oxo, amino groups and the radical R ^{4 is} a chemical bond to the Si atom or to one of the radicals R ¹ , R ² or R ³ , a hydrogen atom, a saturated or unsaturated, straight-chain, branched, or cyclic, substituted or unsubstituted hydrocarbon radical or a substituted or unsubstituted SiIyI or Aluminylgruppe or a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocycle.

Preferred radicals R ¹ , R ² and R ³ in the abovementioned formula (III) are substituted or unsubstituted, straight-chain or branched alkyl radicals. Among these, the alkyl radicals having 1 to 5 carbon atoms and the hydroxyalkyl radicals are preferred, so that preferred anhydrous compositions according to the invention are characterized in that the radicals R ¹ , R ² and R ³ in formula (III) are selected from methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, hydroxymethyl and hydroxyethyl radicals.

Preferred radicals R ⁴ in the abovementioned formula (III) are hydrogen, substituted or unsubstituted, straight-chain or branched alkyl radicals and trialkylsilyl radicals. Among them, preferred are hydrogen, methyl, ethyl, tert-butyl and trimethylsilyl radicals. As bleach booster, at least one silyl carbamate of the formula (IV) may be present in the anhydrous composition according to the invention,

R ²

R ¹ -Si-OC-NR ⁴ R ⁵ (IV)

R ³ O

where the radicals R ¹ , R ² and R ³ independently of one another represent a hydrogen atom, a saturated or unsaturated, straight-chain, branched or cyclic, substituted or unsubstituted hydrocarbon radical or a trialkylsilyl group, preferably a trimethylsilyl group or a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocycle or a halogen, a substituted or unsubstituted hydroxy, oxo, amino groups and the radicals R ⁴ and R ⁵ independently of one another for a chemical bond to the Si atom or to one of the radicals R ¹ , R ² or R ³ , a hydrogen atom, a saturated or unsaturated, straight-chain, branched, or cyclic, substituted or unsubstituted hydrocarbon radical or a substituted or unsubstituted SiIyI or alumyl group or a substituted or unsubstituted aryl group or a substituted or unsubs substituted heterocycle.

Preferred radicals R ¹ , R ² and R ³ in the abovementioned formula (IV) are substituted or unsubstituted, straight-chain or branched alkyl radicals. Among them, the alkyl groups having 1 to 5 carbon atoms and the hydroxyalkyl groups are preferred, so that compositions preferably used are characterized in that the groups R ¹ , R ² and R ³ in formula (IV) are selected from methyl, ethyl, n Propyl, iso-propyl, n-butyl, iso-butyl, terf-butyl, hydroxymethyl and hydroxyethyl radicals.

Preferred radicals R ⁴ and R ⁵ in the abovementioned formula (IV) are hydrogen, substituted or unsubstituted, straight-chain or branched alkyl radicals and trialkylsilyl radicals. Among them, preferred are hydrogen, methyl, ethyl, tert-butyl and trimethylsilyl radicals. As further additional bleach boosters, in the compositions according to the invention preferably at least one compound selected from acetic acid, lactic acid, tartaric acid, citric acid, salicylic acid and ortho-phthalic acid may be contained.

Occasionally, special shades are desired that are not accessible by the sole use of bleach. The bleaching agents according to the invention can therefore, if they are to be used as bleaching and oxidative dyeing or shading agents, furthermore additionally comprise at least one developer component and optionally additionally at least one coupler component.

As developer components are usually primary aromatic amines with another, located in the para or ortho position free or substituted hydroxy or amino group, diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazolone derivatives and 2,4,5,6-tetraaminopyrimidine and its derivatives used.

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 (Ent1)

in which

G ¹ represents a hydrogen atom, a C ₁ - to C ₄ alkyl, C ₁ - to C ₄ - monohydroxyalkyl radical, a C ₂ - to C ₄ polyhydroxyalkyl radical, a (C ₁ - to C ₄₎ - alkoxy ( Ci to 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 is 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 ) -

AIkOXy- (C ₁ - to C ₄ ) -alkyl radical or a C ₁ - to C ₄ -alkyl radical which is substituted by a nitrogen-containing group;

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, C ₁ - to C ₄ -mesylaminoalkoxy or C ₁ - to C ₄ -carbamoylaminoalkoxy;

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-alkylenedioxy group such as an ethylenedioxy group.

Examples of the C ₁ - to C ₄ -alkyl radicals mentioned as substituents in the compounds according to the invention are the groups methyl, ethyl, propyl, isopropyl and butyl. Ethyl and methyl are preferred alkyl radicals. C ₁ -C ₄ -alkoxy radicals which are preferred according to the invention are, for example, a methoxy or an ethoxy group. Furthermore, as preferred examples of a C ₁ to C ₄ hydroxyalkyl group, there may be mentioned a hydroxymethyl, a 2-hydroxyethyl, a 3-hydroxypropyl or a 4-hydroxybutyl group. A 2-hydroxyethyl group is particularly preferred. A particularly preferred C ₂ to C ₄ polyhydroxyalkyl group is the 1, 2-dihydroxyethyl group. Examples of halogen atoms are according to the invention F, Cl or Br atoms, Cl atoms are very particularly preferred. The other terms used are derived according to the invention from the definitions given here. Examples of nitrogen-containing groups of the formula (Ent1) are especially the amino groups, C ₁ - to C ₄ monoalkylamino, C ₁ - to C ₄ dialkylamino, C ₁ - to C ₄ - trialkylammonium, d- to C ₄ -Monohydroxyalkylaminogruppen, imidazolinium and ammonium.

Particularly preferred p-phenylenediamines of the formula (Ent1) are selected 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, 4-N, N-bis (β-hydroxyethyl) amino-2-chloroaniline, 2- (β-hydroxyethyl) -p-phenylenediamine, 2- (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 and 5.8 -Diaminobenzo-1, 4-dioxane and their physiologically acceptable salts.

Very particular preferred p-phenylenediamine derivatives of the formula (Ent1) according to the invention are p-phenylenediamine, p-toluenediamine, 2- (β-hydroxyethyl) -p-phenylenediamine, 2- (α, β-dihydroxyethyl) -p-phenylenediamine and N, N Bis (β-hydroxyethyl) -p-phenylenediamine.

