EP1408919A2 - Novel dyeing composition for dyeing keratinous fibres comprising a particular dicationic monoazo dye - Google Patents

Novel dyeing composition for dyeing keratinous fibres comprising a particular dicationic monoazo dye

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Publication number
EP1408919A2
EP1408919A2 EP02759813A EP02759813A EP1408919A2 EP 1408919 A2 EP1408919 A2 EP 1408919A2 EP 02759813 A EP02759813 A EP 02759813A EP 02759813 A EP02759813 A EP 02759813A EP 1408919 A2 EP1408919 A2 EP 1408919A2
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EP
European Patent Office
Prior art keywords
radical
chosen
radicals
formula
substituted
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EP02759813A
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German (de)
French (fr)
Inventor
Laurent Vidal
Hervé David
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LOreal SA
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LOreal SA
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Publication of EP1408919A2 publication Critical patent/EP1408919A2/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B44/00—Azo dyes containing onium groups
    • C09B44/10—Azo dyes containing onium groups containing cyclammonium groups attached to an azo group by a carbon atom of the ring system
    • C09B44/16—1,3-Diazoles or hydrogenated 1,3-diazoles ; (Benz)imidazolium
    • 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
    • A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/41—Amines
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B44/00—Azo dyes containing onium groups
    • C09B44/10—Azo dyes containing onium groups containing cyclammonium groups attached to an azo group by a carbon atom of the ring system

Definitions

  • the subject of the invention is a new dye composition for dyeing keratin fibers, in particular human hair, containing a particular dicationic monoazo dye, as well as the process for dyeing keratin fibers using such a composition.
  • a subject of the invention is also new diazo monocolor dyes. It is known to dye keratin fibers and in particular human hair with dye compositions containing oxidation dye precursors, generally called oxidation bases, such as ortho or paraphenylenediamines, ortho or paraaminophenols and heterocyclic compounds. These oxidation bases are colorless or weakly colored compounds which, associated with oxidizing products, give rise, through an oxidative condensation process, to colored compounds.
  • couplers or color modifiers the latter being chosen in particular from aromatic metadiamines, metaaminophenols, metadiphenols and certain heterocyclic compounds such as as indole compounds.
  • This oxidation dyeing process consists in applying to the keratin fibers, oxidation bases or a mixture of oxidation bases and couplers with an oxidizing agent, for example hydrogen peroxide, to leave on, then to rinse the fibers.
  • an oxidizing agent for example hydrogen peroxide
  • the resulting colorings are permanent, powerful, and resistant to external agents, in particular to light, bad weather, washing, perspiration and rubbing.
  • Generally applied at basic pH it makes it possible to obtain a dyeing and at the same time a lightening of the fiber which translates in practice by the possibility of obtaining a final coloration lighter than the original color.
  • the lightening of the fiber has the advantageous effect of generating a solid color in the case of gray hair, and in the case of naturally pigmented hair, of bringing out the color, that is to say making it more visible.
  • dye keratin fibers by direct coloring.
  • the method conventionally used in direct dyeing consists in applying to the keratin fibers direct dyes which are colored and coloring molecules having an affinity for the fibers, to allow to pause, then to rinse the fibers. It is known, for example, to use direct dyes of the nitro benzene, anthraquinone, nitropyridine type, dyes of the azo, xanthene, acridine azine type or triarylmethane dyes.
  • the resulting colorings are particularly chromatic colors which are however temporary or semi-permanent because the nature of the interactions which bind the direct dyes to the keratin fiber, and their desorption from the surface and / or from the core of the fiber are responsible for their low dye power and their poor resistance to washing or perspiration.
  • These direct dyes are also generally sensitive to light due to the low resistance of the chromophore vis-à-vis photochemical attacks and lead over time to a fading of the coloring of the hair. In addition, their sensitivity to light is dependent on their uniform or aggregate distribution in the keratin fiber.
  • direct dyes are generally sensitive to the action of oxidizing agents such as hydrogen peroxide, and reducing agents such as sodium bisulfite, which generally make them difficult to use in lightening direct dye compositions based on hydrogen peroxide and based on an alkalizing agent or in oxidation dye compositions in combination with precursors of the oxidation base or coupler type.
  • oxidizing agents such as hydrogen peroxide
  • reducing agents such as sodium bisulfite
  • patent application FR 2 741 798 has described dye compositions containing direct dyes comprising at least one quaternized nitrogen atom of the azo or azomethine type, said compositions being to be mixed extemporaneously at basic pH with an oxidizing composition.
  • These compositions make it possible to obtain colorings with homogeneous, tenacious and brilliant reflections. However, they do not make it possible to dye the keratin fibers with as much power as with oxidation coloring compositions.
  • n is equal to 0 or 1
  • Z represents a 5- or 6-membered cationic heteroaromatic radical of formulas (III) or (IV):
  • X represents NR 3 , S or O
  • Z represents CR 2 or N
  • Y represents CR 4 or N with the following conditions: when X is NR 3 or O and Z is CR 2, then Y is CR 4 or N, when X is S then Z is N or Y is N when X is S and Z is N then and Y is CR 4 X, represents CR 6 or N
  • m is an integer equal to 0,1,2 or 3
  • R L R 3 and R 5 represent, independently of one another, a saturated or unsaturated C 1 -C 4 hydrocarbon chain; linear or branched which can form a carbon ring having 5 to 7 links, possibly aromatic; one or more carbon atoms which can be replaced by an oxygen, nitrogen, halogen or sulfur atom or by an SO 2 group, with the exception of the carbon linked to the nitrogen atom of the ring of formula (III) or (IV); the radicals R 1 ( R 3 or R 5 not comprising a peroxide bond, nor of diazo, nitro or nitroso radicals;
  • R 2 , R 4 and R 6 independently of one another represent a hydrogen atom; a hydrocarbon chain C, -. C 10l saturated or unsaturated, linear or branched which can form a carbon ring having 5 to 7 links, optionally aromatic; one or more carbon atoms which can be replaced by one or more oxygen, nitrogen, sulfur atoms, or by an SO 2 group; the radicals R 2 , R 4 or R 6 not comprising a peroxide bond, nor of diazo, nitro or nitroso radicals; the radicals R 2 and R 4 can together form a carbon aromatic cycle, - V represents an organic or mineral anion,
  • Ai and A 3 represent, independently of one another, a divalent radical of formulas (V) or (VI)
  • n ' is an integer equal to 0, 1, 2 or 3
  • - Y Yz represents C- or NN
  • R 8 and R ′ 8 represent, independently of one another, a non-cationic group chosen from a hydrogen atom, a straight or branched C ⁇ C ⁇ hydrocarbon chain which can form a carbon ring having from 5 to 7 members, optionally aromatic; one or more carbon atoms of the hydrocarbon chain which can be replaced by one or more oxygen, nitrogen, sulfur atoms, or by an SO 2 group with the exception of the carbon linked to the nitrogen atom; the radicals R 8 or
  • R ′ 8 comprising no peroxide bond, nor diazo, nitro or nitroso radicals
  • R 7 , R 9 , R ' 7 and R' 9 independently of one another represent a non-cationic group as defined for R 2 or a cationic group Z 3 , provided that only one of the groups R 7 , R 9 , R ' 7 and R' 9 is cationic
  • R 7 with R 8 respectively R ' 7 with R' 8 can together form a saturated 5 or 6-membered heterocycle
  • Z 3 is a cationic group represented by the following formula (VII)
  • - B represents a hydrocarbon chain comprising from 1 to 15 carbon atoms, linear or branched, which can form one or more rings comprising from 3 to 7 optionally aromatic links, and one or more carbon atoms of which can be replaced by an atom of oxygen, nitrogen, sulfur, or by an SO 2 radical with the exception of the carbon linked to the nitrogen atom; B having no peroxide bond or diazo, nitro or nitroso radicals, -the radical B is linked to D by any of the atoms of the radical D, - n '"can take the value 0 or 1,
  • - p can take the value 0 or 1;
  • T 1t T 2 , T 3 and T 4 independently of each other, represent an oxygen atom; a sulfur atom; a nitrogen atom unsubstituted or substituted by a radical R 14 ; or a carbon atom unsubstituted or substituted by one or two radicals R 14 , identical or different;
  • T 5 represents a nitrogen atom; or a carbon atom unsubstituted or substituted by a radical R 14 ;
  • T 6 can take the same meanings as those indicated below for the radical R 14 , it being understood that T 6 is different from a hydrogen atom;
  • T 6 can, in addition, form with T 6 a saturated or unsaturated ring comprising from 5 to 7 links, each link being unsubstituted or substituted by one or two identical or different R 14 radicals;
  • - two of the adjacent radicals T ⁇ T 2 , T 3 , T 4 and T 5 can also form a ring comprising from 5 to 7 links, each link being independently represented by a carbon atom unsubstituted or substituted by one or two radicals R 14 identical or different, a nitrogen atom substituted or unsubstituted by a radical R 14 , an oxygen atom or a sulfur atom;
  • R 13 and R 14 identical or different, represent a hydrogen atom; a hydrocarbon chain comprising from 1 to 10 carbon atoms, linear or branched, optionally aromatic, and one or more carbon atoms of which may be replaced by an oxygen, nitrogen, sulfur atom, or by an SO 2 group , and of which one or more carbon atoms can, independently of each other, be substituted by one or more halogen atoms; said radical not comprising a peroxide bond or diazo, nitro or nitroso radicals;
  • - V represents an organic or mineral anion
  • Z 2 represents a linear or branched CrC ⁇ hydrocarbon chain which can form a carbon ring having 5 to 7 members, optionally aromatic; one or more carbon atoms which can be replaced by one or more oxygen, nitrogen, sulfur atoms or by an SO 2 group.
  • said radical Z 2 not comprising a peroxide bond, nor of diazo, nitro or nitroso radicals; a cationic group Z 3 as defined above, with the proviso that Z 2 is not cationic when R 7 , R 9 , R 7 'or R 9 ' is cation,
  • a 2 represents a radical of formula (X) corresponding to a carbon, pyridine or pyridazine aromatic radical substituted by a cationic heteroaromatic 5-membered radical, optionally substituted by one or more radicals R 19 of the same definition as R 2 ; a radical of formula (XI):
  • R 15 and R 18 have the same definition as R ⁇ defined above
  • R 16 R 17 , R 19 , R 20 and R 21 have the same definition as R 2 defined above
  • V represents an organic or mineral anion , with the proviso that in formula (I) one of the groups A 1 t Z 2 and A 3 is a cationic group.
  • the radicals R ,, R 3 and R 5 are preferably chosen from a C 1 -C 6 alkyl or alkenyl radical which may be substituted by one or more hydroxy, optionally substituted amino, carboxyl or sulphonic substituents; a phenyl radical which may be substituted by one or more halogen atoms, one or more alkyl groups C 1 -C 4 alkyl, aikoxy C 1 -C 4 alkyl, amino, hydroxy, trifluoromethyl, alkylamino, C, -.
  • methyl radicals are preferred for R ⁇ R 3 and R 5 more particularly; ethyl; hydroxyethyl; aminoethyl; carboxymethyl; carboxyethyl; phenyl; benzyl; heterocycles chosen from pyridyle, imidazolyle, pyrimidinyle.
  • radicals R 1 and R 3 are chosen from methyl groups; ethyl; phenyl; hydroxyethyl; aminoethyl; carboxymethyl; carboxyethyl.
  • the radicals R 2 , R 4 and R 6 are preferably chosen from a hydrogen atom; an alkyl radical, for example methyl, ethyl; a substituted alkyl radical with one or more hydroxy, amino or halogen such as hydroxymethyl, hydroxyethyl, 1,2-dihydroxyethyl, 1,2-dihydroxypropyl, 2,3-dihydroxypropyl, aminomethyl, aminoethyl, aminopropyl; trifluoromethyl; a phenyl radical which may be substituted by one or more substituents chosen from alkyl, hydroxy, amino, alkoxy, carboxyl, trifluoromethyl, sulfonic radicals; benzyl radicals and benzyls substituted by an alkoxy, for example methoxy, or hydroxy, in particular 2-methoxybenzyl, 3-methoxybenzyl, 4-methoxybenzyl, 2-hydroxybenzyl, 3-hydroxybenzyl, 4-hydroxybenzyl; a heterocycle chosen from
  • the preferred radicals R 2 , R 4 and R 6 are hydrogen; an alkyl radical chosen from methyl, ethyl; a substituted alkyl radical chosen from trifluoromethyl; hydroxymethyl, hydroxyethyl, aminomethyl, aminoethyl; benzyl; a phenyl optionally substituted by one or more radicals chosen from methyl, hydroxy, amino and methoxy radicals; 2-methoxybenzyl; 4-methoxybenzyl; 2- hydroxybenzyl; 4-hydroxybenzyl; a heterocycle chosen from pyrrolidinyl, piperidinyl; a methoxy radical; an acyl radical; ; an amino radical; a (di) alkylamino radical in C ⁇ C ,; More particularly, the radicals R 2 R 4 and R 6 are chosen from hydrogen; methyl; ethyl; trifluoromethyl; phenyl; pyrrolidinyl; methoxy; amino.
  • R 8 and R 8 ' are preferably chosen from a C 1 -C 4 alkyl or alkenyl radical which may be substituted by one or more hydroxy, optionally substituted amino, carboxyl substituents; a phenyl radical which may be substituted by one or more halogen atoms, one or more alkyl groups CC 4 aikoxy C t ⁇ O, amino, hydroxy, trifluoromethyl, alkylamino-C ", carboxy or sulfonyl; a heterocycle chosen from imidazole, thiazole, pyridine or pyrimidine; a radical (CH2) p -T- (CH2) q -V 1 R 'where p and q are whole, identical or different, between 1 and 3, R' represents H or methyl and T and V, independently denote an atom of oxygen or a radical NR "with R” denoting a hydrogen or a methyl.
  • R 8 is preferred for R 8 , more particularly the hydrogen radicals; methyl; ethyl; hydroxyethyl; aminoethyl; carboxymethyl; carboxyethyl; phenyl; heterocycles chosen from pyridynyl, imidazolyl, pyrimidinyl. More particularly, the radicals R 8 and R ′ 8 are chosen from hydrogen groups; methyl; ethyl; phenyl; hydroxyethyl; aminoethyl; carboxymethyl; carboxyethyl.
  • B is preferably chosen from an optionally substituted alkyl radical chosen from methyl, ethyl, propyl; hydroxymethyl, hydroxyethyl, aminomethyl, aminoethyl; methoxybenzyl; a heterocycle chosen from piperazinyl. More particularly, the radical B is chosen from methyl; ethyl; propyl; phenyl; piperazinyl; triazine.
  • Rio. Ru. R 12 . R 13 and R 14 are preferably chosen from hydrogen; a C 1 -C 4 alkyl or alkenyl radical which may be substituted with a hydroxy or optionally substituted amino substituent; a phenyl radical which may be substituted by one or more halogen atoms, one or more alkyl groups CC, aikoxy in d- -C 4 alkylamino, hydroxy, trifluoromethyl, alkylamino, C 1 -C 4 alkyl, carboxy or sulfonyl; benzyl which may be substituted by one or more halogen atoms, one or more alkyl, C ⁇ O ,, aikoxy C ⁇ O t, amino, trifluoromethyl; a C r C 4 (poly) aminoalkyl radical; a radical (CH2) p -T- (CH2) q -VR 'where p and q are whole, identical or different, comprised between 1
  • R 10 , R 11f R 12 , R 13 and R 14 are more particularly methyl radicals; ethyl; isopropyl; hydroxyethyl; aminoethyl; phenyl; benzyl; heterocycles chosen from pyridynyl, imidazolyl, pyrimidinyl. More particularly, the radicals R 10 , R ⁇ , R 12 , R 13 and R 14 are chosen from methyl groups; ethyl; phenyl; hydroxyethyl; aminoethyl; carboxymethyl; carboxyethyl.
  • Z1 is preferably chosen from the group consisting of imidazolinium, triazolinium, thiazolinium, pyridinium, pyridazinium radicals optionally substituted on the ring carbon atoms by a methyl, a methoxy, a carboxy, an amino, a phenyl, a pyrrolidine and on the nitrogen atom by a methyl, a 2-hydroxyethyl, a carboxymethyl, a carboxyethyl.
  • Z 2 is preferably chosen from the imidazolium, pyridinium, pyridazinium, pyrimidinium, pyrazinium radicals.
  • a 2 is preferably chosen from pyrazolyl, pyrrolyl, imidazolyl, triazolyl, thiadiazolyl radicals, optionally substituted.
  • a ,, A 3 independently of one another represent an aniline, aminopyridinyl, aminopyridazinyl radical optionally substituted by a hydrogen atom, by an alkyl radical, for example chosen from methyl, ethyl, an alkyl substituted, for example hydroxymethyl, hydroxyethyl , 1,2-dihydroxyethyl, 1,2-dihydroxypropyl, 2,3-dihydroxypropyl, aminomethyl, aminoethyl, aminopropyl; with a trifluoromethyl radical; by a heterocycle chosen from N-pyrrolidinyl, N-piperidinyl, N-morpholine, N-piperazinyl or N-imidazolyl, by an alkoxy radical such as methoxy or ethoxy, by a phosphonyl radical, by a siloxy radical, by a 1,2 radical -diaminoethyl, by a 2,3-diaminopropyl radical, by an
  • the preferred couples (A ⁇ A 3 ) are chosen from (aniline radical, aniline radical), (aniline radical, aminopyridinyl radical), (aminopyridinyl radical, aniline radical), independently, each of the radicals constituting these couples, is optionally substituted by a hydrogen atom, or by an alkyl radical chosen from methyl, ethyl, or by an optionally substituted alkyl radical chosen from hydroxymethyl, 1,2-dihydroxyethyl, aminomethyl, 2-aminoethyl, 1,2-diaminoethyl, 2,3 -diaminopropyl or by a heterocycle chosen from pyrrolidinyl, piperidinyl, or by a methoxy radical; amino; methylamino; dimethylamino; 2-hydroxyethylamino
  • the following pairs (A ⁇ A 3 ) will be chosen more particularly: (aniline radical, aniline radical) optionally substituted by a methyl, ethyl radical, or by a hydroxymethyl radical, 1, 2-dihydroxyethyl, aminomethyl, 2-aminoethyl, 1, 2- diaminoethyl, 2,3-diaminopropyl or by a pyrrolidinyl, piperidinyl radical, or by a methoxy radical; amino; methylamino; dimethylamino; 2-hydroxyethylamino
  • the organic or mineral anions of formulas (I) or (II) can be chosen from a halide such as chloride, bromide, fluoride, iodide; a hydroxide; a sulfate; a hydrogen sulfate; an alkyl d-C 6 ) sulphate such as for example a methyl sulphate or an ethyl sulphate; an acetate; a tartrate; an oxalate; an alkyl ⁇ dC ⁇ sulfonate such as methylsulfonate; an arylsulfonate substituted or unsubstituted by a CC 4 alkyl radical such as for example a 4-toluylsulfonate.
  • a halide such as chloride, bromide, fluoride, iodide
  • a hydroxide such as a sulfate; a hydrogen sulfate
  • the azo dyes of formula (I) are preferably chosen from the following dyes:
  • the preferred compounds which can be synthesized according to the method described in the examples are chosen from
  • the concentration of azo cationic dye of formula (I) can vary between 0.001 and 5% by weight approximately relative to the total weight of the dye composition, and preferably between approximately 0.05 and 2%.
  • the composition of the invention may also comprise an oxidizing agent.
  • This oxidizing agent can be any oxidizing agent conventionally used for bleaching keratin fibers.
  • the oxidizing agent is preferably chosen from hydrogen peroxide, urea peroxide, bramates of alkali metals, persalts such as perborates and persulfates. The use of hydrogen peroxide is particularly preferred.
  • the composition according to the invention can also comprise an oxidation base.
  • This oxidation base can be chosen from the oxidation bases conventionally used in oxidation dyeing, for example paraphenylenediamines, bis-phenylalkylenediamines, para-aminophenols, ortho-aminophenols and heterocyclic bases.
  • paraphenylenediamines there may be more particularly mentioned by way of example, paraphenylenediamine, paratoluylenediamine, 2-chloro paraphenylenediamine, 2,3-dimethyl paraphenylenediamine, 2,6-dimethyl paraphenylenediamine, 2,6-diethyl paraphenylenediamine , 2,5-dimethyl paraphenylenediamine, N, N-dimethyl paraphenylenediamine, N, N-diethyl paraphenylenediamine, N, N-dipropyl paraphenylenediamine, 4-amino N, N-diethyl 3-methyl aniline, N, N-bis- ( ⁇ -hydroxyethyl) paraphenylenediamine, 4-N, N-bis- ( ⁇ - hydroxyethyl) amino 2-methyl aniline, 4-N, N-bis- ( ⁇ -hydroxyethyl) amino 2-chloro aniline , 2- ⁇ -hydroxyethyl
  • paraphenylenediamine paratoluylenediamine, 2-isopropyl paraphenylenediamine, 2- ⁇ -hydroxyethyl paraphenylenediamine, 2- ⁇ -hydroxyethyloxy paraphenylenediamine, 2,6-dimethyl paraphenylenediamine para-phenylenediamine, 2,3-dimethyl para-phenylenediamine, N, N-bis- ( ⁇ -hydroxyethyl) para-phenylenediamine, 2-chloro para-phenylenediamine, 2- ⁇ -acetylaminoethyloxy para-phenylenediamine, and their addition salts with an acid are particularly preferred .
  • the bis-phenylalkylenediamines there may be mentioned by way of example, N, N'-bis- ( ⁇ -hydroxyethyl) N, N'-bis- (4'-aminophenyl) 1, 3-diamino propanol, 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-methyl-aminophenyl) tetramethylenediamine, N.N'-bis- (ethyl) N, N ' -bis- (4'-amino, 3'-methylphenyl) ethylenediamine, 1,8-bis- (2,5
  • para-aminophenol there may be mentioned by way of example, para-aminophenol, 4-amino 3-methyl phenol, 4-amino 3-fluoro phenol, 4-amino 3-hydroxymethyl phenol, 4- amino 2-methyl phenol, 4-amino 2-hydroxymethyl phenol, 4-amino 2-methoxymethyl phenol, 4-amino 2-aminomethyl phenol, 4- amino 2- ( ⁇ -hydroxyethyl aminomethyl) phenol, 4- amino 2-fluoro phenol, and their addition salts with an acid.
  • para-aminophenol 4-amino 3-methyl phenol, 4-amino 3-fluoro phenol, 4-amino 3-hydroxymethyl phenol, 4- amino 2-methyl phenol, 4-amino 2-hydroxymethyl phenol, 4-amino 2-methoxymethyl phenol, 4-amino 2-aminomethyl phenol, 4- amino 2- ( ⁇ -hydroxyethyl aminomethyl) phenol, 4- amino 2-fluoro phenol, and their addition salts with an acid.
  • ortho-aminophenols there may be mentioned by way of example, 2-amino phenol, 2-amino 5-methyl phenol, 2-amino 6-methyl phenol, 5-acetamido 2-amino phenol, and their addition salts with an acid.
  • heterocyclic bases for example, pyridine derivatives, pyrimidine derivatives and pyrazole derivatives.
  • pyridine derivatives mention may be made of the compounds described for example in 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- ( ⁇ -methoxyethyl) amino 3-amino 6-methoxy pyridine, 3,4-diamino pyridine, and their addition salts with an acid.
  • pyrimidine derivatives mention may be made of the compounds described for example in patents DE 2,359,399; JP 88-169,571; JP 05 163 124; EP 0 770 375 or patent application WO 96/15765 such as 2,4,5,6-tetra-aminopyrimidine, 4-hydroxy 2,5,6-triaminopyrimidine, 2-hydroxy 4,5,6-triaminopyrimidine, 2,4-dihydroxy 5,6-diaminopyrimidine, 2,5,6-triaminopyrimidine, and pyrazolo-pyrimidine derivatives such as those mentioned in patent application FR-A-2 750 048 and among which may be mentioned 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
  • composition according to the invention may also contain one or more couplers conventionally used for dyeing keratin fibers.
  • couplers conventionally used for dyeing keratin fibers.
  • couplers mention may in particular be made of metaphenylenediamines, metaaminophenols, metadiphenols, naphthalene couplers and heterocyclic couplers.
  • the coupler (s) are generally present in an amount between 0.001 and 10% by weight approximately of the total weight of the dye composition and more preferably from 0.005 to 6%.
  • the oxidation base (s) are present in an amount preferably between 0.001 to 10% by weight approximately of the total weight of the dye composition, and more preferably from 0.005 to 6%.
  • the addition salts with an acid which can be used in the context of the dye compositions of the invention for the oxidation bases and the couplers are in particular chosen from hydrochlorides, hydrobromides, sulfates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates.
  • the dye composition in accordance with the invention may also contain direct dyes different from those of formula (I), these dyes being able in particular be chosen from nitro dyes of the benzene series, cationic direct dyes, azo direct dyes, methinic direct dyes.
  • the medium suitable for dyeing also called dye support, generally consists of water or of a mixture of water and at least one organic solvent to dissolve the compounds which are not sufficiently soluble in water.
  • organic solvent mention may, for example, be made of lower alkanols at dC 4 , such as ethanol and isopropanol; polyols and polyol ethers such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, monoethyl ether and diethylene glycol monomethyl ether, as well as aromatic alcohols such as benzyl alcohol or phenoxyethanol, and mixtures thereof.
  • the solvents may be present in proportions preferably of between 1 and 40% by weight approximately relative to the total weight of the dye composition, and even more preferably between 5 and 30% by weight approximately.
  • the dye composition in accordance with the invention may also contain various adjuvants conventionally used in compositions for dyeing the hair, such as anionic, cationic, nonionic, amphoteric, zwitterionic surfactants or mixtures thereof, anionic polymers, cationic, nonionic, amphoteric, zwitterionic or mixtures thereof, mineral or organic thickening agents, and in particular associative thickeners anionic, cationic, nonionic and amphoteric, antioxidant agents, penetration agents, sequestering agents, perfumes, buffers, dispersing agents, conditioning agents such as for example volatile or non-volatile silicones, modified or unmodified, film-forming agents, ceramides, preserving agents, opacifying agents.
  • adjuvants are generally present in an amount for each of them of between 0.01 and 20% by weight relative to the weight of the composition.
  • the pH of the dye composition according to the invention is generally between 3 and 12 approximately, and preferably between 5 and 11 approximately. It can be adjusted to the desired value by means of acidifying or basifying agents usually used in dyeing keratin fibers or even using conventional buffer systems.
  • the acidifying agents there may be mentioned, by way of example, mineral or organic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid, lactic acid, sulfonic acids.
  • the basifying agents there may be mentioned, by way of example, ammonia, alkali carbonates, alkanolamines such as mono-, di- and triethanolamines as well as their derivatives, sodium or potassium hydroxides and compounds of formula (III) below:
  • R a, R b, R c and R d, identical or different, represent a hydrogen atom, an alkyl radical -C 4 hydroxyalkyl Cr.
  • the dye composition according to the invention can be in various forms, such as in the form of liquids, creams, gels, or in any other form suitable for dyeing keratin fibers, and in particular human hair.
  • the invention also relates to a direct dyeing process which comprises the application of a dye composition containing a dye of formula (I) as defined above on keratin fibers. After a pause, the keratin fibers are rinsed leaving colored fibers to appear.
  • the application to the fibers of the dye composition containing the azo cationic dye of formula (I) or (II) can be implemented in the presence of an oxidizing agent which causes discoloration of the fiber.
  • This oxidizing agent can be added to the composition containing the cationic azo dye at the time of use or directly on the keratin fiber.
  • the composition containing the azo cationic dye of formula (I) is free from oxidation base and from coupler.
  • the invention also relates to a process for permanent oxidation dyeing which comprises applying to the fibers a dye composition which comprises a dye of formula (I), at least one oxidation base and optionally at least one coupler, in the presence of an oxidizing agent.
  • the oxidation base, the coupler and the oxidizing agent are as defined above.
  • oxidizing agent enzymes among which there may be mentioned peroxidases, 2-electron oxidoreductases such as uricases and 4-electron oxygenases such as laccases.
  • the color can be revealed at acidic, neutral or alkaline pH and the oxidizing agent can be added to the composition of the invention just at the time of use or it can be used from an oxidizing composition containing it , applied to the fibers simultaneously or sequentially to the dye composition.
  • the dye composition is mixed, preferably at the time of use, with a composition containing, in a medium suitable for dyeing, at least one oxidizing agent, this oxidizing agent being present in an amount sufficient to develop a coloration.
  • the mixture obtained is then applied to the keratin fibers. After a pause time of approximately 3 to 50 minutes, preferably approximately 5 to 30 minutes, the keratin fibers are rinsed, washed with shampoo, rinsed again and then dried.
  • the oxidizing composition may also contain various adjuvants conventionally used in compositions for dyeing the hair and as defined above.
  • the pH of the oxidizing composition containing the oxidizing agent is such that after mixing with the dye composition, the pH of the resulting composition applied to the keratin fibers preferably varies between 3 and 12 approximately, and even more preferably between 5 and 11 It can be adjusted to the desired value at means of acidifying or basifying agents usually used in dyeing keratin fibers and as defined above.
  • composition which is finally applied to the keratin fibers can be in various forms, such as in the form of liquids, creams, gels or in any other form suitable for dyeing keratin fibers, and in particular human hair.
  • Another object of the invention is a device with several compartments or "kit” for dyeing in which a first compartment contains the dye composition of the invention and a second compartment contains the oxidizing composition.
  • This device can be equipped with a means enabling the desired mixture to be delivered to the hair, such as the devices described in patent FR-2,586,913 in the name of the applicant.
  • the subject of the invention is also the cationic azo dyes of formula (I) or (II) as defined above in which R 8 is hydrogen.
  • R 8 is hydrogen.
  • These compounds can be obtained from the preparation methods described for example in documents EP 810824, GB 9619573, RO 106572, J. Chem. Res .., Synop. (1998), (10), 648-649, DE 19721619, US 5852179, Synth. Commun 1999, 29 (13), 2271-2276, Org. Lett., 2001, 3, 2583, Org. Lett. 2001, 3, 2757J. Chem. Soc, Perkin Trans. 1, 1998, 2615-2622 and references from these publications.
  • the compounds of formula (II) can be obtained in the following way:
  • compound 1 is in a first step reduced to compound 2 in the presence of hydrogen under pressure and of palladium.
  • This compound subsequently reacts in the presence of sodium nitrite to provide a diazonium salt which can be condensed on imidazole and thus provide compound 3.
  • the double cationization takes place in the presence of dimethylsulfate in ethyl acetate to provide compound 4.
  • the compound 1 suitably chosen will be able to react with a 5-membered heteroaromatic system as defined in the claims (here an imidazole) in the presence of base at reflux.
  • a 5-membered heteroaromatic system as defined in the claims here an imidazole
  • An alternative can be proposed using a copper catalyst, a base, and a ligand, 1,2-diaminocyclohexane at reflux.
  • Compound 3 is obtained by reduction of Compound 2 using palladium under hydrogen pressure.
  • Compound 3 subsequently reacts in the presence of sodium nitrite to provide a diazonium salt which can be condensed on imidazole and thus provide compound 4.
  • the double cationization takes place in the presence of dimethylsulfate in acetate d ethyl to provide compound 5.
  • each composition is mixed with an equal weight of hydrogen peroxide at 20 volumes (6% by weight). Each mixture obtained is applied to locks of gray hair at 90
  • Each lock is evaluated before and after dyeing in the L * a * b * system , using a CM 2002 MINOLTA® spectrophotometer (Illuminant D65).
  • L * a * b * clarity is indicated by the value L * on a scale from 0 to 100 while the chromaticity coordinates are expressed by a * and b * which indicate two axes of color, a * the red-green axis and b * the axis yellow-blue.
  • the higher the value of L the lighter and less intense the color.
  • the lower the value of L the darker or very intense the color.

Abstract

The invention concerns a novel dyeing composition for dying keratinous fibres, in particular human hair, comprising a dicationic monoazo dye, and the dyeing method using said composition and the novel compounds of formulae (I) or (II).

Description

NOUVELLE COMPOSITION TINCTORIALE POUR LA TEINTURE DES FIBRES KERATINIQUES COMPRENANT UN COLORANT MONOAZOÏQUE NOVEL TINCTORIAL COMPOSITION FOR DYEING KERATINIC FIBERS COMPRISING A MONOAZOIC DYE
DICATIONIQUE PARTICULIERSPECIAL INSTRUCTIONS
L'invention a pour objet une nouvelle composition tinctoriale pour la teinture des fibres kératiniques, en particulier des cheveux humains, contenant un colorant monoazoïque dicationique particulier, ainsi que le procédé de teinture des fibres kératiniques mettant en œuvre une telle composition. L'invention a aussi pour objet des colorants monocationiques diazoïques nouveaux. II est connu de teindre les fibres kératiniques et en particulier les cheveux humains avec des compositions tinctoriales contenant des précurseurs de colorant d'oxydation, appelés généralement bases d'oxydation, tels que des ortho ou paraphénylènediamines, des ortho ou paraaminophénols et des composés hétérocycliques. Ces bases d'oxydation sont des composés incolores ou faiblement colorés qui, associés à des produits oxydants, donnent naissance par un processus de condensation oxydative à des composés colorés.The subject of the invention is a new dye composition for dyeing keratin fibers, in particular human hair, containing a particular dicationic monoazo dye, as well as the process for dyeing keratin fibers using such a composition. A subject of the invention is also new diazo monocolor dyes. It is known to dye keratin fibers and in particular human hair with dye compositions containing oxidation dye precursors, generally called oxidation bases, such as ortho or paraphenylenediamines, ortho or paraaminophenols and heterocyclic compounds. These oxidation bases are colorless or weakly colored compounds which, associated with oxidizing products, give rise, through an oxidative condensation process, to colored compounds.
On sait également que l'on peut faire varier les nuances obtenues avec ces bases d'oxydation en les associant à des coupleurs ou modificateurs de coloration, ces derniers étant choisis notamment parmi les métadiamines aromatiques, les métaaminophénols, les metadiphenols et certains composés hétérocycliques tels que des composés indoliques.We also know that we can vary the nuances obtained with these oxidation bases by associating them with couplers or color modifiers, the latter being chosen in particular from aromatic metadiamines, metaaminophenols, metadiphenols and certain heterocyclic compounds such as as indole compounds.
La variété des molécules mises en jeu au niveau des bases d'oxydation et des coupleurs permet l'obtention d'une riche palette de couleurs.The variety of molecules involved in the oxidation bases and couplers allows obtaining a rich palette of colors.