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.

Among the binuclear developer components that can be used in the compositions according to the invention, mention may be made in particular of the compounds which correspond to the following formula (Ent2) and their physiologically tolerated salts:

(Ent2) in which:

Z ¹ and Z ² independently of one another represent a hydroxyl or NH ₂ -ReSt ₁ which is optionally substituted by a C ₁ - to C ₄ -alkyl radical, by a C ₁ - to C ₄ -

Or Y is optionally substituted as part of a bridging ring system, the bridge Y is an alkylene group having 1 to 14 carbon atoms, such as a linear or branched alkylene chain or an alkylene ring, 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 possibly by one or more hydroxyl or C ₁ -

C ₈ alkoxy may be substituted, 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 -

Polyhydroxyalkyl 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 are each independently

Hydrogen atom, a direct bond to the bridging Y or a C ₁ - to C ₄ -

Alkyl radical, with the provisos that the compounds of formula (Ent2) contain only one bridge Y per molecule, and

- The compounds of formula (Ent2) contain at least one amino group which carries at least one hydrogen atom.

The substituents used in formula (Ent2) are inventively defined analogous to the above statements.

Preferred binuclear developer components of the formula (Ent2) are in particular: 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-methylaminophenyl) tetramethylenediamine, N ₁ N'-diethyl-N, N ' bis- (4'-amino-3'-methylphenyl) ethylenediamine, bis (2-hydroxy-5- aminophenyl) methane, 1, 3-bis- (2,5-diaminophenoxy) -propan-2-ol, 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 its physiologically acceptable salts.

Very particularly preferred binuclear developer components of the formula (Ent2) are 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 and 1, 10-bis (2 ', 5'-diaminophenyl) -1, 4,7,10-tetraoxadecane or one of its physiologically acceptable salts.

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 (Ent3)

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, C ₁ to C ₄ aminoalkyl, hydroxy (C ₁ to C ₄ ) alkylamino, C ₁ to C ₄ hydroxyalkoxy, C ₁ to C ₄ -hydroxyalkyl- (C ₁ -C ₄ ) -aminoalkyl or (C ₁ -C ₄ -alkylamino) - (C ₁ -C ₄ ) -alkyl, and

G ¹⁴ is 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 _r 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, C ₁ - to C ₄ -alkyl radical, a Cr to C ₄ - monohydroxyalkyl radical, a C ₂ - to C ₄ polyhydroxyalkyl radical, a phenyl radical or a benzyl radical, and

G ¹⁶ is hydrogen or a halogen atom.

The substituents used in formula (Ent3) are defined according to the invention analogously to the above statements.

Preferred p-aminophenols of the formula (Ent3) 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, A-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- (diethylaminomethyl) phenol and their physiologically acceptable salts.

Very particularly preferred compounds of the formula (Ent3) are p-aminophenol, A-amino-3-methylphenol, 4-amino-2-aminomethylphenol, 4-amino-2- (α, β-dihydroxyethyl) phenol and 4-amino 2- (diethylaminomethyl) -phenol.

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.

Further, the developer component may be selected from heterocyclic developer components such as the pyridine, pyrimidine, pyrazole, pyrazole pyrimidine derivatives and their physiologically acceptable salts.

Preferred pyridine derivatives are, in particular, the compounds described in the patents GB 1 026 978 and GB 1 153 196, such as 2,5-diamino-pyridine, 2- (4'-methoxyphenyl) amino-3-amino-pyridine, 2,3-diamino-6-methoxy-pyridine, 2- (β-

Methoxyethyl) amino-3-amino-6-methoxy-pyridine and 3,4-diamino-pyridine. Preferred pyrimidine derivatives are, in particular, the compounds described in German patent DE 2 359 399, Japanese laid-open specification JP 02019576 A2 or in published patent application WO 96/15765, such as 2,4,5,6-tetraaminopyrimidine, 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, in particular, the compounds described in patents DE 3 843 892, DE 4 133 957 and patent applications WO 94/08969, WO 94/08970, EP-740 931 and DE 195 43 988, such as 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- (2-aminoethyl) amino-1,3-dimethylpyrazole, 3,4,5- Triaminopyrazole, 1-methyl-3,4,5-triaminopyrazole, 3,5-diamino-1-methyl-4-methylaminopyrazole and 3,5-diamino-4- (β-hydroxyethyl) amino-1-methylpyrazole.

Preferred pyrazolopyrimidine derivatives are, in particular, the derivatives of the pyrazolo [1,5-a] opyrimidine of the following formula (Ent4) and their tautomeric forms, if a tautomeric equilibrium exists:

(Ent4)

D- to C ₄ alkyl radical, an aryl radical, a hydroxyalkyl radical to C _4, a C ₂ - - G ^17, G ^18, G ¹⁹ and G ²⁰ are independently a hydrogen atom, a C ₁ to C ₄ - Polyhydroxyalkylrest a (d- to C ₄ ^ AIkOXy- (C ₁ - to C ₄ ) -alkyl radical, a C ₁ - to C ₄ -Aminoalkylrest, which may optionally be protected by an acetyl-ureide or a sulfonyl radical, a (C ₁ - to C ₄₎ alkylamino (C ₁ - to C ₄₎ - alkyl group, a DK (C ₁ - to C ₄₎ alkyl] - (C _r to C ₄₎ aminoalkyl, wherein the dialkyl Radicals optionally form a carbon cycle or a heterocycle with 5 or 6 chain members, a C ₁ - to C ₄ -hydroxyalkyl or a di- (C ₁ - to C ₄ ) - [hydroxyalkyl] - (C _r 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 -hydroxyalkyl group, a C ₂ - to C ₄ - polyhydroxyalkyl radical, a C ₁ - to C ₄ -Aminoalkylrest, a (C ₁ - to C ₄₎ alkylamino (Cr to _C4) alkyl, a di - [(C _r to C ₄₎ alkyl] - (C ₁ - to C ₄₎ aminoalkyl, wherein the dialkyl residues optionally form a carbocycle or a heterocycle with 5 or 6 chain links, a C ₁ - to C ₄ hydroxyalkyl or a di- (C ₁ - to C ₄ hydroxyalkyl) aminoalkyl group, an amino group, a C ₁ - to C ₄ - Alkyl or di- (C ₁ - to C ₄ -hydroxyalkyl) amino, a halogen atom, a carboxylic acid group or a 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 and n has the value 0 or 1, with the proviso that the sum of p + q is not 0, if p + q is 2, n is 0, and the groups NG ^{17 are} G ¹⁸ and NG ¹⁹ G ²⁰ occupy the positions (2,3); (5,6); (6,7); (3,5) or (3,7); wweennnn pp ++ qq gglleeiicchh 11 iisstt ,, nn the former WWeerrtt 11 hhaatt ,, and and the dGrruppppeen NG ¹⁷ G ¹⁸ (or NG ¹⁹ G ²⁰ ) and the group OH occupy the positions (2,3); (5,6); (6,7); (3,5) or (3,7);