Ce procédé de coloration d'oxydation consiste à appliquer sur le fibres kératiniques, des bases d'oxydation ou un mélange de bases d'oxydation et de coupleurs avec un agent oxydant, par exemple de l'eau oxygénée, à laisser pauser, puis à rincer les fibres. Les colorations qui en résultent sont permanentes, puissantes, et résistantes aux agents extérieurs, notamment à la lumière, aux intempéries, aux lavages, à la transpiration et aux frottements. Généralement appliquées à pH basique, il permet d'obtenir une teinture et simultanément un éclaircissement de la fibre qui se traduit en pratique par la possibilité d'obtenir une coloration finale plus claire que la couleur d'origine. En outre, l'éclaircissement de la fibre a pour effet avantageux d'engendrer une couleur unie dans le cas des cheveux gris, et dans le cas de cheveux naturellement pigmentés, de faire ressortir la couleur, c'est à dire de la rendre plus visible. Il est aussi connu de teindre les fibres kératiniques par une coloration directe. Le procédé classiquement utilisé en coloration directe consiste à appliquer sur les fibres kératiniques des colorants directs qui sont des molécules colorées et colorantes ayant une affinité pour les fibres, à laisser pauser, puis à rincer les fibres. II est connu par exemple d'utiliser des colorants directs du type nitrés benzèniques, anthraquinoniques, nitropyridiniques, des colorants du type azoïques, xanthéniques, acridiniques aziniques ou des colorants triarylméthane.This oxidation dyeing process consists in applying to the keratin fibers, oxidation bases or a mixture of oxidation bases and couplers with an oxidizing agent, for example hydrogen peroxide, to leave on, then to rinse the fibers. The resulting colorings are permanent, powerful, and resistant to external agents, in particular to light, bad weather, washing, perspiration and rubbing. Generally applied at basic pH, it makes it possible to obtain a dyeing and at the same time a lightening of the fiber which translates in practice by the possibility of obtaining a final coloration lighter than the original color. In addition, the lightening of the fiber has the advantageous effect of generating a solid color in the case of gray hair, and in the case of naturally pigmented hair, of bringing out the color, that is to say making it more visible. It is also known to dye keratin fibers by direct coloring. The method conventionally used in direct dyeing consists in applying to the keratin fibers direct dyes which are colored and coloring molecules having an affinity for the fibers, to allow to pause, then to rinse the fibers. It is known, for example, to use direct dyes of the nitro benzene, anthraquinone, nitropyridine type, dyes of the azo, xanthene, acridine azine type or triarylmethane dyes.
Les colorations qui en résultent sont des colorations particulièrement chromatique qui sont cependant temporaires ou semi-permanentes car la nature des interactions qui lient les colorants directs à la fibre keratinique, et leur désorption de la surface et/ou du cœur de la fibre sont responsables de leur faible puissance tinctoriale et de leur mauvaise tenue aux lavages ou à la transpiration. Ces colorants directs sont en outre généralement sensibles à la lumière du fait de la faible résistance du chromophore vis-à-vis des attaques photochimiques et conduisent dans le temps à un affadissement de la coloration des cheveux. En outre, leur sensibilité à la lumière est dépendante de leur répartition uniforme ou en agrégats dans la fibre keratinique.The resulting colorings are particularly chromatic colors which are however temporary or semi-permanent because the nature of the interactions which bind the direct dyes to the keratin fiber, and their desorption from the surface and / or from the core of the fiber are responsible for their low dye power and their poor resistance to washing or perspiration. These direct dyes are also generally sensitive to light due to the low resistance of the chromophore vis-à-vis photochemical attacks and lead over time to a fading of the coloring of the hair. In addition, their sensitivity to light is dependent on their uniform or aggregate distribution in the keratin fiber.
Il est connu d'utiliser des colorants directs en combinaison avec des agents oxydants. Cependant, les colorants directs sont généralement sensibles à l'action des agents oxydants tels que l'eau oxygénée, et les agents réducteurs tels que le bisulfite de sodium, ce qui les rendent généralement difficilement utilisables dans les compositions de teinture directe éclaircissantes à base d'eau oxygénée et à base d'un agent alcalinisant ou dans des compositions de teinture d'oxydation en association avec des précurseurs du type bases d'oxydation ou coupleurs.It is known to use direct dyes in combination with oxidizing agents. However, direct dyes are generally sensitive to the action of oxidizing agents such as hydrogen peroxide, and reducing agents such as sodium bisulfite, which generally make them difficult to use in lightening direct dye compositions based on hydrogen peroxide and based on an alkalizing agent or in oxidation dye compositions in combination with precursors of the oxidation base or coupler type.
Par exemple, il a été proposé dans les demandes de brevets FR-1 584 965 et JP-062 711 435 de teindre les cheveux avec des compositions de teinture à base de colorants directs nitrés et/ou de colorants dispersés azoïques et d'eau oxygénée ammoniacale en appliquant sur les cheveux un mélange desdits colorants et dudit oxydant, réalisé juste avant l'emploi. Mais les colorations obtenues se sont révélées insuffisamment tenaces et disparaissent aux shampooings en laissant apparaître l'éclaircissement de la fibre capillaire. Une telle coloration devient inesthétique en évoluant au cours du temps. On a également proposé dans les demandes de brevets JP-53 95693 et JP-55 022638 de teindre les cheveux avec des compositions à base de colorants directs cationiques de type oxazine et d'eau oxygénée ammoniacale, en appliquant sur les cheveux, dans une première étape, de l'eau oxygénée ammoniacale, puis dans une seconde étape, une composition à base du colorant direct oxazinique. Cette coloration n'est pas satisfaisante, en raison du fait qu'elle nécessite un procédé rendu trop lent par les temps de pause des deux étapes successives. Si par ailleurs on applique sur les cheveux un mélange extemporané du colorant direct oxazinique avec de l'eau oxygénée ammoniacale, on ne colore pas, ou du moins, on obtient une coloration de la fibre capillaire qui est presque inexistante.For example, it has been proposed in patent applications FR-1,584,965 and JP-062,711,435 to dye the hair with dye compositions based on direct nitro dyes and / or disperse dyes azo and hydrogen peroxide ammonia by applying to the hair a mixture of said dyes and said oxidant, produced just before use. However, the colorings obtained have proved to be insufficiently tenacious and disappear with shampooing, revealing the lightening of the hair fiber. Such coloring becomes unsightly by evolving over time. It has also been proposed in patent applications JP-53 95693 and JP-55 022638 to dye the hair with compositions based on cationic direct dyes of the oxazine type and ammoniacal hydrogen peroxide, by applying to the hair, in a first step, ammoniacal hydrogen peroxide, then in a second step, a composition based on the direct oxazine dye. This coloration is not satisfactory, due to the fact that it requires a process made too slow by the pause times of the two successive stages. If, on the other hand, an extemporaneous mixture of the direct oxazine dye with ammonia hydrogen peroxide is applied to the hair, it does not color, or at least, a coloring of the hair fiber is obtained which is almost nonexistent.
Plus récemment, la demande de brevet FR 2 741 798 a décrit des compositions tinctoriales contenant des colorants directs comportant au moins un atome d'azote quaternisé du type azoïque ou azométhine, lesdites compositions étant à mélanger extemporanément à pH basique à une composition oxydante. Ces compositions permettent d'obtenir des colorations avec des reflets homogènes, tenaces et brillants. Cependant, elles ne permettent pas de teindre les fibres kératiniques avec autant de puissance qu'avec des compostions de coloration d'oxydation.More recently, patent application FR 2 741 798 has described dye compositions containing direct dyes comprising at least one quaternized nitrogen atom of the azo or azomethine type, said compositions being to be mixed extemporaneously at basic pH with an oxidizing composition. These compositions make it possible to obtain colorings with homogeneous, tenacious and brilliant reflections. However, they do not make it possible to dye the keratin fibers with as much power as with oxidation coloring compositions.
Il existe donc un réel besoin de rechercher des colorants directs chromatiques qui permettent de teindre les fibres kératiniques aussi puissamment que les colorants d'oxydation, qui soient aussi stables qu'eux à la lumière, soient également résistants aux intempéries, aux lavages et à la transpiration, et en outre, suffisamment stables en présence d'agents oxydants et réducteurs pour pouvoir obtenir simultanément un éclaircissement de la fibre soit par utilisation de compositions directes eclaircissantes les contenant, soit par l'utilisation de compositions de coloration d'oxydation les contenant. Il existe aussi un réel besoin de rechercher des colorants directs qui permettent de teindre les fibres kératiniques pour obtenir une gamme très large de couleurs, en particulier très chromatiques, sans oublier les nuances dites « fondamentale » comme les noirs et les marrons. Ces buts sont atteints avec la présente invention qui a pour objet une composition pour la teinture des fibres kératiniques et en particulier des fibres kératiniques humaines telles que les cheveux, comprenant au moins un colorant monoazoïque dicationique de formules (I) ou (II) suivantes :There is therefore a real need to look for direct chromatic dyes which make it possible to dye keratin fibers as powerfully as oxidation dyes, which are as stable as they are in light, are also resistant to weathering, washing and perspiration, and in addition, sufficiently stable in the presence of oxidizing and reducing agents to be able to simultaneously obtain a lightening of the fiber either by the use of direct lightening compositions containing them, or by the use of oxidation coloring compositions containing them. There is also a real need to look for direct dyes which make it possible to dye keratin fibers in order to obtain a very wide range of colors, in particular very chromatic, without forgetting the so-called "fundamental" shades such as blacks and browns. These objects are achieved with the present invention which relates to a composition for dyeing keratin fibers and in particular fibers human keratin such as the hair, comprising at least one dicationic monoazo dye of formulas (I) or (II) below:
ZrN=N-Ar(A3)n -Z2 (I)Z r N = NA r (A 3 ) n -Z 2 (I)
ZrN=N-A2 (II) formules dans lesquellesZ r N = NA 2 (II) formulas in which
• n est égal à 0 ou 1 ,• n is equal to 0 or 1,
• Z, représente un radical hétéroaromatique cationique à 5 ou 6 chaînons de formules (III) ou (IV) :• Z, represents a 5- or 6-membered cationic heteroaromatic radical of formulas (III) or (IV):
où or
X représente NR3, S ou O, Z représente CR2 ou N et Y représente CR4 ou N avec les conditions suivantes : lorsque X est NR3 ou O et Z est CR2, alors Y est CR4 ou N, lorsque X est S alors Z est N ou Y est N lorsque X est S et Z est N alors et Y est CR4 X, représente CR6 ou N, m est un nombre entier égal à 0,1,2 ou 3,X represents NR 3 , S or O, Z represents CR 2 or N and Y represents CR 4 or N with the following conditions: when X is NR 3 or O and Z is CR 2, then Y is CR 4 or N, when X is S then Z is N or Y is N when X is S and Z is N then and Y is CR 4 X, represents CR 6 or N, m is an integer equal to 0,1,2 or 3,
RL R3 et R5 représentent indépendamment l'un de l'autre une chaîne hydrocarbonée en C^C^, saturée ou insaturée ; linéaire ou ramifiée pouvant former un cycle carboné ayant de 5 à 7 chaînons, éventuellement aromatique ; un ou plusieurs atomes de carbone pouvant être remplacés par un atome d'oxygène, d'azote, d'halogènes, de soufre ou par un groupement SO2, à l'exception du carbone relié à l'atome d'azote du cycle de formule (III) ou (IV) ; les radicaux R1( R3 ou R5 ne comportant pas de liaison peroxyde, ni de radicaux diazo, nitro ou nitroso ;R L R 3 and R 5 represent, independently of one another, a saturated or unsaturated C 1 -C 4 hydrocarbon chain; linear or branched which can form a carbon ring having 5 to 7 links, possibly aromatic; one or more carbon atoms which can be replaced by an oxygen, nitrogen, halogen or sulfur atom or by an SO 2 group, with the exception of the carbon linked to the nitrogen atom of the ring of formula (III) or (IV); the radicals R 1 ( R 3 or R 5 not comprising a peroxide bond, nor of diazo, nitro or nitroso radicals;
R2, R4 et R6 représentent indépendamment l'un de l'autre un atome d'hydrogène ; une chaîne hydrocarbonée en C.,-C10l saturée ou insaturée, linéaire ou ramifiée pouvant former un cycle carboné ayant de 5 à 7 chaînons, éventuellement aromatique ; un ou plusieurs atomes de carbone pouvant être remplacés par un ou plusieurs atomes d'oxygène, d'azote, de soufre, ou par un groupement SO2 ; les radicaux R2, R4 ou R6 ne comportant pas de liaison peroxyde, ni de radicaux diazo, nitro ou nitroso ; les radicaux R2 et R4 peuvent former ensemble un cycle aromatique carboné, - V représente un anion organique ou minéral,R 2 , R 4 and R 6 independently of one another represent a hydrogen atom; a hydrocarbon chain C, -. C 10l saturated or unsaturated, linear or branched which can form a carbon ring having 5 to 7 links, optionally aromatic; one or more carbon atoms which can be replaced by one or more oxygen, nitrogen, sulfur atoms, or by an SO 2 group; the radicals R 2 , R 4 or R 6 not comprising a peroxide bond, nor of diazo, nitro or nitroso radicals; the radicals R 2 and R 4 can together form a carbon aromatic cycle, - V represents an organic or mineral anion,
• Ai et A3 représentent, indépendamment l'un de l'autre, un radical divalent de formules (V) ou (VI)• Ai and A 3 represent, independently of one another, a divalent radical of formulas (V) or (VI)
dans lesquelles n' est un nombre entier égal à 0, 1 , 2 ou 3, n" est un nombre entier égal à 0 ou 1 , - Y Yzreprésente C- ou N-N, lorsque n = 0, alors la liaison a du groupement A, de la formule (V) est relié à la fonction Z2 de la formule (I) ou, lorsque n .= 0, alors la liaison b' du groupement A, de la formule (VI) est reliée à la fonction Z2 de la formule (I), - lorsque n = 1 , alors la liaison a du groupement A, de la formule (V) est reliée au in which n 'is an integer equal to 0, 1, 2 or 3, n "is an integer equal to 0 or 1, - Y Yz represents C- or NN, when n = 0, then the bond a of group A , of formula (V) is linked to function Z 2 of formula (I) or, when n. = 0, then the bond b 'of group A, of formula (VI) is linked to function Z 2 of formula (I), - when n = 1, then the bond a of group A, of formula (V) is linked to
C, du groupement A3 de formule (V), la liaison a du groupement A3 de formuleC, of group A 3 of formula (V), the bond a of group A 3 of formula
(V) étant reliée à la fonction Z2 de la formule (I) ou, lorsque n = 1 , alors la liaison a du groupement A, de la formule (V) est reliée au carbone porteur de la liaison a' du groupement A3 de la formule (VI), la liaison b' étant reliée à la fonction Z2 de la formule (I), lorsque n = 1 , alors la liaison b' du groupement A, de la formule (VI) est reliée au carbone C, du groupement A3 de formule (V), la liaison a étant reliée à la fonction Z2 de la formule (I) ou, lorsque n = 1 , alors la liaison b' du groupement A^ de la formule (VI) est reliée au carbone porteur de la liaison a' du groupement A3 de formule (VI), la liaison b' du groupement A3 de la formule (VI) étant reliée à la fonction Z2 de la formule (I),(V) being linked to the function Z 2 of formula (I) or, when n = 1, then the bond a of group A, of formula (V) is connected to the carbon carrying the bond a 'of group A 3 of formula (VI), the bond b 'being linked to the function Z 2 of formula (I), when n = 1, then the bond b 'of the group A, of formula (VI) is linked to the carbon C, of the group A 3 of formula (V), the bond a being connected to the function Z 2 of the formula ( I) or, when n = 1, then the bond b 'of the group A ^ of formula (VI) is linked to the carbon carrying the bond a' of the group A 3 of formula (VI), the bond b 'of the group A 3 of formula (VI) being linked to the function Z 2 of formula (I),
R8 et R'8 représentent indépendamment l'un de l'autre un groupe non cationique choisi parmi un atome hydrogène, une chaîne hydrocarbonée en C^C^, linéaire ou ramifiée pouvant former un cycle carboné ayant de 5 à 7 chaînons, éventuellement aromatique ; un ou plusieurs atomes de carbone de la chaîne hydrocarbonée pouvant être remplacés par un ou plusieurs atomes d'oxygène, d'azote, de soufre, ou par un groupement SO2 à l'exception du carbone relié à l'atome d'azote ; les radicaux R8 ouR 8 and R ′ 8 represent, independently of one another, a non-cationic group chosen from a hydrogen atom, a straight or branched C ^ C ^ hydrocarbon chain which can form a carbon ring having from 5 to 7 members, optionally aromatic; one or more carbon atoms of the hydrocarbon chain which can be replaced by one or more oxygen, nitrogen, sulfur atoms, or by an SO 2 group with the exception of the carbon linked to the nitrogen atom; the radicals R 8 or
R'8 ne comportant pas de liaison peroxyde, ni de radicaux diazo, nitro ou nitroso ;R ′ 8 comprising no peroxide bond, nor diazo, nitro or nitroso radicals;
R7, R9, R'7 et R'9 représente indépendamment l'un de l'autre un groupe non cationique tel que défini pour R2 ou un groupe cationique Z3, à la condition qu'un seul des groupes R7, R9, R'7 et R'9 est cationiqueR 7 , R 9 , R ' 7 and R' 9 independently of one another represent a non-cationic group as defined for R 2 or a cationic group Z 3 , provided that only one of the groups R 7 , R 9 , R ' 7 and R' 9 is cationic
R7 avec R8, respectivement R'7 avec R'8 peuvent former ensemble un hétérocycle à 5 ou 6 chaînons saturé,R 7 with R 8 , respectively R ' 7 with R' 8 can together form a saturated 5 or 6-membered heterocycle,
Z3 est un groupe cationique représenté par la formule (VII) suivanteZ 3 is a cationic group represented by the following formula (VII)
— (B)„, D (VII) dans laquelle :- (B) „, D (VII) in which:
- B représente une chaîne hydrocarbonée comportant de 1 à 15 atomes de carbone, linéaire ou ramifiée, pouvant former un ou plusieurs cycles comportant de 3 à 7 chaînons éventuellement aromatiques, et dont un ou plusieurs atomes de carbone peuvent être remplacés par un atome d'oxygène, d'azote, de soufre, ou par un radical SO2 à l'exception du carbone relié à l'atome d'azote ; B ne comportant pas de liaison peroxyde ni de radicaux diazo, nitro ou nitroso, -le radical B est relié à D par l'un quelconque des atomes du radical D, - n'" peut prendre la valeur 0 ou 1 ,- B represents a hydrocarbon chain comprising from 1 to 15 carbon atoms, linear or branched, which can form one or more rings comprising from 3 to 7 optionally aromatic links, and one or more carbon atoms of which can be replaced by an atom of oxygen, nitrogen, sulfur, or by an SO 2 radical with the exception of the carbon linked to the nitrogen atom; B having no peroxide bond or diazo, nitro or nitroso radicals, -the radical B is linked to D by any of the atoms of the radical D, - n '"can take the value 0 or 1,
- D est choisi parmi les groupes cationiques de formules (VIII) et (IX) suivantes : dans lesquelles :- D is chosen from the cationic groups of formulas (VIII) and (IX) below: in which :
- p peut prendre la valeur 0 ou 1 ;- p can take the value 0 or 1;
- T1t T2, T3 et T4, indépendamment les uns des autres, représentent un atome d'oxygène ; un atome de soufre ; un atome d'azote non substitué ou substitué par un radical R14 ; ou un atome de carbone non substitué ou substitué par un ou deux radicaux R14, identiques ou différents ;- T 1t T 2 , T 3 and T 4 , independently of each other, represent an oxygen atom; a sulfur atom; a nitrogen atom unsubstituted or substituted by a radical R 14 ; or a carbon atom unsubstituted or substituted by one or two radicals R 14 , identical or different;
- T5 représente un atome d'azote ; ou un atome de carbone non substitué ou substitué par un radical R14 ;- T 5 represents a nitrogen atom; or a carbon atom unsubstituted or substituted by a radical R 14 ;
- T6 peut prendre les mêmes significations que celles indiquées ci-dessous pour le radical R14, étant entendu que T6 est différent d'un atome d'hydrogène ;- T 6 can take the same meanings as those indicated below for the radical R 14 , it being understood that T 6 is different from a hydrogen atom;
- T, ou T5 peuvent, en outre, former avec T6 un cycle saturé ou insaturé comportant de 5 à 7 chaînons, chaque chaînon étant non substitué ou substitué par un ou deux radicaux R14 identiques ou différents ; - deux des radicaux adjacents T^ T2, T3, T4 et T5 peuvent en outre former un cycle comportant de 5 à 7 chaînons, chaque chaînon étant indépendamment représenté par un atome de carbone non substitué ou substitué par un ou deux radicaux R14 identiques ou différents, un atome d'azote substitué ou non substitué par un radical R14, un atome d'oxygène ou un atome de soufre ;- T, or T 5 can, in addition, form with T 6 a saturated or unsaturated ring comprising from 5 to 7 links, each link being unsubstituted or substituted by one or two identical or different R 14 radicals; - two of the adjacent radicals T ^ T 2 , T 3 , T 4 and T 5 can also form a ring comprising from 5 to 7 links, each link being independently represented by a carbon atom unsubstituted or substituted by one or two radicals R 14 identical or different, a nitrogen atom substituted or unsubstituted by a radical R 14 , an oxygen atom or a sulfur atom;
- Rio. Rn. 12. R13 et R14, identiques ou différents représentent un atome d'hydrogène ; une chaîne hydrocarbonée comportant de 1 à 10 atomes de carbone, linéaire ou ramifiée, éventuellement aromatiques, et dont un ou plusieurs atomes de carbone peuvent être remplacés par un atome d'oxygène, d'azote, de soufre, ou par un groupe SO2, et dont un ou plusieurs atomes de carbone peuvent, indépendamment les uns des autres, être substitués par un ou plusieurs atomes d'halogène ; ledit radical ne comportant pas de liaison peroxyde ni de radicaux diazo, nitro ou nitroso ;- Rio. Rn. 1 2 . R 13 and R 14, identical or different, represent a hydrogen atom; a hydrocarbon chain comprising from 1 to 10 carbon atoms, linear or branched, optionally aromatic, and one or more carbon atoms of which may be replaced by an oxygen, nitrogen, sulfur atom, or by an SO 2 group , and of which one or more carbon atoms can, independently of each other, be substituted by one or more halogen atoms; said radical not comprising a peroxide bond or diazo, nitro or nitroso radicals;
- R10, Ru et R12 peuvent également former, deux à deux avec l'atome d'azote quaternaire auquel ils sont rattachés, un ou plusieurs cycles saturés comportant de 5 à 7 chaînons, chaque chaînon étant indépendamment représenté par un atome de carbone non substitué ou substitué par un ou deux radicaux R14 identiques ou différents, un atome d'azote non substitué ou substitué par un radical R14 , un atome d'oxygène , ou un atome de soufre, -lorsque n'" = 0, alors le groupement de formule (IX) peut être relié au composé de formule (V) et (VI) directement par l'atome d'azote de l'ammonium quaternaire, R13 représentant dans ce cas une simple liaison,- R 10 , Ru and R 12 can also form, two by two with the quaternary nitrogen atom to which they are attached, one or more saturated rings comprising from 5 to 7 links, each link being independently represented by a carbon atom unsubstituted or substituted by one or two identical or different R 14 radicals, a nitrogen atom unsubstituted or substituted by an R 14 radical, an oxygen atom, or a sulfur atom, -when n '"= 0, then the group of formula (IX) can be linked to the compound of formula (V) and (VI) directly by the nitrogen atom of the quaternary ammonium, R 13 representing in this case a single bond,
- V représente un anion organique ou minéral,- V represents an organic or mineral anion,
• Z2 représente une chaîne hydrocarbonée en CrC^, linéaire ou ramifiée pouvant former un cycle carboné ayant de 5 à 7 chaînons, éventuellement aromatique ; un ou plusieurs atomes de carbone pouvant être remplacés par un ou plusieurs atomes d'oxygène, d'azote, de soufre ou par un groupement SO2. ledit radical Z2 ne comportant pas de liaison peroxyde, ni de radicaux diazo, nitro ou nitroso ; un groupe cationique Z3 tel que défini ci-dessus, avec la réserve que Z2 n'est pas cationique lorsque R7, R9, R7' ou R9' est cationique,• Z 2 represents a linear or branched CrC ^ hydrocarbon chain which can form a carbon ring having 5 to 7 members, optionally aromatic; one or more carbon atoms which can be replaced by one or more oxygen, nitrogen, sulfur atoms or by an SO 2 group. said radical Z 2 not comprising a peroxide bond, nor of diazo, nitro or nitroso radicals; a cationic group Z 3 as defined above, with the proviso that Z 2 is not cationic when R 7 , R 9 , R 7 'or R 9 ' is cation,
• A2 représente un radical de formule (X) correspondant à un radical aromatique carboné, pyridinique ou pyridazinique substitué par un radical hétéroaromatique cationique à 5 chaînons, éventuellement substitué par un ou plusieurs radicaux R19 de même définition que R2 ; un radical de formule (XI) :• A 2 represents a radical of formula (X) corresponding to a carbon, pyridine or pyridazine aromatic radical substituted by a cationic heteroaromatic 5-membered radical, optionally substituted by one or more radicals R 19 of the same definition as R 2 ; a radical of formula (XI):
dans lesquelles r est un entier égal à 0 ou 1 , - q est un entier égal à 0, 1 , 2 ou 3, s est un entier égal à 0, 1 , 2, 3 , 4 ou 5, t est un entier égal à 0, 1 ou 2. Y3=Y4 représente C=C, C=N ou N=N, si r = 0 alors X représente O, S, NR18ι CR20, - si r = 1 alors X représente CR20 in which r is an integer equal to 0 or 1, - q is an integer equal to 0, 1, 2 or 3, s is an integer equal to 0, 1, 2, 3, 4 or 5, t is an equal integer at 0, 1 or 2. Y 3 = Y 4 represents C = C, C = N or N = N, if r = 0 then X represents O, S, NR 18ι CR 20 , - if r = 1 then X represents CR 20
R15 et R18 ont la même définition que R^ définie ci-dessus, R16 R17, R19 , R20et R21ont la même définition que R2 définie ci-dessus, V" représente un anion organique ou minéral, avec la condition que dans la formule (I) un des groupes A1 t Z2 et A3 est un groupe cationique.R 15 and R 18 have the same definition as R ^ defined above, R 16 R 17 , R 19 , R 20 and R 21 have the same definition as R 2 defined above, V "represents an organic or mineral anion , with the proviso that in formula (I) one of the groups A 1 t Z 2 and A 3 is a cationic group.
Selon l'invention, lorsqu'il est indiqué pour les groupes R,, R3, R5, R2, R4l According to the invention, when it is indicated for the groups R ,, R 3 , R 5 , R 2 , R 4l
R6. Rβ- Rβ'. R7. . R9,R'9,B, R10 R„ R12 R13 R14 Z2 qu'un ou plusieurs des atomes de carbone peuvent être remplacés par un atome d'oxygène, d'azote, d'halogène, de soufre ou par un groupement SO2, et/ou que ces groupes sont insaturés, cela signifie que l'on peut, à titre d'exemple, faire les transformations suivantes : R 6 . Rβ- Rβ '. R7. . R 9 , R ' 9 , B, R 10 R „R 12 R 13 R 14 Z 2 that one or more of the carbon atoms may be replaced by an oxygen, nitrogen, halogen or sulfur atom or by an SO 2 group, and / or that these groups are unsaturated, this means that the following transformations can be made, for example:
-CH— H peut devenir ', ° H -CH— H can become ', ° H
peut devenircan become
peut devenircan become
peut devenir can become
-CH2-CH3 peut devenir ', ° CH3-CH 2 -CH 3 can become ', ° CH 3
Selon la présente invention, les radicaux R,, R3 et R5 sont de préférence choisis parmi un radical alkyle ou alcényle en C^C, pouvant être substitué par un ou plusieurs substituants hydroxy, amino éventuellement substitué, carboxyl , sulfonique; un radical phényle pouvant être substitué par un ou plusieurs atomes d'halogène, un ou plusieurs groupes alkyle en C1-C4, aikoxy en C1-C4, amino, hydroxy, trifluorométhyle, alkylamino en C.,-C4, carboxy ou sulfonyle ; un radical benzyle pouvant être substitué par un ou plusieurs atomes d'halogène, un ou plusieurs groupes alkyle en C1-C4, aikoxy en C^C», amino, trifluorométhyle ; un hétérocycle choisi parmi l'imidazole, le thiazole, la pyridine ou la pyrimidine ; un radical (CH2)p-T-(CH2)q-V1R' où p et q sont entiers, identiques ou différents, compris entre 1 et 3, R' représente H ou méthyle et T et V désignent indépendamment un atome d'oxygène ou un radical NR" avec R" désignant un hydrogène ou un méthyle. Selon la présente invention définie ci-dessus, on préfère pour R^ R3 et R5 plus particulièrement les radicaux méthyle ; éthyle ; hydroxyéthyle ; aminoéthyle ; carboxyméthyle ; carboxyéthyle ; phényle ; benzyle ; les hétérocycles choisis parmi pyridyle, imidazolyle, pyrimidinyle.According to the present invention, the radicals R ,, R 3 and R 5 are preferably chosen from a C 1 -C 6 alkyl or alkenyl radical which may be substituted by one or more hydroxy, optionally substituted amino, carboxyl or sulphonic substituents; a phenyl radical which may be substituted by one or more halogen atoms, one or more alkyl groups C 1 -C 4 alkyl, aikoxy C 1 -C 4 alkyl, amino, hydroxy, trifluoromethyl, alkylamino, C, -. C 4, carboxy or sulfonyl; a benzyl radical which may be substituted by one or more halogen atoms, one or more C 1 -C 4 alkyl, C 1 -C 4 alkoxy, amino, trifluoromethyl; a heterocycle chosen from imidazole, thiazole, pyridine or pyrimidine; a radical (CH2) p -T- (CH2) q -V 1 R 'where p and q are whole, identical or different, comprised between 1 and 3, R' represents H or methyl and T and V independently denote an atom d oxygen or a radical NR "with R" denoting hydrogen or methyl. According to the present invention defined above, methyl radicals are preferred for R ^ R 3 and R 5 more particularly; ethyl; hydroxyethyl; aminoethyl; carboxymethyl; carboxyethyl; phenyl; benzyl; heterocycles chosen from pyridyle, imidazolyle, pyrimidinyle.
Plus particulièrement, les radicaux R^ et R3 sont choisis parmi les groupes méthyle ; éthyle ; phényle ; hydroxyéthyle ; aminoéthyle ; carboxyméthyl ; carboxyéthyle.More particularly, the radicals R 1 and R 3 are chosen from methyl groups; ethyl; phenyl; hydroxyethyl; aminoethyl; carboxymethyl; carboxyethyl.
Les radicaux R2, R4 et R6 sont de préférence choisis parmi un atome d'hydrogène ; un radical alkyle par exemple méthyle, éthyle ; un radical alkyle substitué par un ou plusieurs hydroxy, amino ou un halogène comme hydroxyméthyle, hydroxyéthyle, 1 ,2-dihydroxyéthyle, 1 ,2-dihydroxypropyle, 2,3-dihydroxypropyle, aminométhyle, aminoéthyle, aminopropyle ; trifluorométhyle ; un radical phényle pouvant être substitué par un ou plusieurs substituants choisis parmi les radicaux alkyle, hydroxy, amino, alcoxy, carboxyle, trifluorométhyle, sulfonique ; les radicaux benzyle et les benzyles substitués par un alcoxy, par exemple méthoxy, ou hydroxy notamment 2-méthoxybenzyle, 3-méthoxybenzyle, 4-méthoxybenzyle, 2- hydroxybenzyle, 3-hydroxybenzyle, 4-hydroxybenzyle ; un hétérocycle choisi parmi N- pyrrolidinyle, N-pipéridinyle, N-morpholine, N-pipérazinyle ou N-imidazolyle ; un radical alcoxy comme méthoxy ou éthoxy ; un radical phosphonyle ; un radical siloxy un radical amino ; un radical (di)alkylamino en C^C^ un radical acyle ; un radical acylamino ; un radical sulfonamide ; un radical uréido ; un radical sulfonylamino.The radicals R 2 , R 4 and R 6 are preferably chosen from a hydrogen atom; an alkyl radical, for example methyl, ethyl; a substituted alkyl radical with one or more hydroxy, amino or halogen such as hydroxymethyl, hydroxyethyl, 1,2-dihydroxyethyl, 1,2-dihydroxypropyl, 2,3-dihydroxypropyl, aminomethyl, aminoethyl, aminopropyl; trifluoromethyl; a phenyl radical which may be substituted by one or more substituents chosen from alkyl, hydroxy, amino, alkoxy, carboxyl, trifluoromethyl, sulfonic radicals; benzyl radicals and benzyls substituted by an alkoxy, for example methoxy, or hydroxy, in particular 2-methoxybenzyl, 3-methoxybenzyl, 4-methoxybenzyl, 2-hydroxybenzyl, 3-hydroxybenzyl, 4-hydroxybenzyl; a heterocycle chosen from N-pyrrolidinyl, N-piperidinyl, N-morpholine, N-piperazinyl or N-imidazolyl; an alkoxy radical such as methoxy or ethoxy; a phosphonyl radical; a siloxy radical an amino radical; a (di) C 1 -C 4 alkylamino radical an acyl radical; an acylamino radical; a sulfonamide radical; a ureido radical; a sulfonylamino radical.
Les radicaux R2, R4 et R6 préférés sont l'hydrogène ; un radical alkyle choisi parmi méthyle, éthyle ; un radical alkyle substitué choisi parmi trifluorométhyle; hydroxyméthyle, hydroxyéthyle, aminométhyle, aminoéthyle ; un benzyle ; un phényl éventuellement substitué par un ou plusieurs radicaux choisis parmi les radicaux méthyle, hydroxy, amino, méthoxy ; 2-méthoxybenzyle ; 4-méthoxybenzyle ; 2- hydroxybenzyle ; 4-hydroxybenzyle ; un hétérocycle choisi parmi pyrrolidinyle, pipéridinyle ; un radical méthoxy ; un radical acyle ; ; un radical amino ; un radical (di)alkylamino en C^C,; Plus particulièrement, les radicaux R2 R4 et R6sont choisis parmi l'hydrogène ; méthyle ; éthyle ; trifluorométhyle ; phényle ; pyrrolidinyle ; méthoxy ; amino.The preferred radicals R 2 , R 4 and R 6 are hydrogen; an alkyl radical chosen from methyl, ethyl; a substituted alkyl radical chosen from trifluoromethyl; hydroxymethyl, hydroxyethyl, aminomethyl, aminoethyl; benzyl; a phenyl optionally substituted by one or more radicals chosen from methyl, hydroxy, amino and methoxy radicals; 2-methoxybenzyl; 4-methoxybenzyl; 2- hydroxybenzyl; 4-hydroxybenzyl; a heterocycle chosen from pyrrolidinyl, piperidinyl; a methoxy radical; an acyl radical; ; an amino radical; a (di) alkylamino radical in C ^ C ,; More particularly, the radicals R 2 R 4 and R 6 are chosen from hydrogen; methyl; ethyl; trifluoromethyl; phenyl; pyrrolidinyl; methoxy; amino.