The substituents used in formula (Ent4) are defined according to the invention analogously to the above statements. When the pyrazolo [1,5-a] pyrimidine of the above formula (Ent4) contains a hydroxy group at one of the 2, 5 or 7 positions of the ring system, there is a tautomeric equilibrium which is shown, for example, in the following scheme:

Among the pyrazolo [1, 5-a] pyrimidines of the above formula (Ent4) may be mentioned in particular:

Pyrazolo [1,5-a] pyrimidine-3,7-diamine;

2,5-dimethyl-pyrazolo [1,5-a] pyrimidine-3,7-diamine;

Pyrazolo [1,5-a] pyrimidine-3,5-diamine;

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-5-ol;

2- (3-aminopyrazolo [1,5-a] pyrimidin-7-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 - [(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] pyrimidine-3,7-diamine;

3-amino-7-dimethylamino-2,5-dimethylpyrazolo [1,5-a] pyrimidine; and their physiologically acceptable salts and their tautomeric forms when tautomeric equilibrium is present.

The pyrazolo [1, 5-a] pyrimidines of the above formula (Ent4) can be prepared as described in the literature by cyclization from an aminopyrazole or hydrazine. As coupler components m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenol derivatives and heterocyclic compounds are generally used.

According to preferred coupler components are

- M-aminophenol and its derivatives such as 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 and 2,4-dichloro 3-aminophenol,

- o-aminophenol and its derivatives, m-diaminobenzene and its derivatives such as 2,4-Diaminophenoxy- ethanol, 1, 3-bis (2 ', 4'-diaminophenoxy) propane, _l 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-yl-phenyl) -amino] -ethanol, 3-amino-4- (2-methoxy ethoxy) -5-methylphenylamine and 1-amino-3-bis (2'-hydroxyethyl) aminobenzene, o-diaminobenzene and its derivatives such as 3,4-diaminobenzoic acid and 2,3-diamino-i-methylbenzene,

Di- or trihydroxybenzene derivatives such as resorcinol, resorcinol monomethyl ether, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 2-chlororesorcinol, 4-chlororesorcinol, pyrogallol and 1,2,4-trihydroxybenzene, pyridine derivatives such as 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 and 3,5-diamino-2,6-dimethoxypyridine, naphthalene derivatives such as 1-naphthol, 2-methyl-1-naphthol, 2- Hydroxymethyl-1-naphthol, 2-hydroxyethyl-1-naphthol, 1, 5-dihydroxynaphthalene, 1, 6 Dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,7-

Dihydroxynaphthalene and 2,3-dihydroxynaphthalene,

Morpholine derivatives such as 6-hydroxybenzomorpholine and 6-aminobenzomorpholine,

Quinoxaline derivatives such as 6-methyl-1,2,3,4-tetrahydroquinoxaline,

Pyrazole derivatives such as 1-phenyl-3-methylpyrazol-5-one,

Indole derivatives such as 4-hydroxyindole, 6-hydroxyindole and 7-hydroxyindole,

Pyrimidine derivatives such as 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, or

- Methylendioxybenzolderivate such as 1-hydroxy-3,4-methylenedioxybenzene, 1-amino-3,4-methylenedioxybenzene and 1 - (2'-hydroxyethyl) amino-3,4-methylenedioxybenzene and their physiologically acceptable salts.

Particularly preferred coupler components according to the invention are 1-naphthol, 1, 5, 2,7- and 1, 7-dihydroxynaphthalene, 3-aminophenol, 5-amino-2-methylphenol, 2-amino-3-hydroxypyridine, resorcinol, 4-chlororesorcinol , 2-chloro-6-methyl-3-aminophenol, 2-methyl resorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol and 2,6-dihydroxy-3,4-dimethylpyridine and the physiologically acceptable salts of the abovementioned compounds.

The agents according to the invention may preferably contain the developer components in an amount of from 0.005 to 10% by weight, preferably from 0.1 to 5% by weight, based in each case on the total agent.

The compositions of the invention may contain the coupler components preferably in an amount of 0.005 to 10 wt .-%, preferably from 0.1 to 5 wt .-%, each based on the total agent.

The developer and coupler components are usually used in free form. In the case of substances having amino groups, however, it may be preferable to use them in salt form, in particular in the form of the hydrochlorides and hydrobromides. In a further embodiment, the bleaching agents according to the invention may contain, in addition to the alkalizing agent combination according to the invention, additionally alkali metal hydroxides and alkaline earth metal hydroxides, carbonates, bicarbonates, hydroxycarbonates and carbamides, as well as alkali phosphates as alkalizing agents.

The bleaching agents according to the invention preferably contain the additional alkalizing agents in amounts of from 0.2 to 25% by weight, in particular from 0.5 to 10% by weight.

In a further embodiment, the bleaching agents according to the invention additionally contain further structurally improving active ingredients. Such active ingredients which improve hair structure represent vitamins and their derivatives or precursors. Panthenol and its physiologically tolerated derivatives are particularly preferred according to the invention. Such derivatives are in particular the esters and ethers of panthenol as well as cationically derivatized panthenols. Individual representatives are, for example, the panthenol triacetate, the panthenol monoethyl ether and its monoacetate and also the cationic panthenol derivatives disclosed in WO 92/13829 A1. An inventively preferred panthenol derivative is also its precursor pantolactone. Panthenol is preferred within this group. Another example of a structurally improving vitamin is pyridoxine (vitamin B6).