R8 et R8' sont de préférence choisis parmi un radical alkyle ou alcényle en C1-C4 pouvant être substitué par un ou plusieurs substituants hydroxy, amino éventuellement substitué, carboxyl ; un radical phényle pouvant être substitué par un ou plusieurs atomes d'halogène, un ou plusieurs groupes alkyle en C C4, aikoxy en C^Ot, amino, hydroxy, trifluorométhyle, alkylamino en Ci-C», carboxy ou sulfonyle ; un hétérocycle choisi parmi l'imidazole, le thiazole, la pyridine ou la pyrimidine ; un radical (CH2)p-T-(CH2)q-V1R' où p et q sont entiers, identiques ou différents, compris entre 1 et 3, R' représente H ou méthyle et T et V, désignent indépendamment un atome d'oxygène ou un radical NR" avec R" désignant un hydrogène ou un méthyle. Selon la présente invention définie ci-dessus, on préfère pour R8, R'„ plus particulièrement les radicaux Hydrogène ; méthyle ; éthyle ; hydroxyéthyle ; aminoéthyle ; carboxyméthyle ; carboxyéthyle ; phényle ; les hétérocycles choisis parmi pyridynyle, imidazolyle, pyrimidinyle. Plus particulièrement, les radicaux R8 et R'8 sont choisis parmi les groupes hydrogène ; méthyle ; éthyle ; phényle ; hydroxyéthyle .; aminoéthyle ; carboxyméthyl ; carboxyéthyle.R 8 and R 8 'are preferably chosen from a C 1 -C 4 alkyl or alkenyl radical which may be substituted by one or more hydroxy, optionally substituted amino, carboxyl substituents; a phenyl radical which may be substituted by one or more halogen atoms, one or more alkyl groups CC 4 aikoxy C t ^ O, amino, hydroxy, trifluoromethyl, alkylamino-C ", carboxy or sulfonyl; a heterocycle chosen from imidazole, thiazole, pyridine or pyrimidine; a radical (CH2) p -T- (CH2) q -V 1 R 'where p and q are whole, identical or different, between 1 and 3, R' represents H or methyl and T and V, independently denote an atom of oxygen or a radical NR "with R" denoting a hydrogen or a methyl. According to the present invention defined above, R 8 is preferred for R 8 , more particularly the hydrogen radicals; methyl; ethyl; hydroxyethyl; aminoethyl; carboxymethyl; carboxyethyl; phenyl; heterocycles chosen from pyridynyl, imidazolyl, pyrimidinyl. More particularly, the radicals R 8 and R ′ 8 are chosen from hydrogen groups; methyl; ethyl; phenyl; hydroxyethyl; aminoethyl; carboxymethyl; carboxyethyl.
B est de préférence choisi parmi un radical alkyle éventuellement substitué choisi parmi méthyle, éthyle, propyle ; hydroxyméthyle, hydroxyéthyle, aminométhyle, aminoéthyle ; un méthoxybenzyle ; un hétérocycle choisi parmi pipérazinyle . Plus particulièrement, le radical B est choisi parmi méthyle ; éthyle ; propyle ; phényle ; pypérazinyle ; triazine.B is preferably chosen from an optionally substituted alkyl radical chosen from methyl, ethyl, propyl; hydroxymethyl, hydroxyethyl, aminomethyl, aminoethyl; methoxybenzyl; a heterocycle chosen from piperazinyl. More particularly, the radical B is chosen from methyl; ethyl; propyl; phenyl; piperazinyl; triazine.
Rio. Ru. R12. R13 et R14 sont de préférence choisis parmi un hydrogène ; un radical alkyle ou alcényle en C,-C4 pouvant être substitué par un substituant hydroxy, amino éventuellement substitué; un radical phényle pouvant être substitué par un ou plusieurs atomes d'halogène, un ou plusieurs groupes alkyle en C C, aikoxy en d- C4, amino, hydroxy, trifluorométhyle, alkylamino en C1-C4, carboxy ou sulfonyle ; un radical benzyle pouvant être substitué par un ou plusieurs atomes d'halogène, un ou plusieurs groupes alkyle en C^O,, aikoxy en C^Ot, amino, trifluorométhyle ; un radical (poly)aminoalkyl en CrC4 ; un radical (CH2)p-T-(CH2)q-VR' où p et q sont entiers, identiques ou différents, compris entre 1 et 3, R' représente H ou méthyle et T et V désignent indépendamment un atome d'oxygène ou un radical NR" avec R" désignant un hydrogène ou un méthyle, un radical sulfonyl.Rio. Ru. R 12 . R 13 and R 14 are preferably chosen from hydrogen; a C 1 -C 4 alkyl or alkenyl radical which may be substituted with a hydroxy or optionally substituted amino substituent; a phenyl radical which may be substituted by one or more halogen atoms, one or more alkyl groups CC, aikoxy in d- -C 4 alkylamino, hydroxy, trifluoromethyl, alkylamino, C 1 -C 4 alkyl, carboxy or sulfonyl; benzyl which may be substituted by one or more halogen atoms, one or more alkyl, C ^ O ,, aikoxy C ^ O t, amino, trifluoromethyl; a C r C 4 (poly) aminoalkyl radical; a radical (CH2) p -T- (CH2) q -VR 'where p and q are whole, identical or different, comprised between 1 and 3, R' represents H or methyl and T and V independently denote an oxygen atom or a radical NR "with R" denoting hydrogen or methyl, a sulfonyl radical.
Selon la présente invention définie ci-dessus, on préfère pour R10, R11f R12, R13 et R14 plus particulièrement les radicaux méthyle ; éthyle ; isopropyle ; hydroxyéthyle ; aminoéthyle ; phényle ; benzyle ; les hétérocycles choisis parmi pyridynyle, imidazolyle, pyrimidinyle. Plus particulièrement, les radicaux R10, R^, R12, R13 et R14 sont choisis parmi les groupes méthyle ; éthyle ; phényle ; hydroxyéthyle ; aminoéthyle ; carboxyméthyl ; carboxyéthyle.According to the present invention defined above, preferred for R 10 , R 11f R 12 , R 13 and R 14 are more particularly methyl radicals; ethyl; isopropyl; hydroxyethyl; aminoethyl; phenyl; benzyl; heterocycles chosen from pyridynyl, imidazolyl, pyrimidinyl. More particularly, the radicals R 10 , R ^, R 12 , R 13 and R 14 are chosen from methyl groups; ethyl; phenyl; hydroxyethyl; aminoethyl; carboxymethyl; carboxyethyl.
Z1 est de préférence choisi parmi le groupe constitué des radicaux imidazolinium , triazolinium, thiazolinium, pyridinium, pyridazinium éventuellement substitué sur les atomes de carbone du cycle par un méthyl, un méthoxy, un carboxy, un amino, un phényl, une pyrrolidine et sur l'atome d'azote par un méthyl, un 2- hydroxyethyl, un carboxyméthyl, un carboxyethyl.Z1 is preferably chosen from the group consisting of imidazolinium, triazolinium, thiazolinium, pyridinium, pyridazinium radicals optionally substituted on the ring carbon atoms by a methyl, a methoxy, a carboxy, an amino, a phenyl, a pyrrolidine and on the nitrogen atom by a methyl, a 2-hydroxyethyl, a carboxymethyl, a carboxyethyl.
Z2 est de préférence choisi parmi les radicaux imidazolium, pyridinium, pyridazinium, pyrimidinium, pyrazinium. A2 est de préférence choisi parmi les radicaux pyrazolyle, pyrrolyle, imidazolyle, triazolyle, thiadiazolyle, éventuellement substitué.Z 2 is preferably chosen from the imidazolium, pyridinium, pyridazinium, pyrimidinium, pyrazinium radicals. A 2 is preferably chosen from pyrazolyl, pyrrolyl, imidazolyl, triazolyl, thiadiazolyl radicals, optionally substituted.
A,, A3 représentent indépendamment l'un de l'autre un radical aniline, aminopyridinyle, aminopyridazinyle éventuellement substitué par un atome d'hydrogène, par un radical alkyle par exemple choisi parmi méthyle, éthyle, un alkyl substitué par exemple hydroxyméthyle, hydroxyéthyle, 1 ,2-dihydroxyéthyle, 1 ,2- dihydroxypropyle, 2,3-dihydroxypropyle, aminométhyle, aminoéthyle, aminopropyle ; par un radical trifluorométhyle ; par un hétérocycle choisi parmi N-pyrrolidinyle, N- pipéridinyle, N-morpholine, N-pipérazinyle ou N-imidazolyle, par un radical alcoxy comme méthoxy ou éthoxy, par un radical phosphonyle, par un radical siloxy, par un radical 1,2-diaminoéthyle, par un radical 2,3-diaminopropyle, par un radical acyle, par un radical acylamino, par un radical sulfonamide, par un radical uréido, par un radical sulfonylamino.A ,, A 3 independently of one another represent an aniline, aminopyridinyl, aminopyridazinyl radical optionally substituted by a hydrogen atom, by an alkyl radical, for example chosen from methyl, ethyl, an alkyl substituted, for example hydroxymethyl, hydroxyethyl , 1,2-dihydroxyethyl, 1,2-dihydroxypropyl, 2,3-dihydroxypropyl, aminomethyl, aminoethyl, aminopropyl; with a trifluoromethyl radical; by a heterocycle chosen from N-pyrrolidinyl, N-piperidinyl, N-morpholine, N-piperazinyl or N-imidazolyl, by an alkoxy radical such as methoxy or ethoxy, by a phosphonyl radical, by a siloxy radical, by a 1,2 radical -diaminoethyl, by a 2,3-diaminopropyl radical, by an acyl radical, by an acylamino radical, by a sulfonamide radical, by a ureido radical, by a sulfonylamino radical.
Les couples (A^ A3) préférés sont choisis parmi (radical aniline, radical aniline), (radical aniline, radical aminopyridinyle), (radical aminopyridinyle, radical aniline), De façon indépendante, chacun des radicaux constituant ces couples, est éventuellement substitué par un atome d'hydrogène, ou par un radical alkyle choisi parmi méthyle, éthyle, ou par un radical alkyle éventuellement substitué choisi parmi hydroxyméthyle, 1 ,2-dihydroxyéthyle, aminométhyle, 2-aminoéthyle, 1 ,2-diaminoéthyle, 2,3-diaminopropyle ou par un hétérocycle choisi parmi pyrrolidinyle, pipéridinyle, ou par un radical méthoxy ; amino ; méthylamino ; dimethylamino ; 2-hydroxyethylaminoThe preferred couples (A ^ A 3 ) are chosen from (aniline radical, aniline radical), (aniline radical, aminopyridinyl radical), (aminopyridinyl radical, aniline radical), independently, each of the radicals constituting these couples, is optionally substituted by a hydrogen atom, or by an alkyl radical chosen from methyl, ethyl, or by an optionally substituted alkyl radical chosen from hydroxymethyl, 1,2-dihydroxyethyl, aminomethyl, 2-aminoethyl, 1,2-diaminoethyl, 2,3 -diaminopropyl or by a heterocycle chosen from pyrrolidinyl, piperidinyl, or by a methoxy radical; amino; methylamino; dimethylamino; 2-hydroxyethylamino
On choisira plus particulièrement les couples (A^ A3) suivants : (radical aniline, radical aniline) éventuellement subtitué par un radical méthyle, éthyle, ou par un radical hydroxyméthyle, 1 ,2-dihydroxyéthyle, aminométhyle, 2-aminoéthyle, 1 ,2- diaminoéthyle, 2,3-diaminopropyle ou par un radical pyrrolidinyle, pipéridinyle, ou par un radical méthoxy ; amino ; méthylamino ; dimethylamino ; 2-hydroxyethylaminoThe following pairs (A ^ A 3 ) will be chosen more particularly: (aniline radical, aniline radical) optionally substituted by a methyl, ethyl radical, or by a hydroxymethyl radical, 1, 2-dihydroxyethyl, aminomethyl, 2-aminoethyl, 1, 2- diaminoethyl, 2,3-diaminopropyl or by a pyrrolidinyl, piperidinyl radical, or by a methoxy radical; amino; methylamino; dimethylamino; 2-hydroxyethylamino
Dans le cadre de l'invention, les anions organiques ou minéraux des formules (I) ou (II) peuvent être choisi parmi un halogénure tel que chlorure, bromure, fluorure, iodure ; un hydroxyde ; un sulfate ; un hydrogénosulfate ; un alky d- C6)sulfate tel que par exemple un méthylsulfate ou un éthylsulfate ; un acétate ; un tartrate ; un oxalate ; un alky^d-C^sulfonate tel que méthylsulfonate ; un arylsulfonate substitué ou non substitué par un radical alkyle en C C4 tel que par exemple un 4-toluylsulfonate.In the context of the invention, the organic or mineral anions of formulas (I) or (II) can be chosen from a halide such as chloride, bromide, fluoride, iodide; a hydroxide; a sulfate; a hydrogen sulfate; an alkyl d-C 6 ) sulphate such as for example a methyl sulphate or an ethyl sulphate; an acetate; a tartrate; an oxalate; an alkyl ^ dC ^ sulfonate such as methylsulfonate; an arylsulfonate substituted or unsubstituted by a CC 4 alkyl radical such as for example a 4-toluylsulfonate.
Dans le cadre de l'invention, les colorants azoiques de formule (I) sont de préférence choisis parmi les colorants suivants :In the context of the invention, the azo dyes of formula (I) are preferably chosen from the following dyes:
De préférene, les composés préférés et qui peuvent être synthétisés selon ratoire décrit dans les exemples sont choisis parmi La concentration en colorant cationique azoïque de formule (I) peut varier entre 0,001 et 5% en poids environ par rapport au poids total de la composition tinctoriale, et de préférence entre environ 0,05 et 2%.Preferably, the preferred compounds which can be synthesized according to the method described in the examples are chosen from The concentration of azo cationic dye of formula (I) can vary between 0.001 and 5% by weight approximately relative to the total weight of the dye composition, and preferably between approximately 0.05 and 2%.