Furthermore, polyvinylpyrrolidone (PVP) is known for its fibrous structure-improving properties and preferred according to the invention.

Further, according to the invention particularly effective, structurally improving compounds are the aldehydes. Particularly preferred examples are formaldehyde and formaldehyde-releasing compounds, such as methoxymethyl esters, dimethylol (thio) urea derivatives, oxazolidine derivatives, N-hydroxymethylmaleimide, hexamethylenetetramine and its derivatives, hydantoin derivatives, pyridinium-substituted Dimethyl ethers, imidazolidinylurea derivatives, isothiazolinones, 2-bromo-2-nitropropanediol and 5-bromo-5-nitro-1,3-dioxane. Further particularly preferred aldehydes are acetaldehyde, glyoxal, glyceraldehyde and glutaric dialdehyde. Another suitable group of structurally-improving active ingredients are plant extracts.

Usually these extracts are produced by extraction of the whole plant. However, in individual cases it may also be preferred to prepare the extracts exclusively from flowers and / or leaves of the plant.

With regard to the plant extracts which can be used according to the invention, particular reference is made to the extracts listed in the table beginning on page 44 of the 3rd edition of the guideline for the ingredient declaration of cosmetic products, published by the Industrial Association for Personal Care and Detergent e.V. (IKW), Frankfurt.

The extracts of oak bark, stinging nettle, witch hazel, hops, chamomile, burdock root, horsetail, hawthorn, lime blossom, almond, aloe vera, spruce needle, horse chestnut, sandalwood, juniper, coconut, mango, apricot, lime, wheat, kiwi, Melon, orange, grapefruit, sage, rosemary, birch, mallow, meadowfoam, quenelle, yarrow, thyme, lemon balm, toadstool, coltsfoot, marshmallow, meristem, green tea, ginseng and ginger root are preferred.

Particularly preferred are the extracts of oak bark, stinging nettle, witch hazel, hops, chamomile, burdock root, horsetail, lime blossom, almond, aloe vera, coconut, mango, apricot, lime, wheat, kiwi, melon, orange, grapefruit, sage, rosemary, birch , Meadowfoam, quenelle, yarrow, toadstool, meristem, green tea, ginseng and ginger root.

Especially suitable for the compositions according to the invention are the extracts of almond, aloe vera, coconut, mango, apricot, lime, wheat, kiwi, melon and green tea.

As extraction agent for the preparation of said plant extracts water, alcohols and mixtures thereof can be used. Among the alcohols are lower alcohols such as ethanol and isopropanol, but especially polyhydric alcohols such as ethylene glycol and propylene glycol, both as the sole extractant and in admixture with water. Plant extracts based on water / propylene glycol in a ratio of 1:10 to 10: 1 have proven to be particularly suitable.

The plant extracts can be used according to the invention both in pure and in diluted form. If they are used in diluted form, they usually contain about 2 to 80 wt .-% of active substance and as a solvent used in their extraction agent or extractant mixture.

Furthermore, it may be preferred to use in the compositions according to the invention mixtures of several, especially two, different plant extracts.

Likewise preferred according to the invention as structure-improving active ingredients are honey extracts. These extracts are obtained in an analogous manner to the plant extracts and usually contain 1-10 wt .-%, in particular 3-5 wt .-%, of active substance. Water / propylene glycol mixtures may also be preferred extractants here.

Further structurally improving active substances are protein hydrolysates, in particular elastin, collagen, keratin, milk protein, soy protein, almond protein and wheat protein hydrolysates, their condensation products with fatty acids and quaternized protein hydrolysates. Highly degraded keratin hydrolysates are particularly preferred having molecular weights in the range of 400 to 800. Further, quaternized protein hydrolyzates, such as for example, under the trade designations Gluadin ^® WQ (INCI name: Laurdimonium Hydroxypropyl Hydrolyzed Wheat Protein) and Crotein ^® Q (INCI name: Hydroxypropyltrimonium Hydrolyzed collagen) are sold, particularly preferred according to the invention.

Besides the quaternized protein hydrolysates, quaternary polymers are inventively preferred restructuring compounds are the polymers (name INCI: Polyquaternium-2) under the trade names Mirapol ^® A15 are particularly preferred., Onamer ^® M (INCI name: Polyquaternium-1) and Merquat ^® 100 (INCI name: Polyquaternium-6) Polymer JR 400 (INCI name: Polyquaternium-10) are distributed.

Also fiber structure-improving agents are mono-, di- and oligosaccharides such as glucose, galactose, fructose, fructose, sucrose and lactose. Furthermore, derivatives of these pentoses, hexoses and heptoses, such as the corresponding on- and uronic acids (sugar acids), sugar alcohols, sugar amines, such as N-glucosamine, and glycosides, and with C ₄ -C ₃₀ fatty alcohols etherified pentoses, hexoses and heptoses to be used according to the invention. The sugar acids can be used according to the invention in free form, in the form of their salts, preferably calcium, magnesium and zinc salts, and in the form of their esters or lactones. Preferred sugar acids are gluconic acid, gluconic acid γ-lactone, lactobionic acid, glucuronic acid and its mono- or dilactones, pangamic acid, sugar acid, mannose and its mono- or dilactones, as well as mucic acid and its mono- or dilactones. Preferred sugar alcohols are sorbitol, mannitol and dulcitol. Preferred glycosides are the methylglucosides. Glucose, N-glucosamine and gluconic acid are particularly preferred from this group.

Certain amino acids can also be used in the context of the present invention as hair structure-improving active ingredients. Examples are the amino acids serine, threonine and tyrosine described in DE-195 22 569, to which reference is expressly made. Further, derivatives of serine, such as the serine phosphate, are also preferred according to the invention. Serine is a particularly preferred fiber structure-improving agent.