La composition de l'invention peut de plus comprendre un agent oxydant. Cet agent oxydant peut être n'importe quel agent oxydant utilisé de façon classique pour la décoloration des fibres kératiniques. L'agent oxydant est choisi de préférence parmi le peroxyde d'hydrogène, le peroxyde d'urée, les bramâtes de métaux alcalins, les persels tels que les perborates et les persulfates. L'utilisation du peroxyde d'hydrogène est particulièrement préférée. La composition selon l'invention peut de plus comprendre une base d'oxydation. Cette base d'oxydation peut être choisie parmi les bases d'oxydation classiquement utilisées en teinture d'oxydation, par exemple les paraphénylènediamines, les bis-phénylalkylènediamines, les para-aminophénols, les ortho-aminophénols et les bases hétérocycliques. Parmi les paraphénylènediamines, on peut plus particulièrement citer à titre d'exemple, la paraphénylènediamine, la paratoluylènediamine, la 2-chloro paraphénylènediamine, la 2,3-diméthyl paraphénylènediamine, la 2,6-diméthyl paraphénylènediamine, la 2,6-diéthyl paraphénylènediamine, la 2,5-diméthyl paraphénylènediamine, la N,N-diméthyl paraphénylènediamine, la N,N-diéthyl paraphénylènediamine, la N,N-dipropyl paraphénylènediamine, la 4-amino N,N-diéthyl 3-méthyl aniline, la N,N-bis-(β-hydroxyéthyl) paraphénylènediamine, la 4-N,N-bis-(β- hydroxyéthyl)amino 2-méthyl aniline, la 4-N,N-bis-(β-hydroxyéthyl)amino 2-chloro aniline, la 2-β-hydroxyéthyl paraphénylènediamine, la 2-fluoro paraphénylènediamine, la 2-isopropyl paraphénylènediamine, la N-(β-hydroxypropyl) paraphénylènediamine, la 2-hydroxyméthyl paraphénylènediamine, la N,N-diméthyl 3-méthyl paraphénylènediamine, la N,N-(éthyl, β-hydroxyéthyl) paraphénylènediamine, la N-(β,γ- dihydroxypropyl) paraphénylènediamine, la N-(4'-aminophényl) paraphénylènediamine, la N-phényl paraphénylènediamine, la 2-β-hydroxyéthyloxy paraphénylènediamine, la 2-β-acétylaminoéthyloxy paraphénylènediamine, la N-(β-méthoxyéthyl) paraphénylènediamine, la 4 aminophenyl pyrrolidine, le 2 thiényl paraphenylene diamine, le 2-β hydroxyéthylamino 5-amino toluène et leurs sels d'addition avec un acide. Parmi les paraphénylènediamines citées ci-dessus, la paraphénylènediamine, la paratoluylènediamine, la 2-isopropyl paraphénylènediamine, la 2-β-hydroxyéthyl paraphénylènediamine, la 2-β-hydroxyéthyloxy paraphénylènediamine, la 2,6-diméthyl paraphénylènediamine, la 2,6-diéthyl paraphénylènediamine, la 2,3-diméthyl paraphénylènediamine, la N,N-bis-(β- hydroxyéthyl) paraphénylènediamine, la 2-chloro paraphénylènediamine, la 2-β-acétylaminoéthyloxy paraphénylènediamine, et leurs sels d'addition avec un acide sont particulièrement préférées.The composition of the invention may also comprise an oxidizing agent. This oxidizing agent can be any oxidizing agent conventionally used for bleaching keratin fibers. The oxidizing agent is preferably chosen from hydrogen peroxide, urea peroxide, bramates of alkali metals, persalts such as perborates and persulfates. The use of hydrogen peroxide is particularly preferred. The composition according to the invention can also comprise an oxidation base. This oxidation base can be chosen from the oxidation bases conventionally used in oxidation dyeing, for example paraphenylenediamines, bis-phenylalkylenediamines, para-aminophenols, ortho-aminophenols and heterocyclic bases. Among the paraphenylenediamines, there may be more particularly mentioned by way of example, paraphenylenediamine, paratoluylenediamine, 2-chloro paraphenylenediamine, 2,3-dimethyl paraphenylenediamine, 2,6-dimethyl paraphenylenediamine, 2,6-diethyl paraphenylenediamine , 2,5-dimethyl paraphenylenediamine, N, N-dimethyl paraphenylenediamine, N, N-diethyl paraphenylenediamine, N, N-dipropyl paraphenylenediamine, 4-amino N, N-diethyl 3-methyl aniline, N, N-bis- (β-hydroxyethyl) paraphenylenediamine, 4-N, N-bis- (β- hydroxyethyl) amino 2-methyl aniline, 4-N, N-bis- (β-hydroxyethyl) amino 2-chloro aniline , 2-β-hydroxyethyl paraphenylenediamine, 2-fluoro paraphenylenediamine, 2-isopropyl paraphenylenediamine, N- (β-hydroxypropyl) paraphenylenediamine, 2-hydroxymethyl paraphenylenediamine, N, N-dimethyl 3-methyl paraphenylen , N- (ethyl, β-hydroxyethyl) paraphenylenediamine, N - (β, γ- dihydroxypropyl) paraphenylenediamine, N- (4'-aminophenyl) paraphenylenediamine, N-phenyl paraphenylenediamine, 2-β-hydroxyethyloxy paraphenylenediamine, 2-β-acetylaminoethyloxy paraphenylenediamine ) paraphenylenediamine, 4 aminophenyl pyrrolidine, 2 thienyl paraphenylene diamine, 2-β hydroxyethylamino 5-amino toluene and their addition salts with an acid. Among the paraphenylenediamines mentioned above, paraphenylenediamine, paratoluylenediamine, 2-isopropyl paraphenylenediamine, 2-β-hydroxyethyl paraphenylenediamine, 2-β-hydroxyethyloxy paraphenylenediamine, 2,6-dimethyl paraphenylenediamine para-phenylenediamine, 2,3-dimethyl para-phenylenediamine, N, N-bis- (β-hydroxyethyl) para-phenylenediamine, 2-chloro para-phenylenediamine, 2-β-acetylaminoethyloxy para-phenylenediamine, and their addition salts with an acid are particularly preferred .
Parmi les bis-phénylalkylènediamines, on peut citer à titre d'exemple, le N,N'-bis-(β-hydroxyéthyl) N,N'-bis-(4'-aminophényl) 1 ,3-diamino propanol, la N,N'-bis- (β-hydroxyéthyl) N,N'-bis-(4'-aminophényl) éthylenediamine, la N,N'-bis-(4- aminophényl) tétraméthylènediamine, la N,N'-bis-(β-hydroxyéthyl) N,N'-bis-(4- aminophényl) tétraméthylènediamine, la N,N'-bis-(4-méthyl-aminophényl) tétraméthylènediamine, la N.N'-bis-(éthyl) N,N'-bis-(4'-amino, 3'-méthylphényl) éthylenediamine, le 1 ,8-bis-(2,5-diamino phénoxy)-3,6-dioxaoctane, et leurs sels d'addition avec un acide.Among the bis-phenylalkylenediamines, there may be mentioned by way of example, N, N'-bis- (β-hydroxyethyl) N, N'-bis- (4'-aminophenyl) 1, 3-diamino propanol, 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-methyl-aminophenyl) tetramethylenediamine, N.N'-bis- (ethyl) N, N ' -bis- (4'-amino, 3'-methylphenyl) ethylenediamine, 1,8-bis- (2,5-diamino phenoxy) -3,6-dioxaoctane, and their addition salts with an acid.
Parmi les para-aminophénols, on peut citer à titre d'exemple, le para- aminophénol, le 4-amino 3-méthyl phénol, le 4-amino 3-fluoro phénol, le 4-amino 3- hydroxyméthyl phénol, le 4-amino 2-méthyl phénol, le 4-amino 2-hydroxyméthyl phénol, le 4-amino 2-méthoxyméthyl phénol, le 4-amino 2-aminométhyl phénol, le 4- amino 2-(β-hydroxyéthyl aminométhyl) phénol, le 4-amino 2-fluoro phénol, et leurs sels d'addition avec un acide.Among the para-aminophenols, there may be mentioned by way of example, para-aminophenol, 4-amino 3-methyl phenol, 4-amino 3-fluoro phenol, 4-amino 3-hydroxymethyl phenol, 4- amino 2-methyl phenol, 4-amino 2-hydroxymethyl phenol, 4-amino 2-methoxymethyl phenol, 4-amino 2-aminomethyl phenol, 4- amino 2- (β-hydroxyethyl aminomethyl) phenol, 4- amino 2-fluoro phenol, and their addition salts with an acid.
Parmi les ortho-aminophénols, on peut citer à titre d'exemple, le 2-amino phénol, le 2-amino 5-méthyl phénol, le 2-amino 6-méthyl phénol, le 5-acétamido 2-amino phénol, et leurs sels d'addition avec un acide.Among the ortho-aminophenols, there may be mentioned by way of example, 2-amino phenol, 2-amino 5-methyl phenol, 2-amino 6-methyl phenol, 5-acetamido 2-amino phenol, and their addition salts with an acid.
Parmi les bases hétérocycliques, on peut citer à titre d'exemple, les dérivés pyridiniques, les dérivés pyrimidiniques et les dérivés pyrazoliques.Among the heterocyclic bases that may be mentioned, for example, pyridine derivatives, pyrimidine derivatives and pyrazole derivatives.
Parmi les dérivés pyridiniques, on peut citer les composés décrits par exemple dans les brevets GB 1 026 978 et GB 1 153 196, comme la 2,5-diamino pyridine, la 2-(4-méthoxyphényl)amino 3-amino pyridine, la 2,3-diamino 6-méthoxy pyridine, la 2-(β-méthoxyéthyl)amino 3-amino 6-méthoxy pyridine, la 3,4-diamino pyridine, et leurs sels d'addition avec un acide. Parmi les dérivés pyrimidiniques, on peut citer les composés décrits par exemple dans les brevets DE 2 359 399 ; JP 88-169 571 ; JP 05 163 124 ; EP 0 770 375 ou demande de brevet WO 96/15765 comme la 2,4,5,6-tétra-aminopyrimidine, la 4-hydroxy 2,5,6-triaminopyrimidine, la 2-hydroxy 4,5,6-triaminopyrimidine, la 2,4-dihydroxy 5,6-diaminopyrimidine, la 2,5,6-triaminopyrimidine, et les dérivés pyrazolo-pyrimidiniques tels ceux mentionnés dans la demande de brevet FR-A-2 750 048 et parmi lesquels on peut citer la pyrazolo-[1,5-a]-pyrimidine-3,7-diamine ; la 2,5- diméthyl pyrazolo-[1 ,5-a]-pyrimidine-3,7-diamine ; la pyrazolo-[1 ,5-a]-pyrimidine-3,5- diamine ; la 2,7-diméthyl pyrazolo-[1 ,5-a]-pyrimidine-3,5-diamine ; le 3-amino pyrazolo- [1 ,5-a]-pyrimidin-7-ol ; le 3-amino pyrazolo-[1 ,5-a]-pyrimidin-5-ol ; le 2-(3-amino pyrazolo-[1 ,5-a]-pyrimidin-7-ylamino)-éthanol, le 2-(7-amino pyrazolo-[1 ,5-a]-pyrimidin- 3-ylamino)-éthanol, le 2-[(3-amino-pyrazolo[1 ,5-a]pyrimidin-7-yl)-(2-hydroxy-éthyl)- amino]-éthanol, le 2-[(7-amino-pyrazolo[1 ,5-a]pyrimidin-3-yl)-(2-hydroxy-éthyl)-amino]- éthanol, la 5,6-diméthyl pyrazolo-[1,5-a]-pyrimidine-3,7-diamine, la 2,6-diméthyl pyrazolo-[1 ,5-a]-pyrimidine-3,7-diamine, la 2, 5, N 7, N 7-tetraméthyl pyrazolo-[1 ,5-a]- pyrimidine-3,7-diamine, la 3-amino-5-méthyl-7-imidazolylpropylamino pyrazolo-[1 ,5-a]- pyrimidine et leurs sels d'addition avec un acide et leurs formes tautomères, lorsqu'il existe un équilibre tautomérique.Among the pyridine derivatives, mention may be made of the compounds described for example in 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, 3,4-diamino pyridine, and their addition salts with an acid. Among the pyrimidine derivatives, mention may be made of the compounds described for example in patents DE 2,359,399; JP 88-169,571; JP 05 163 124; EP 0 770 375 or patent application WO 96/15765 such as 2,4,5,6-tetra-aminopyrimidine, 4-hydroxy 2,5,6-triaminopyrimidine, 2-hydroxy 4,5,6-triaminopyrimidine, 2,4-dihydroxy 5,6-diaminopyrimidine, 2,5,6-triaminopyrimidine, and pyrazolo-pyrimidine derivatives such as those mentioned in patent application FR-A-2 750 048 and among which may be mentioned 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-amino pyrazolo- [1,5-a] -pyrimidin-7-ol; 3-amino pyrazolo- [1,5-a] -pyrimidin-5-ol; 2- (3-amino pyrazolo- [1,5-a] -pyrimidin-7-ylamino) ethanol, 2- (7-amino pyrazolo- [1,5-a] -pyrimidin-3-ylamino) - ethanol, 2 - [(3-amino-pyrazolo [1, 5-a] pyrimidin-7-yl) - (2-hydroxy-ethyl) - amino] -ethanol, 2 - [(7-amino-pyrazolo [ 1, 5-a] pyrimidin-3-yl) - (2-hydroxy-ethyl) -amino] - ethanol, 5,6-dimethyl pyrazolo- [1,5-a] -pyrimidine-3,7-diamine, 2,6-dimethyl pyrazolo- [1,5-a] -pyrimidine-3,7-diamine, 2,5,5 N 7, N 7-tetramethyl pyrazolo- [1,5-a] - pyrimidine-3, 7-diamine, 3-amino-5-methyl-7-imidazolylpropylamino pyrazolo- [1, 5-a] - pyrimidine and their addition salts with an acid and their tautomeric forms, when there is a tautomeric equilibrium.
Parmi les dérivés pyrazoliques, on peut citer les composés décrits dans les brevets DE 3 843 892, DE 4 133 957 et demandes de brevet WO 94/08969, WO 94/08970, FR-A-2 733 749 et DE 195 43 988 comme le 4,5-diamino 1-méthyl pyrazole, le 4,5-diamino l-(β-hydroxyéthyl) pyrazole, le 3,4-diamino pyrazole, le 4,5- diamino 1-(4'-chlorobenzyl) pyrazole, le 4,5-diamino 1,3-diméthyl pyrazole, le 4,5-diamino 3-méthyl 1-phényl pyrazole, le 4,5-diamino 1-méthyl 3-phényl pyrazole, le 4-amino 1 ,3-diméthyl 5-hydrazino pyrazole, le 1-benzyl 4,5-diamino 3-méthyl pyrazole, le 4,5-diamino 3-tert-butyl 1-méthyl pyrazole, le 4,5-diamino 1-tert-butyl 3-méthyl pyrazole, le 4,5-diamino l-(β-hydroxyéthyl) 3-méthyl pyrazole, le 4,5-diamino 1-éthyl 3- méthyl pyrazole, le 4,5-diamino 1-éthyl 3-(4'-méthoxyphényl) pyrazole, le 4,5-diamino 1-éthyl 3-hydroxyméthyl pyrazole, le 4,5-diamino 3-hydroxyméthyl 1-méthyl pyrazole, le 4,5-diamino 3-hydroxyméthyl 1-isopropyl pyrazole, le 4,5-diamino 3-méthyl 1-isopropyl pyrazole, le 4-amino 5-(2'-aminoéthyl)amino 1 ,3-diméthyl pyrazole, le 3,4,5-triamino pyrazole, le 1-méthyl 3,4,5-triamino pyrazole, le 3,5-diamino 1-méthyl 4- méthylamino pyrazole, le 3,5-diamino 4-(β-hydroxyéthyl)amino 1-méthyl pyrazole, et leurs sels d'addition avec un acide.Among the pyrazole derivatives, mention may be made of the compounds described in patents DE 3 843 892, DE 4 133 957 and patent applications WO 94/08969, WO 94/08970, FR-A-2 733 749 and DE 195 43 988 as 4,5-diamino 1-methyl pyrazole, 4,5-diamino l- (β-hydroxyethyl) pyrazole, 3,4-diamino pyrazole, 4,5-diamino 1- (4'-chlorobenzyl) pyrazole, 4,5-diamino 1,3-dimethyl pyrazole, 4,5-diamino 3-methyl 1-phenyl pyrazole, 4,5-diamino 1-methyl 3-phenyl pyrazole, 4-amino 1, 3-dimethyl 5-hydrazino pyrazole, 1-benzyl 4,5-diamino 3-methyl pyrazole, 4,5-diamino 3-tert-butyl 1-methyl pyrazole, 4,5-diamino 1-tert-butyl 3-methyl pyrazole , 4,5-diamino l- (β-hydroxyethyl) 3-methyl pyrazole, 4,5-diamino 1-ethyl 3- methyl pyrazole, 4,5-diamino 1-ethyl 3- (4'-methoxyphenyl) pyrazole, 4,5-diamino 1-ethyl 3-hydroxymethyl pyrazole, 4,5-diamino 3-hydroxymethyl 1-methyl pyrazole, 4,5-diamino 3-hydroxymethyl 1-isopropyl pyrazole, 4,5-diamino 3-methyl 1-isopropyl pyrazole, 4-amino 5- (2'-aminoethyl) amino 1, 3-dimethyl pyrazole, 3,4,5-triamino pyrazole, 1-methyl 3,4,5-triamino pyrazole , 3,5-diamino 1-methyl 4- methylamino pyrazole, 3,5-diamino 4- (β-hydroxyethyl) amino 1-methyl pyrazole, and their addition salts with an acid.
La composition selon l'invention peut contenir de plus un ou plusieurs coupleurs conventionnellement utilisés pour la teinture de fibres kératiniques. Parmi ces coupleurs, on peut notamment citer les métaphénylènediamines, les métaaminophénols, les metadiphenols, les coupleurs naphtaléniques et les coupleurs hétérocycliques.The composition according to the invention may also contain one or more couplers conventionally used for dyeing keratin fibers. Among these couplers, mention may in particular be made of metaphenylenediamines, metaaminophenols, metadiphenols, naphthalene couplers and heterocyclic couplers.
A titre d'exemple, on peut citer le 2-méthyl 5-aminophénol, le 5-N-(β- hydroxyéthyl)amino 2-méthyl phénol, le 6-chloro-2-méthyl-5-aminophénol, le 3-amino phénol, le 1 ,3-dihydroxy benzène, le 1 ,3-dihydroxy 2-méthyl benzène, le 4-chloro 1 ,3- dihydroxy benzène, le 2,4-diamino l-(β-hydroxyéthyloxy) benzène, le 2-amino 4-(β- hydroxyéthylamino) 1-méthoxybenzène, le 1,3-diamino benzène, le 1 ,3-bis-(2,4- diaminophénoxy) propane, la 3-uréido aniline, le 3-uréido 1 -dimethylamino benzène, le sésamol, le 1-β-hydroxyéthylamino-3,4-méthylènedioxybenzène, l'α-naphtol, le 2 méthyl-1-naphtol, le 6-hydroxy indole, le 4-hydroxy indole, le 4-hydroxy N-méthyl indole, la 2-amino-3-hydroxy pyridine, la 6- hydroxy benzomorpholine la 3,5-diamino- 2,6-diméthoxypyridine, le 1-N-(β-hydroxyéthyl)amino-3,4-méthylène dioxybenzène, le 2,6-bis-(β-hydroxyéthylamino)toluène et leurs sels d'addition avec un acide.By way of example, mention may be made of 2-methyl 5-aminophenol, 5-N- (β-hydroxyethyl) amino 2-methyl phenol, 6-chloro-2-methyl-5-aminophenol, 3-amino phenol, 1,3-dihydroxy benzene, 1,3-dihydroxy 2-methyl benzene, 4-chloro 1,3-dihydroxy benzene, 2,4-diamino l- (β-hydroxyethyloxy) benzene, 2- amino 4- (β- hydroxyethylamino) 1-methoxybenzene, 1,3-diamino benzene, 1, 3-bis- (2,4-diaminophenoxy) propane, 3-ureido aniline, 3-ureido 1 -dimethylamino benzene , sesamol, 1-β-hydroxyethylamino-3,4-methylenedioxybenzene, α-naphthol, 2 methyl-1-naphtol, 6-hydroxy indole, 4-hydroxy indole, 4-hydroxy N-methyl indole, 2-amino-3-hydroxy pyridine, 6-hydroxy benzomorpholine 3,5-diamino-2,6-dimethoxypyridine, 1-N- (β-hydroxyethyl) amino-3,4-methylene dioxybenzene, 2,6-bis- (β-hydroxyethylamino) toluene and their addition salts with an acid.
Dans la composition de la présente invention, le ou les coupleurs sont en général présents en quantité comprise entre 0,001 et 10 % en poids environ du poids total de la composition tinctoriale et plus préférentiellement de 0,005 à 6 %. La ou les bases d'oxydation sont présentes en quantité de préférence comprise entre 0,001 à 10 % en poids environ du poids total de la composition tinctoriale, et plus préférentiellement de 0,005 à 6 %. D'une manière générale, les sels d'addition avec un acide utilisables dans le cadre des compositions tinctoriales de l'invention pour les bases d'oxydation et les coupleurs sont notamment choisis parmi les chlorhydrates, les bromhydrates, les sulfates, les citrates, les succinates, les tartrates, les lactates, les tosylates, les benzènesulfonates, les phosphates et les acétates. La composition tinctoriale conforme à l'invention peut en outre contenir des colorants directs différents de ceux de formule (I), ces colorants pouvant notamment être choisis parmi les colorants nitrés de la série benzénique, les colorants directs cationiques, les colorants directs azoïques, les colorants directs méthiniques.In the composition of the present invention, the coupler (s) are generally present in an amount between 0.001 and 10% by weight approximately of the total weight of the dye composition and more preferably from 0.005 to 6%. The oxidation base (s) are present in an amount preferably between 0.001 to 10% by weight approximately of the total weight of the dye composition, and more preferably from 0.005 to 6%. In general, the addition salts with an acid which can be used in the context of the dye compositions of the invention for the oxidation bases and the couplers are in particular chosen from hydrochlorides, hydrobromides, sulfates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates. The dye composition in accordance with the invention may also contain direct dyes different from those of formula (I), these dyes being able in particular be chosen from nitro dyes of the benzene series, cationic direct dyes, azo direct dyes, methinic direct dyes.
Le milieu approprié pour la teinture appelé aussi support de teinture est généralement constitué par de l'eau ou par un mélange d'eau et d'au moins un solvant organique pour solubiliser les composés qui ne seraient pas suffisamment solubles dans l'eau. A titre de solvant organique, on peut par exemple citer les alcanols inférieurs en d-C4, tels que l'éthanol et l'isopropanol ; les polyols et éthers de polyols comme le 2-butoxyéthanol, le propylèneglycol, le monométhyléther de propylèneglycol, le monoéthyléther et le monométhyléther du diéthylèneglycol, ainsi que les alcools aromatiques comme l'alcool benzylique ou le phénoxyéthanol, et leurs mélanges.The medium suitable for dyeing, also called dye support, generally consists of water or of a mixture of water and at least one organic solvent to dissolve the compounds which are not sufficiently soluble in water. As organic solvent, mention may, for example, be made of lower alkanols at dC 4 , such as ethanol and isopropanol; polyols and polyol ethers such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, monoethyl ether and diethylene glycol monomethyl ether, as well as aromatic alcohols such as benzyl alcohol or phenoxyethanol, and mixtures thereof.
Les solvants peuvent être présents dans des proportions de préférence comprises entre 1 et 40 % en poids environ par rapport au poids total de la composition tinctoriale, et encore plus préférentiellement entre 5 et 30 % en poids environ.The solvents may be present in proportions preferably of between 1 and 40% by weight approximately relative to the total weight of the dye composition, and even more preferably between 5 and 30% by weight approximately.
La composition tinctoriale conforme à l'invention peut également renfermer divers adjuvants utilisés classiquement dans les compositions pour la teinture des cheveux, tels que des agents tensio-actifs anioniques, cationiques, non-ioniques, amphotères, zwittérioniques ou leurs mélanges, des polymères anioniques, cationiques, non-ioniques, amphotères, zwittérioniques ou leurs mélanges, des agents épaississants minéraux ou organiques, et en particulier les épaississants associatifs polymères anioniques, cationiques, non ioniques et amphotères, des agents antioxydants, des agents de pénétration, des agents séquestrants, des parfums, des tampons, des agents dispersants, des agents de conditionnement tels que par exemple des silicones volatiles ou non volatiles, modifiées ou non modifiées, des agents filmogènes, des céramides, des agents conservateurs, des agents opacifiants. Ces adjuvants ci dessus sont en général présents en quantité comprise pour chacun d'eux entre 0,01 et 20 % en poids par rapport au poids de la composition.The dye composition in accordance with the invention may also contain various adjuvants conventionally used in compositions for dyeing the hair, such as anionic, cationic, nonionic, amphoteric, zwitterionic surfactants or mixtures thereof, anionic polymers, cationic, nonionic, amphoteric, zwitterionic or mixtures thereof, mineral or organic thickening agents, and in particular associative thickeners anionic, cationic, nonionic and amphoteric, antioxidant agents, penetration agents, sequestering agents, perfumes, buffers, dispersing agents, conditioning agents such as for example volatile or non-volatile silicones, modified or unmodified, film-forming agents, ceramides, preserving agents, opacifying agents. These above adjuvants are generally present in an amount for each of them of between 0.01 and 20% by weight relative to the weight of the composition.
Bien entendu, l'homme de l'art veillera à choisir ce ou ces éventuels composés complémentaires de manière telle que les propriétés avantageuses attachées intrinsèquement à la composition de teinture d'oxydation conforme à l'invention ne soient pas, ou substantiellement pas, altérées par la ou les adjonctions envisagées. Le pH de la composition tinctoriale conforme à l'invention est généralement compris entre 3 et 12 environ, et de préférence entre 5 et 11 environ. Il peut être ajusté à la valeur désirée au moyen d'agents acidifiants ou alcalinisants habituellement utilisés en teinture des fibres kératiniques ou bien encore à l'aide de systèmes tampons classiques.Of course, those skilled in the art will take care to choose this or these optional additional compounds in such a way that the advantageous properties intrinsically attached to the oxidation dye composition according to the invention are not, or not substantially, altered. by the addition (s) envisaged. The pH of the dye composition according to the invention is generally between 3 and 12 approximately, and preferably between 5 and 11 approximately. It can be adjusted to the desired value by means of acidifying or basifying agents usually used in dyeing keratin fibers or even using conventional buffer systems.
Parmi les agents acidifiants, on peut citer, à titre d'exemple, les acides minéraux ou organiques comme l'acide chlorhydrique, l'acide orthophosphorique, l'acide sulfurique, les acides carboxyliques comme l'acide acétique, l'acide tartrique, l'acide citrique, l'acide lactique, les acides sulfoniques. Parmi les agents alcalinisants on peut citer, à titre d'exemple, l'ammoniaque, les carbonates alcalins, les alcanolamines telles que les mono-, di- et triéthanolamines ainsi que leurs dérivés, les hydroxydes de sodium ou de potassium et les composés de formule (III) suivante :Among the acidifying agents, there may be mentioned, by way of example, mineral or organic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid, lactic acid, sulfonic acids. Among the basifying agents, there may be mentioned, by way of example, ammonia, alkali carbonates, alkanolamines such as mono-, di- and triethanolamines as well as their derivatives, sodium or potassium hydroxides and compounds of formula (III) below:
Ra χ RbRa χ Rb
N wA (IH)N wA (IH)
/ ^/ ^
Rc Rd dans laquelle W est un reste propylene éventuellement substitué par un groupement hydroxyle ou un radical alkyle en d-C4 ; Ra, Rb, Rc et Rd, identiques ou différents, représentent un atome d'hydrogène, un radical alkyle en d-C4 ou hydroxyalkyle en Cr .Rc Rd in which W is a propylene residue optionally substituted by a hydroxyl group or a dC 4 alkyl radical; R a, R b, R c and R d, identical or different, represent a hydrogen atom, an alkyl radical -C 4 hydroxyalkyl Cr.
La composition tinctoriale selon l'invention peut se présenter sous des formes diverses, telles que sous forme de liquides, de crèmes, de gels, ou sous toute autre forme appropriée pour réaliser une teinture des fibres kératiniques, et notamment des cheveux humains.The dye composition according to the invention can be in various forms, such as in the form of liquids, creams, gels, or in any other form suitable for dyeing keratin fibers, and in particular human hair.
L'invention a aussi pour objet un procédé de teinture directe qui comprend l'application d'une composition tinctoriale contenant un colorant de formule (I) telle que définie précédemment sur les fibres kératiniques. Après un temps de pause, les fibres kératiniques sont rincées laissant apparaître des fibres colorées.The invention also relates to a direct dyeing process which comprises the application of a dye composition containing a dye of formula (I) as defined above on keratin fibers. After a pause, the keratin fibers are rinsed leaving colored fibers to appear.
L'application sur les fibres de la composition tinctoriale contenant le colorant cationique azoïque de formule (I) ou (II) peut être mise en œuvre en présence d'agent oxydant ce qui provoque la décoloration de la fibre. Cet agent oxydant peut être ajouté à la composition contenant le colorant cationique azoïque au moment de l'emploi ou directement sur la fibre keratinique. Selon un mode de réalisation particulier, la composition contenant le colorant cationique azoïque de formule (I) est exempte de base d'oxydation et de coupleur.The application to the fibers of the dye composition containing the azo cationic dye of formula (I) or (II) can be implemented in the presence of an oxidizing agent which causes discoloration of the fiber. This oxidizing agent can be added to the composition containing the cationic azo dye at the time of use or directly on the keratin fiber. According to a particular embodiment, the composition containing the azo cationic dye of formula (I) is free from oxidation base and from coupler.
L'invention a aussi pour objet un procédé de teinture d'oxydation permanente qui comprend l'application sur les fibres d'une composition tinctoriale qui comprend un colorant de formule (I), au moins une base d'oxydation et optionnellement au moins un coupleur, en présence d'un agent oxydant.The invention also relates to a process for permanent oxidation dyeing which comprises applying to the fibers a dye composition which comprises a dye of formula (I), at least one oxidation base and optionally at least one coupler, in the presence of an oxidizing agent.
La base d'oxydation, le coupleur et l'agent oxydant sont tels que définis précédemment. Dans le cadre de la teinture d'oxydation permanente, il est aussi possible d'utiliser comme agent oxydant des enzymes parmi lesquelles on peut citer les peroxydases, les oxydo-réductases à 2 électrons telles que les uricases et les oxygénases à 4 électrons comme les laccases.The oxidation base, the coupler and the oxidizing agent are as defined above. In the context of the permanent oxidation dye, it is also possible to use as oxidizing agent enzymes among which there may be mentioned peroxidases, 2-electron oxidoreductases such as uricases and 4-electron oxygenases such as laccases.
La couleur peut être révélée à pH acide, neutre ou alcalin et l'agent oxydant peut être ajouté à la composition de l'invention juste au moment de l'emploi ou il peut être mis en œuvre à partir d'une composition oxydante le contenant, appliquée sur les fibres simultanément ou séquentiellement à la composition tinctoriale.The color can be revealed at acidic, neutral or alkaline pH and the oxidizing agent can be added to the composition of the invention just at the time of use or it can be used from an oxidizing composition containing it , applied to the fibers simultaneously or sequentially to the dye composition.
Dans le cas de la teinture d'oxydation permanente ou de la teinture directe, la composition tinctoriale est mélangée, de préférence au moment de l'emploi, à une composition contenant, dans un milieu approprié pour la teinture, au moins un agent oxydant, cet agent oxydant étant présent en une quantité suffisante pour développer une coloration. Le mélange obtenu est ensuite appliqué sur les fibres kératiniques. Après un temps de pause de 3 à 50 minutes environ, de préférence 5 à 30 minutes environ, les fibres kératiniques sont rincées, lavées au shampooing, rincées à nouveau puis séchées.In the case of permanent oxidation dyeing or direct dyeing, the dye composition is mixed, preferably at the time of use, with a composition containing, in a medium suitable for dyeing, at least one oxidizing agent, this oxidizing agent being present in an amount sufficient to develop a coloration. The mixture obtained is then applied to the keratin fibers. After a pause time of approximately 3 to 50 minutes, preferably approximately 5 to 30 minutes, the keratin fibers are rinsed, washed with shampoo, rinsed again and then dried.
La composition oxydante peut également renfermer divers adjuvants utilisés classiquement dans les compositions pour la teinture des cheveux et tels que définis précédemment.The oxidizing composition may also contain various adjuvants conventionally used in compositions for dyeing the hair and as defined above.
Le pH de la composition oxydante renfermant l'agent oxydant est tel qu'après mélange avec la composition tinctoriale, le pH de la composition résultante appliquée sur les fibres kératiniques varie de préférence entre 3 et 12 environ, et encore plus préférentiellement entre 5 et 11. Il peut être ajusté à la valeur désirée au moyen d'agents acidifiants ou alcalinisants habituellement utilisés en teinture des fibres kératiniques et tels que définis précédemment.The pH of the oxidizing composition containing the oxidizing agent is such that after mixing with the dye composition, the pH of the resulting composition applied to the keratin fibers preferably varies between 3 and 12 approximately, and even more preferably between 5 and 11 It can be adjusted to the desired value at means of acidifying or basifying agents usually used in dyeing keratin fibers and as defined above.
La composition qui est finalement appliquée sur les fibres kératiniques peut se présenter sous des formes diverses, telles que sous forme de liquides, de crèmes, de gels ou sous toute autre forme appropriée pour réaliser une teinture des fibres kératiniques, et notamment des cheveux humains.The composition which is finally applied to the keratin fibers can be in various forms, such as in the form of liquids, creams, gels or in any other form suitable for dyeing keratin fibers, and in particular human hair.
Un autre objet de l'invention est un dispositif à plusieurs compartiments ou "kit" de teinture dans lequel un premier compartiment renferme la composition tinctoriale de l'invention et un deuxième compartiment renferme la composition oxydante. Ce dispositif peut être équipé d'un moyen permettant de délivrer sur les cheveux le mélange souhaité, tel que les dispositifs décrits dans le brevet FR-2 586 913 au nom de la demanderesse.Another object of the invention is a device with several compartments or "kit" for dyeing in which a first compartment contains the dye composition of the invention and a second compartment contains the oxidizing composition. This device can be equipped with a means enabling the desired mixture to be delivered to the hair, such as the devices described in patent FR-2,586,913 in the name of the applicant.
Enfin l'invention a également pour objet les colorants azoïques cationiques de formule (I) ou (II) telle que définie précédemment dans lesquels R8 est l'hydrogène. Ces composés peuvent être obtenus à partir des procédés de préparation décrits par exemple dans les documents EP 810824, GB 9619573, RO 106572, J.Chem. Res.., Synop. (1998), (10), 648-649, DE 19721619, US 5852179, Synth. Commun 1999, 29(13), 2271-2276, Org. Lett., 2001 , 3, 2583, Org. Lett. 2001 , 3, 2757J. Chem. Soc, Perkin Trans. 1 , 1998, 2615-2622 et références issues de ces publications. En particulier, les composés de formule (II) peuvent être obtenus de la façon suivante :Finally, the subject of the invention is also the cationic azo dyes of formula (I) or (II) as defined above in which R 8 is hydrogen. These compounds can be obtained from the preparation methods described for example in documents EP 810824, GB 9619573, RO 106572, J. Chem. Res .., Synop. (1998), (10), 648-649, DE 19721619, US 5852179, Synth. Commun 1999, 29 (13), 2271-2276, Org. Lett., 2001, 3, 2583, Org. Lett. 2001, 3, 2757J. Chem. Soc, Perkin Trans. 1, 1998, 2615-2622 and references from these publications. In particular, the compounds of formula (II) can be obtained in the following way:
Voie 1 :Track 1:
44
D'une façon générale, le composé 1 est dans une première étape réduit en composé 2 en présence d'hydrogène sous pression et de palladium. Ce composé réagit par la suite en présence de nitrite de sodium pour fournir un sel de diazonium qui peut être condensé sur l'imidazole et ainsi fournir le composé 3. La double cationisation s'effectue en présence de dimethylsulfate dans l'acétate d'éthyle pour fournir le composé 4. Voie 2 :In general, compound 1 is in a first step reduced to compound 2 in the presence of hydrogen under pressure and of palladium. This compound subsequently reacts in the presence of sodium nitrite to provide a diazonium salt which can be condensed on imidazole and thus provide compound 3. The double cationization takes place in the presence of dimethylsulfate in ethyl acetate to provide compound 4. Track 2:
D'une façon générale, le composé 1 choisit de façon adéquate pourra réagir avec un 5 système hétéroaromatique à 5 chaînons tel que défini dans les revendications (ici un imidazole) en présence de base à reflux. Une alternative peut être proposé en utilisant un catalyseur au cuivre, une base, et un ligand, le 1 ,2-diaminocyclohexane à reflux. Le composé 3 est obtenu par réduction du composé 2 en utilisant du palladium sous pression d'hydrogène. Le composé 3 réagit par la suite en présence de nitrite de 0 sodium pour fournir un sel de diazonium qui peut être condensé sur l'imidazole et ainsi fournir le composé 4. La double cationisation s'effectue en présence de dimethylsulfate dans l'acétate d'éthyle pour fournir le composé 5.Generally, the compound 1 suitably chosen will be able to react with a 5-membered heteroaromatic system as defined in the claims (here an imidazole) in the presence of base at reflux. An alternative can be proposed using a copper catalyst, a base, and a ligand, 1,2-diaminocyclohexane at reflux. Compound 3 is obtained by reduction of Compound 2 using palladium under hydrogen pressure. Compound 3 subsequently reacts in the presence of sodium nitrite to provide a diazonium salt which can be condensed on imidazole and thus provide compound 4. The double cationization takes place in the presence of dimethylsulfate in acetate d ethyl to provide compound 5.