Likewise to improve the structure certain acids, in particular α-hydroxycarboxylic acids, and their salts can be used. Structurally-improving acids which are preferred according to the invention are lactic acid, malic acid, tartaric acid, glyceric acid and maleic acid. Lactic acid and glyceric acid are particularly preferred. Furthermore, special phosphonic acids and their salts improve the structure of keratin-containing fibers. Phosphonic acids preferred according to the invention are the n-octylphosphonic acid and the n-decylphosphonic acid. Furthermore, lipid-soluble ester alcohols or ester polyols are known for their structure-improving action. They are considered to be lipid-soluble if 5% by weight of these products in cetyl alcohol dissolve clearly at 80 ° C.

The ester alcohols or ester polyols which are suitable according to the invention are obtainable by reacting an epoxy fatty acid ester with water or mono- or polyhydric alcohols having 1-10 carbon atoms with opening of the epoxide ring and forming a vicinal dihydroxyethyl or hydroxyalkoxyethyl group. The epoxy fatty acid ester may also be an epoxidation product of a technical fatty acid ester with proportions of saturated fatty acids. However, the epoxy oxygen content should be at least 3% by weight, preferably 5-10% by weight.

The epoxy fatty acid esters are either epoxidized fatty acid esters of monohydric alcohols, e.g. epoxidized oleic acid methyl ester, linoleic acid methyl ester, ricinoleic acid methyl ester or epoxidized fatty acid esters of polyhydric alcohols, e.g. Glycerol monooleate or propylene glycol monooleate or epoxidized fatty acid triglycerides, e.g. Oleic acid triglyceride or unsaturated oils, e.g. Olive oil, soybean oil, sunflower oil, linseed oil, rapeseed oil.

Especially interesting from a technical point of view are unsaturated fatty acid methyl ester epoxides from unsaturated vegetable fatty acids. For example, the reaction product of a vegetable oil fatty acid methyl ester epoxide with a polyol having 2 to 6 C atoms and 2 to 6 hydroxyl groups is particularly preferred as ester polyol. As polyols, e.g. Ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, butanediol, pentanediol, hexanediol, glycerol, trimethylolpropane, pentaerythritol, sorbitol or diglycerol.

Especially good is the reaction product of a Pflanzenfettsäuremethylester epoxidate with trimethylolpropane and having a hydroxyl number of 350 is doing for the novel bleach ester polyol - 450. Such a product based on Sojaölfettsäuremethylester epoxide and trimethylolpropane is available under the trade name Sovermol ^® 760th Furthermore, vitamin B ₃ can be used as structure-improving active ingredient. Under this name, the compounds nicotinic acid and nicotinamide (niacinamide) are often performed. According to the invention, the nicotinic acid amide is preferred.

Vitamin H can also be used as structurally improving active ingredient in the context of the present invention. Vitamin H is the compound (3aS, 4S, 6aR) -2-oxohexa-hydrothienol [3,4-d] imidazole-4-valeric acid, for which, however, the trivial name biotin has meanwhile prevailed.

Structure-improving active ingredients which are particularly preferred according to the invention are selected from panthenol, physiologically tolerated panthenol derivatives, mono-, di- and oligosaccharides, serine, lactic acid, glyceric acid, niacinamide, vitamin B6, polyvinylpyrrolidone, glucose, gluconic acid, biotin and the lipid-soluble ester alcohols or ester polyols.

The agents according to the invention preferably contain the structure-improving active compounds in amounts of from 0.1 to 5% by weight, more preferably in amounts of from 0.2 to 2% by weight.

In a preferred embodiment of the present invention, the agents further contain a magnesium compound. The agents according to the invention can be further optimized by adding the Mg ²⁺ cations with regard to their structure-retaining properties. Preferred magnesium compounds are inorganic and organic Mg ²⁺ salts, such as the halides, the carbonates and bicarbonates, the acetate and the citrate.

The compositions according to the invention may furthermore contain all active substances, additives and auxiliaries known for such preparations. In many cases, the bleaching agents additionally contain at least one surfactant, with both anionic and zwitterionic, ampholytic, nonionic and cationic surfactants being suitable in principle. In many cases, however, it has proved to be advantageous to select the surfactants from anionic, zwitterionic or nonionic surfactants. Suitable anionic surfactants 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 as well as mono-, di- and trialkanolammonium salts with 2 or 3 C atoms in the alkanol group, linear fatty acids having 10 to 22 C atoms (Soap),

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, acylsarcosides having 10 to 18 C Atoms in the acyl group, acyltaurides having 10 to 18 C atoms in the acyl group, acyl isethionates having 10 to 18 C atoms in the acyl group,

Sulfobemsteinsäuremono- 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 alkane sulfonates 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 ₁ in the R preferably a linear alkyl group with 10 bis 18 C atoms and x = 0 or 1 to 12,

Blends 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,

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. Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids having 10 to 18 C 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.

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 the N-alkyl-NN dimethylammonium glycinates, for example cocoalkyldimethylammonium glycinate, N-acylaminopropyl N, N-dimethylammonium glycinates, for example cocoacylaminopropyldimethylammonium glycinate, and 2-alkyl-3-carboxymethyl-3-hydroxyethylimidazolines having in each case 8 to 18 C A preferred zwitterionic surfactant is the fatty acid amide derivative known under the INCI name cocamidopropyl betaine.

Ampholytic surfactants are surface-active compounds which, in the ₃ H-group in addition to a C ₈ .i ₈ alkyl or acyl group in the molecule at least one free amino group and at least one -COOH or -SO and which are capable of forming inner salts , Examples of suitable ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each having about 8 to 18 C Atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethyl aminopropionate and C _{_2-18} acyl sarcosine.

Nonionic surfactants contain as hydrophilic group z. B. a polyol group, a polyalkylenglykolethergruppe or a combination of polyol and Polyglykolether- group. Such compounds are, for example Addition products of 2 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide onto linear fatty alcohols having 8 to 22 carbon atoms, to fatty acids containing 12 to 22 carbon atoms and to alkylphenols having 8 to 15 carbon atoms in the alkyl group,

- C _{_2-22} fatty acid monoesters and diesters of addition products of 1 to 30 mol ethylene oxide onto glycerol,

C _{8-22 alkyl} mono- and oligoglycosides and their ethoxylated analogs,

Adducts of 5 to 60 moles of ethylene oxide with castor oil and hydrogenated castor oil,

- Addition products of ethylene oxide to sorbitan fatty acid esters

- Addition products of ethylene oxide to fatty acid alkanolamides.

Examples of the cationic surfactants which can be used in the bleaching agents according to the invention are, in particular, quaternary ammonium compounds. Preference is given to ammonium halides such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, eg. Cetyltrimethylammonium chloride, stearylthymethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride. Further cationic surfactants which can be used according to the invention are the quaternized protein hydrolysates.

Also suitable in the present invention are cationic silicone oils 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; diquaternary polydimethylsiloxanes, Quaternium-80).

Alkylamidoamines, in particular fatty acid amidoamines, such as the ^{stearylamidopropyldimethylamine} obtainable under the name Tego ^Amid® S 18, are distinguished not only by a good conditioning action but also by their good biodegradability. Also very good biodegradability quaternary Esterverbindungen, so-called "esterquats", such as the methyl marketed under the trademark Stepantex ^® Hydroxyalkyldialkoyloxyalkyl-ammonium methosulfates and the products sold under the trademark Dehyquart ^® products such as Dehyquart ^® AU-46.

An example of a suitable cationic surfactant quaternary sugar derivative is the commercial product Glucquat ^® 100, according to INCI nomenclature a "lauryl methyl Gluceth-10 Hydroxypropyl Dimonium Chloride".

The compounds containing alkyl groups used as surfactants may each be uniform substances. However, it is usually preferred to start from the production of these substances from native plant or animal raw materials, so as to obtain substance mixtures with different, depending on the particular raw material alkyl chain lengths.

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 homologues which are 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, on the other hand, are obtained when, for example, hydrotalcites, alkaline earth metal salts of ether carboxylic acids, alkaline earth metal oxides, hydroxides or alkoxides are used as catalysts. The use of products with narrow homolog distribution may be preferred.

Furthermore, the bleaching agents according to the invention may preferably also contain a conditioning agent selected from the group consisting of cationic surfactants, cationic polymers, alkylamidoamines, paraffin oils, vegetable oils and synthetic oils.

Cationic polymers may be preferred as conditioning agents. These are usually polymers containing a quaternary nitrogen atom, for example in the form of an ammonium group. 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. polymeric dimethyldiallylammonium salts and their copolymers with acrylic acid and esters and amides of acrylic acid and methacrylic acid. Under the names Merquat ^® 100 (Poly (dimethyldiallylammoniurnchlorid)), Merquat ^® 550 (dimethyldiallylammonium chloride-acrylamide copolymer) and Merquat ^® 280 (dimethyldiallylammonium chloride-acrylic acid copolymer commercially available products are examples of such cationic polymers.

Copolymers of vinylpyrrolidone with quaternized derivatives of dialkylamino acrylate and methacrylate, such as diethyl sulfate quaternized vinylpyrrolidone-dimethylaminomethacrylate copolymers. Such compounds are sold under the names Gafquat ^® 734 and Gafquat ^® 755 commercially. Vinylpyrrolidone-Methoimidazoliniumchlorid copolymers, such as those available under the name Luviquat ^® , quaternized polyvinyl alcohol and those under the names Polyquatemium 2, Polyquatemium 17, Polyquaternium 18 and

Polyquaternium 27 known polymers with quaternary nitrogen atoms in the polymer main chain.

Particular preference is given to cationic polymers of the four first-mentioned groups, with very particular preference being given to polyquaternium-2, polyquaternium-10 and polyquaternium-22.

Further suitable conditioning agents are silicone oils, in particular dialkyl and alkylaryl siloxanes, such as, for example, dimethylpolysiloxane and methylphenylpolysiloxane, and also their alkoxylated and quaternized analogs. Examples of such silicones are the products marketed by Dow Corning under the designations DC 190, DC 200, DC 344, DC 345 and DC 1401 and the commercial products Q2-7224 (manufacturer: Dow Corning; a stabilized trimethylsilylamodimethicone), Dow Corning ^® 929 Emulsion (containing a hydroxylamino-modified silicone which is also known as amodimethicone), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil ^® - Quat 3270 and 3272 (manufacturer: Th. Goldschmidt, di-quaternary polydimethylsiloxanes, quaternium-80).

Also usable as conditioning active ingredients are paraffin oils, synthetically produced oligomeric alkenes and vegetable oils such as jojoba oil, sunflower oil, orange oil, almond oil, wheat germ oil and peach kernel oil, and tocopherol acetate.

Likewise suitable hair-conditioning compounds are phospholipids, for example soya lecithin, egg lecithin and cephalins.

Further active agents, auxiliaries and additives are, for example, nonionic polymers such as, for example, vinylpyrrolidone / inyl acrylate copolymers, polyvinylpyrrolidone and vinylpyrrolidone / vinyl acetate copolymers and polysiloxanes, zwitterionic and amphoteric polymers such as, for example, acrylamidopropyltrimethylammonium chloride / acrylate copolymers and octylacrylamide / methylmethacrylate copolymers. lat / tert-butylaminoethyl methacrylate γ-hydroxypropyl methacrylate copolymers, anionic polymers such as polyacrylic acids, crosslinked polyacrylic acids, vinyl acetate / crotonic acid copolymers, vinylpyrrolidone / vinyl acrylate copolymers,

Vinyl acetate / butyl maleate / isobornyl acrylate copolymers, methyl vinyl ether / maleic anhydride copolymers and acrylic acid / ethyl acrylate / N-tert-butyl acrylamide terpolymers,

Thickeners such as agar-agar, guar gum, alginates, xanthan gum, gum arabicum, karaya gum, locust bean gum, linseed gums, dextrans, cellulose derivatives, e.g. For example, methylcellulose, hydroxyalkylcellulose and carboxymethylcellulose, starch fractions and derivatives such as amylose, amylopectin and dextrins, clays such. B. bentonite or fully synthetic hydrocolloids such as polyvinyl alcohol, structurants such as maleic acid and lactic acid, Protein hydrolysates, in particular elastin, collagen, keratin, milk protein, soy protein and wheat protein hydrolysates, their condensation products with fatty acids and quaternized protein hydrolysates, perfume oils, cyclodextrins,

Solvents and mediators such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol, dimethyl isosorbide and diethylene glycol, quaternized amines such as methyl-1-alkylamidoethyl-2-alkylimidazolinium methosulfate defoamers such as silicones, dyes for dyeing the agent,

Antidandruff active ingredients such as Piroctone Olamine, zinc Omadine and Climbazole, light stabilizers, in particular derivatized benzophenones, cinnamic acid derivatives and triazines,

Substances for adjusting the pH, such as, for example, customary acids, in particular edible acids and bases,

Active ingredients such as allantoin, pyrrolidonecarboxylic acids and their salts as well as bisabolol, cholesterol,

Bodying agents such as sugar esters, polyol esters or polyol alkyl ethers, fats and waxes such as spermaceti, beeswax, montan wax and paraffins, fatty acid alkanolamides,

Complexing agents such as EDTA, NTA ₁ β-alaninediacetic acid and phosphonic acids, swelling and penetrating substances such as glycerol, propylene glycol monoethyl ether, carbonates, bicarbonates, guanidines, ureas and primary, secondary and tertiary phosphates,

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.

With regard to further optional components and the amounts of these components used, reference is expressly made to those relevant to the person skilled in the art Manuals, eg. B. Kh. Schrader, bases and formulations of cosmetics, 2nd edition, Hüthig book publisher, Heidelberg, 1989, referenced.

A second object of the invention is the use of a composition of the first subject of the invention for whitening and / or bleaching keratin-containing fibers, in particular human hair.

A third object of the present invention is a process for whitening and / or bleaching keratin-containing fibers, in particular human hair, in which the fibers are treated with the above-described agent of the first subject of the invention.

The bleaches of the first subject of the invention are preferably prepared shortly before use on the fiber by blending various components. For this purpose, a component 1, which contains in a cosmetic carrier at least one inorganic persalt, with a component 2, containing in a cosmetic carrier at least one oxidizing agent, in particular hydrogen peroxide, and a component 3, in a cosmetic carrier as alkalizing a mixture of at least two constituents A and B, of which

A is selected from amino acids and oligopeptides with at least one compound according to formula (I) and / or its physiologically acceptable salts,

in which R ¹ , R ² , R ³ and R ⁴ are defined as described above and

B is selected from at least one alkanolamine, mixed to form a homogeneous application mixture, wherein the mixture has a pH greater than pH 7, in particular from pH 8 to 12, and is free of ammonia.

The components 1, 2 and 3 are free of ammonia and preferably additionally free of ammonium ion-containing, ie (NH ₄ ⁺ ) -containing compounds. Component 1 is preferably present as a solid, which may be formulated in the form of a granulate, a tablet or a powder. If the component 1 is present as a powder, it is again preferable to dedust the powder, for example by means of di-n-octyl ether or other oils.

The concentration of the hydrogen peroxide solution of the component 2 is determined on the one hand by the legal requirements and on the other hand by the desired effect; As a rule, 6 to 12 percent solutions in water are used.

Component 3 is preferably present as a cream, paste, a W / O emulsion, an O / W emulsion or as an oil.

A fourth subject of the invention is therefore a sales unit or kit containing at least three separately stored compositions, wherein

(i) in a first container, a composition used in a cosmetic

Carrier contains at least one inorganic persalt, (ii) in a second container, a composition which is in a cosmetic

Carrier contains at least one oxidizing agent and

(iii) in a third container, at least one composition containing in a cosmetic carrier, as alkalizing agent, a mixture of at least two components A and B, of which

A is selected from at least one compound according to formula (I) and / or its physiologically acceptable salts,

in which R ¹ , R ² , R ³ and R ⁴ are defined as described above and

B is selected from at least one alkanolamine stored. The compositions of the first, second and third containers, or all compositions of the kit, which are mixed to obtain a composition according to the invention are free of ammonia.

The embodiments of the first subject of the invention apply mutatis mutandis for the subject invention two to four.

The following examples are intended to illustrate the subject matter of the present invention without, however, limiting it.

B e i s p e e l e

The following raw materials were used to prepare the example formulations:

Carbopol ^® ETD 2020 crosslinked acrylic acid copolymer, a white powder (INCI name: Acrylates / C10-30 alkyl acrylates crosspolymer) (Noveon)

Gluadin ^® AGP wheat protein hydrolyzate, yellow powder (INCI name: Hydrolyzed Wheat Protein) (Cognis)

Dow Corning 193 ^Fluid® Silicone Glycol Copolymer (INCI name: PEG-12 Dimethicone) (Dow Corning)

Synthalen ^® K polyacrylic acid (about 89% active ingredient content, INCI name: Carbomer) (3V Sigma)

Cetiol ^® V oleic acid decyl ester (INCI name: Decyl Oleate) (Cognis)

Lanette ^® N mixture of 90 parts by weight of cetylstearyl alcohol and 10 parts by weight Natriumcetylstearylsulfatl (INCI name: Cetearyl Alcohol, Sodium Cetearyl Sulfate) (Cognis)

Phospholipid EFA * approx. 30% solids in water / propylene glycol (INCI name: Linoleamidopropyl PG-Dimonium

Chlorides phosphates) (Uniqema)

Cutina GMS SE ^® white powder (INCI name: Glyceryl Stearate SE) (Cognis) Mirapol ^® A-15 Poly [N- (3- (dimethylammonium) propyl] -N '- [3- ethylenoxyethylendimethyl-ammonium) propyl] - urea-di-chloride (at least 62% active ingredient in water, INCI name: Polyquaternium-2) (Rhodia)

Unless otherwise indicated, all quantities are% by weight based on the total weight of the respective composition. The recipes of Reinforcing powder according to Table 1 and the bleaching cream according to Table 2 were provided using known manufacturing methods.

Table 1: reinforcing powder wt.%

Potassium peroxodisulfate 15.00

Sodium peroxodisulfate 15.00

Sodium metasilicate 15.00

Carbopol ^® ETD 2020 3.00

Paraffin Liquidum 3.00

Magnesium carbonate 20.00

Gluadin ^® AGP 1, 00

Talcum 28.00

Table 2: Bleaching cream B1 B2

Wt.% Wt.%

Dow Corning 193 ^Fluid® 0.20 0.20

Synthalen® ^® K 0.04 0.04

Cetiol ^® V 2.30 2.30

Lanette ^® N 14.00 14.00

Cetearyl alcohol 3.90 3.90

Cutina ^® GMS SE 6.00 6.00

Phospholipid EFA 0.10 0.10

tetrasodium

(Na ₄ EDTA) 0.80 0.80

Monoethanolamine 4.00 4.00

Ascorbic acid 0.10 0.10

L-serine 0.50 0.50

Mirapol A-15 0.20 0.20

Imidazole - 4.00

Perfume 0.60 0.60

Water ad 100 ad 100 There were added 20 g of the amplifier powder of table 1 with 15 g of one of Blonding shown in Table 2 were mixed and then 30 was the commercial developer dispersion g (Oxigenta ^® from. Schwarzkopf with 6 wt .-% hydrogen peroxide) was added and stirred in. The ready-to-use bleaching agent was applied to a middle brown natural hair tress (Kerling), left for a period of 35 minutes at room temperature, rinsed and dried.

This procedure was carried out both with bleaching cream B1 to obtain a bleaching agent V1 not according to the invention and bleaching cream B2 to obtain a bleaching agent E1 according to the invention.

Thereafter, the strands were measured colorimetrically using the Datacolor SF 6000X measuring instrument (Datacolor) in the measuring range from 380 to 700 nm wavelength. In addition to the color difference to the initial hair ΔL, the color strength was determined according to Kubelka-Munk as the integral of the surface of the spectral absorption and scattering coefficients K / S of 380 to 500 nm (cf. DIN 55986). The smaller the value of the integral, the less colored, i. the more bleached, the hair is compared to the starting hair.

Table 3: Colorimetric measurements

The bleaching agent E1 according to the invention gives a stronger lightening with the alkalizing agent of imidazole derivative and alkanolamine than a bleaching agent V1 which contains an alkanolamine as the alkalizing agent.

Claims

Patent claims

1. A composition for lightening keratin-containing fibers, in particular human hair, which have a pH greater than pH 7, in particular from pH 8.0 to 12.0, are free of ammonia and in a cosmetic carrier (a) at least one inorganic persalt , (b) at least one oxidizing agent and (c) as alkalizing agent a mixture of at least two components A and B, of which

wherein

R ¹ is a hydrogen atom, an optionally substituted

Aryl group or a (Ci-C ₆ ) alkyl group, R ² is a hydrogen atom, a carboxaldehyde group, a

(Ci-C ₆ ) alkyl group or a nitro group, R ³ is a hydrogen atom, a carboxy (C ₁ -C ₆ ) alkyl group, an amino (C ₁ -C ₆ ) alkyl group, a carboxyl group, a

Carboxaldehyde group, a (C ₁ -C ₆ ) -alkyl group, a nitro group, a 2-amino-3-hydroxypropyl group or a group -CH ₂ -

CH (NH ₂ ) -COOH, R ⁴ represents a hydrogen atom, a carboxaldehyde group or a carboxyl group, and

B is selected from at least one alkanolamine.

2. Composition according to claim 1, characterized in that the alkalizing agent A is selected from at least one member of the group of histamine, D- Histidine, L-histidine, DL-histidine, D-histidinol, L-histidinol, DL-histidinol, imidazole, imidazole-4-acetic acid, imidazole-4-carboxylic acid, imidazole-4,5-dicarboxylic acid, imidazole-2-carboxaldehyde, imidazole-4-carboxaldehyde, imidazole-5-carboxaldehyde, 2-nitroimidazole, 4-nitroimidazole, 4-methylimidazole-5-carboxaldehyde, N-methylimidazole-2-carboxaldehyde, 4-methylimidazole, 2-methylimidazole, N-methylimidazole, N- (4-aminophenyl) -imidazole, as well as the physiologically acceptable salts of the aforementioned compounds.

3. Composition according to one of claims 1 or 2, characterized in that the alkalizing agent A in amounts of 0.1 to 10 wt .-%, based on the total agent, is included.

4. Composition according to one of claims 1 to 3, characterized in that the alkalizing agent B is selected from at least one member of the group which is formed from 2-aminoethanol (monoethanolamine), monoisopropanolamine, 2-amino-2-methyl-propanol, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol and 2-amino-2-methylbutanol.

5. Composition according to one of claims 1 to 4, characterized in that the alkalizing agent B in amounts of 0.1 to 10 wt .-%, based on the total agent, is included.

6. Composition according to one of claims 1 to 5, characterized in that they additionally contain at least one compound of amino acids and / or oligopeptides, these each having at least two amino groups and at least one -COOH or -SO 3 H group and their 2.5% solution in water in each case has a pH greater than 9.0.

7. Composition according to claim 6, characterized in that the alkalizing agent C is selected from α-amino acids.

8. Composition according to claim 6 or 7, characterized in that the alkalizing agent C is lysine and / or arginine.

9. Composition according to one of claims 1 to 8, characterized in that they have a pH of 9 to 11.

10. Composition according to one of claims 1 to 9, characterized in that they additionally contain at least one surfactant.

11. Use of a composition according to any one of claims 1 to 10 for whitening and / or bleaching keratinhaltiger fibers, in particular human hair.

12. A method for whitening and / or bleaching keratin fibers, in particular human hair, characterized in that the fibers are treated with an agent according to any one of claims 1 to 10.

13. Kit containing at least three separately stored compositions, wherein

(i) in a first container, a composition used in a cosmetic

Carrier comprises at least one inorganic persalt, (ii) in a second container a composition containing at least one oxidizing agent in a cosmetic carrier and (iii) in a third container, at least one composition containing in a cosmetic carrier as alkalizing agent a mixture of at least two components A and B, of which

in which R ¹ , R ² , R ³ and R ^{4 are} as defined in claim 1 and

B is selected from at least one alkanolamine stored.