Les exemples qui suivent servent à illustrer l'invention sans toutefois 5 présenter un caractère limitatif. The examples which follow serve to illustrate the invention without, however, being limiting in nature.
EXEMPLES DE SYNTHESEEXAMPLES OF SYNTHESIS
Exemple n°1 : préparation d'un composé de formuleExample 1: Preparation of a compound of formula
(1) (2)(1) (2)
2 HCOO-2 HCOO-
, Dans un ballon tout équipé on charge 0,05 g de composé (1), 0,04 g de composé (2), 0,3 ml de triéthylamine et 0.8 ml de DMF sec. Le mélange est laissé à température ambiante pendant 1 heure puis porté à 45°C. Le mélange reactionnel est ensuite filtré sur bϋchner. Le précipité est lavé avec quelques gouttes d'éthanol. Un volume V d'acétate d'éthyle est alors ajouté à la solution filtrée. Un nouveau précipité est formé puis filtré sur bϋchner. Celui-ci est alors séché sous vide. Après purification, une poudre de couleur rouge très foncée brillante est obtenue. On obtient ainsi un colorant donnant une teinture fushia, 0.05 g of compound (1), 0.04 g of compound (2), 0.3 ml of triethylamine and 0.8 ml of dry DMF are loaded into a fully equipped flask. The mixture is left at room temperature for 1 hour and then brought to 45 ° C. The reaction mixture is then filtered through a bϋchner. The precipitate is washed with a few drops of ethanol. A volume V of ethyl acetate is then added to the filtered solution. A new precipitate is formed and then filtered through bϋchner. This is then dried under vacuum. After purification, a very dark shiny red powder is obtained. This gives a dye giving a fuchsia dye
Les caractéristiques en absorption UV de ce produit sont les suivantes : UV (acétonitrile-eau 50/50) λmax = 513 nmThe UV absorption characteristics of this product are as follows: UV (acetonitrile-water 50/50) λ max = 513 nm
Analyses :Analyzes :
RMN 1H : (400MHz-DMSO) ppm :1H NMR: (400MHz-DMSO) ppm:
3.99 (s-3H ) ; 4.02 (s-3H ) ; 4.11(s-3H) ; 7.24(d-2H, J = 9.13 Hz) ;7.30 (m-3H) ; 7.45 (d-3.99 (s-3H); 4.02 (s-3H); 4.11 (s-3H); 7.24 (d-2H, J = 9.13 Hz); 7.30 (m-3H); 7.45 (d-
2H, J = 9.75 Hz) ; 7.63 (s-2H) ; 8.05 (d-2H, J = 12 Hz) Exemple n°2 : préparation d'un composé de formule2H, J = 9.75 Hz); 7.63 (s-2H); 8.05 (d-2H, J = 12 Hz) Example 2: Preparation of a compound of formula
(1) (3)(1) (3)
2 HCOO-2 HCOO-
Dans un ballon tout équipé on charge 0,05 g de composé (1), 0,037 g de composé (3), 0,3 ml de triéthylamine et 0,8 ml de DMF sec. Le mélange est laissé à température ambiante pendant 1 heure puis porté à 45°C. Le mélange reactionnel est ensuite filtré sur bϋchner. Le précipité est lavé avec quelques gouttes d'éthanol. Un volume V d'acétate d'éthyle est alors ajouté à la solution filtrée. Un nouveau précipité est formé puis filtré sur bϋchner. Celui-ci est alors séché sous vide. Après purification, une poudre de couleur rouge très foncée brillante est obtenue.0.05 g of compound (1), 0.037 g of compound (3), 0.3 ml of triethylamine and 0.8 ml of dry DMF are loaded into a fully equipped flask. The mixture is left at room temperature for 1 hour and then brought to 45 ° C. The reaction mixture is then filtered through a bϋchner. The precipitate is washed with a few drops of ethanol. A volume V of ethyl acetate is then added to the filtered solution. A new precipitate is formed and then filtered through bϋchner. This is then dried under vacuum. After purification, a very dark shiny red powder is obtained.
Les caractéristiques en absorption UV de ce produit sont les suivantes UV (acétonitrile-eau 50/50) λmax = 516 nmThe UV absorption characteristics of this product are as follows UV (acetonitrile-water 50/50) λ max = 516 nm
Analyses :Analyzes :
Masse ESI+ : m/z = 398[M +] m/z = 200[M272 + H]ESI + mass: m / z = 398 [M + ] m / z = 200 [M 2 72 + H]
RMN 1 H : (400MHz-DMSO) ppm :1 H NMR: (400MHz-DMSO) ppm:
4.01 (s-6H) ; 7.09 (m-1H) ; 7.30(m-1H) ; 7.44 (m-5H) ; 7.74 (s-2H) ; 8 (m-4H) ; 8.36 (m- 1H) ; 10.14 (s-2H). On obtient ainsi un colorant donnant une teinture fushia.4.01 (s-6H); 7.09 (m-1H); 7.30 (m-1H); 7.44 (m-5H); 7.74 (s-2H); 8 (m-4H); 8.36 (m- 1H); 10.14 (s-2H). A dye is thus obtained giving a fuchsia dye.
EXEMPLES DE TEINTUREDYEING EXAMPLES
On a préparé les compositions tinctoriales suivantes (teneurs en mole):The following dye compositions were prepared (mole contents):
Au moment de l'emploi, chaque composition est mélangée avec un poids égal d'eau oxygénée à 20 volumes (6% en poids). Chaque mélange obtenu est appliqué sur des mèches de cheveux gris à 90At the time of use, each composition is mixed with an equal weight of hydrogen peroxide at 20 volumes (6% by weight). Each mixture obtained is applied to locks of gray hair at 90
% de blancs, permanentes (BP) ou naturel (BN) (1 g de mèche pour 10 g de solution). Après 20 min de pose, les mèches sont rincées, lavées avec un shampooing standard, rincées à nouveau puis séchées.% of whites, permanent (BP) or natural (BN) (1 g of wick for 10 g of solution). After 20 min of laying, the locks are rinsed, washed with a standard shampoo, rinsed again and then dried.
Chaque mèche est évaluée avant et après la teinture dans le système L*a*b*, au moyen d'un spectrophotomètre CM 2002 MINOLTA ®, (Illuminant D65). Dans l'espace L*a*b*. la clarté est indiquée par la valeur L* sur une échelle de 0 à 100 alors que les coordonnées chromatiques sont exprimées par a* et b* qui indiquent deux axes de couleur, a* l'axe rouge-vert et b* l'axe jaune- bleu. Selon ce système, plus la valeur de L est élevée, plus la couleur est claire et peu intense. Inversement, plus la valeur de L est faible, plus la couleur est foncée ou très intense.Each lock is evaluated before and after dyeing in the L * a * b * system , using a CM 2002 MINOLTA® spectrophotometer (Illuminant D65). In the space L * a * b * . clarity is indicated by the value L * on a scale from 0 to 100 while the chromaticity coordinates are expressed by a * and b * which indicate two axes of color, a * the red-green axis and b * the axis yellow-blue. According to this system, the higher the value of L, the lighter and less intense the color. Conversely, the lower the value of L, the darker or very intense the color.
Les résultats de teinture suivants ont été obtenus. The following dye results were obtained.

Claims

REVENDICATIONS
1. Composition pour la teinture des fibres kératiniques et en particulier des fibres kératiniques humaines telles que les cheveux, comprenant au moins un colorant monoazoïque dicationique de formules (I) ou (II) suivantes :1. Composition for dyeing keratin fibers and in particular human keratin fibers such as the hair, comprising at least one dicationic monoazo dye of formulas (I) or (II) below:
Z1-N=N-A1-(A3)n -Z2 (I)Z 1 -N = NA 1 - (A 3 ) n -Z 2 (I)
ZrN=N-A2 (n)Z r N = NA 2 (n)
• formules dans lesquelles• formulas in which
• n est égal à 0 ou 1 ,• n is equal to 0 or 1,
• Z représente un radical hétéroaromatique cationique à 5 ou 6 chaînons de formules (III) ou (IV) :• Z represents a 5 or 6-membered cationic heteroaromatic radical of formulas (III) or (IV):
où - X représente NR3, S ou O, Z représente CR2 ou N et Y représente CR4 ou N avec les conditions suivantes : lorsque X est NR3 ou O et Z est CR2, alors Y est CR4 ou N, lorsque X est S alors Z est N ou Y est N lorsque X est S et Z est N alors et Y est CR4 - X, représente CR6 ou N, m est un nombre entier égal à 0,1 ,2 ou 3, where - X represents NR 3 , S or O, Z represents CR 2 or N and Y represents CR 4 or N with the following conditions: when X is NR 3 or O and Z is CR 2, then Y is CR 4 or N, when X is S then Z is N or Y is N when X is S and Z is N then and Y is CR 4 - X, represents CR 6 or N, m is an integer equal to 0.1, 2 or 3,
R1f R3 et R5 représentent indépendamment l'un de l'autre une chaîne hydrocarbonée en d-do. saturée ou insaturée ; linéaire ou ramifiée pouvant former un cycle carboné ayant de 5 à 7 chaînons, éventuellement aromatique ; un ou plusieurs atomes de carbone pouvant être remplacés par un atome d'oxygène, d'azote, d'halogènes, de soufre ou par un groupement SO , à l'exception du carbone relié à l'atome d'azote du cycle de formule (III) ou (IV) ; les radicaux R R3 ou R5 ne comportant pas de liaison peroxyde, ni de radicaux diazo, nitro ou nitroso ;R 1f R 3 and R 5 independently of one another represent a d-do hydrocarbon chain. saturated or unsaturated; linear or branched which can form a carbon ring having 5 to 7 links, possibly aromatic; one or more carbon atoms which can be replaced by an oxygen, nitrogen, halogen or sulfur atom or by an SO group, with the exception of the carbon linked to the nitrogen atom of the cycle of formula (III) or (IV); the RR 3 or R 5 radicals comprising no peroxide bond, nor diazo, nitro or nitroso radicals;
R2, R4 et R6 représentent indépendamment l'un de l'autre un atome d'hydrogène ; une chaîne hydrocarbonée en d-C10, saturée ou insaturée, linéaire ou ramifiée pouvant former un cycle carboné ayant de 5 à 7 chaînons, éventuellement aromatique ; un ou plusieurs atomes de carbone pouvant être remplacés par un ou plusieurs atomes d'oxygène, d'azote, de soufre, ou par un groupement SO2 ; les radicaux R2, R4 ou R6 ne comportant pas de liaison peroxyde, ni de radicaux diazo, nitro ou nitroso ; les radicaux R2 et R4 peuvent former ensemble un cycle aromatique carboné,R 2 , R 4 and R 6 independently of one another represent a hydrogen atom; a saturated or unsaturated, linear or branched dC 10 hydrocarbon chain which can form a carbon ring having from 5 to 7 members, optionally aromatic; one or more carbon atoms which can be replaced by one or more oxygen, nitrogen, sulfur atoms, or by an SO 2 group; the radicals R 2 , R 4 or R 6 not comprising a peroxide bond, nor of diazo, nitro or nitroso radicals; the radicals R 2 and R 4 can together form a carbon aromatic cycle,
- V représente un anion organique ou minéral,- V represents an organic or mineral anion,
• A! et A3 représentent, indépendamment l'un de l'autre, un radical divalent de formules (V) ou (VI)• A ! and A 3 represent, independently of one another, a divalent radical of formulas (V) or (VI)
dans lesquelles n' est un nombre entier égal à 0, 1 , 2 ou 3, n" est un nombre entier égal à 0 ou 1 , γι-Y2 représente C-N ou N-N, - lorsque n = 0, alors la liaison a du groupement de la formule (V) est relié à la fonction Z2 de la formule (I) ou, lorsque n = 0, alors la liaison 6' du groupement A de la formule (VI) est reliée à la fonction Z2 de la formule (I), lorsque n = 1 , alors la liaison a du groupement A, de la formule (V) est reliée au d du groupement A3 de formule (V), la liaison a du groupement A3 de formule in which n 'is an integer equal to 0, 1, 2 or 3, n "is an integer equal to 0 or 1, γ ι-Y 2 represents CN or NN, - when n = 0, then the bond has of the group of formula (V) is linked to the function Z 2 of formula (I) or, when n = 0, then the 6 ′ bond of group A of the formula (VI) is linked to the function Z 2 of formula (I), when n = 1, then the bond a of group A, of formula (V) is linked to the d of group A 3 of formula (V), the bond a of group A 3 of formula
(V) étant reliée à la fonction Z2 de la formule (I) ou, lorsque n = 1 , alors la liaison a du groupement A, de la formule (V) est reliée au carbone porteur de la liaison a' du groupement A3 de la formule (VI), la liaison b' étant reliée à la fonction Z2 de la formule (I), lorsque n = 1 , alors la liaison b' du groupement A^ de la formule (VI) est reliée au carbone d du groupement A3 de formule (V), la liaison a étant reliée à la fonction(V) being connected to the function Z 2 of the formula (I) or, when n = 1, then the bond a of the group A, of the formula (V) is linked to the carbon carrying the bond a 'of the group A 3 of the formula (VI), the bond b' being linked to the function Z 2 of formula (I), when n = 1, then the bond b 'of the group A ^ of the formula (VI) is linked to the carbon d of the group A 3 of formula (V), the bond a being connected to the function
Z2 de la formule (I) ou, lorsque n = 1 , alors la liaison b' du groupement A de la formule (VI) est reliée au carbone porteur de la liaison a' du groupement A3 de formule (VI), la liaison b' du groupement A3 de la formule (VI) étant reliée à la fonction Z2 de la formule (I), - R8 et R'8 représentent indépendamment l'un de l'autre un groupe non cationique choisi parmi un atome hydrogène, une chaîne hydrocarbonée en CrC10, linéaire ou ramifiée pouvant former un cycle carboné ayant de 5 à 7 chaînons, éventuellement aromatique ; un ou plusieurs atomes de carbone de la chaîne hydrocarbonée pouvant être remplacés par un ou plusieurs atomes d'oxygène, d'azote, de soufre, ou par un groupement SO2 à l'exception du carbone relié à l'atome d'azote ; les radicaux R8 ou R'8 ne comportant pas de liaison peroxyde, ni de radicaux diazo, nitro ou nitroso ;Z 2 of formula (I) or, when n = 1, then the bond b 'of group A of formula (VI) is linked to the carbon carrying the bond a' of group A 3 of formula (VI), the bond b 'of group A 3 of formula (VI) being linked to the function Z 2 of formula (I), - R 8 and R' 8 independently of one another represent a non-cationic group chosen from a hydrogen atom, a C r C 10 hydrocarbon chain, linear or branched, which may form a carbon ring having 5 to 7 members, optionally aromatic; one or more carbon atoms of the hydrocarbon chain which can be replaced by one or more oxygen, nitrogen, sulfur atoms, or by an SO 2 group with the exception of the carbon linked to the nitrogen atom; the radicals R 8 or R ′ 8 comprising no peroxide bond, nor of diazo, nitro or nitroso radicals;
R7, R9, R'7 et R'g représente indépendamment l'un de l'autre un groupe non cationique tel que défini pour R2 ou un groupe cationique Z3, à la condition qu'un seul des groupes R7, R9, R'7 et R'g est cationique, - R7 avec R„, respectivement R'7 avec R'8 peuvent former ensemble un hétérocycle à 5 ou 6 chaînons saturé,R 7 , R 9 , R ' 7 and R'g independently of one another represent a non-cationic group as defined for R 2 or a cationic group Z 3 , provided that only one of the groups R 7 , R 9 , R ' 7 and R' g is cationic, - R 7 with R „, respectively R ' 7 with R' 8 can together form a saturated 5- or 6-membered heterocycle,
Z3 est un groupe cationique représenté par la formule (VII) suivanteZ 3 is a cationic group represented by the following formula (VII)
— (B)n, D (VII) dans laquelle : - B représente une chaîne hydrocarbonée comportant de 1 à 15 atomes de carbone, linéaire ou ramifiée, pouvant former un ou plusieurs cycles comportant de 3 à 7 chaînons éventuellement aromatiques, et dont un ou plusieurs atomes de carbone peuvent être remplacés par un atome d'oxygène, d'azote, de soufre, ou par un radical SO2 à l'exception du carbone relié à l'atome d'azote ; B ne comportant pas de liaison peroxyde ni de radicaux diazo, nitro ou nitroso, -le radical B est relié à D par l'un quelconque des atomes du radical D, - n'" peut prendre la valeur 0 ou 1,- (B) n , D (VII) in which: - B represents a hydrocarbon chain comprising from 1 to 15 carbon atoms, linear or branched, which can form one or more rings comprising from 3 to 7 optionally aromatic links, and one of which or several carbon atoms can be replaced by an oxygen, nitrogen, sulfur atom, or by an SO 2 radical with the exception of the carbon linked to the nitrogen atom; B having no peroxide bond or diazo, nitro or nitroso radicals, the radical B is linked to D by any of the atoms of the radical D, - n '"can take the value 0 or 1,
- D est choisi parmi les groupes cationiques de formules (VIII) et (IX) suivantes :- D is chosen from the cationic groups of formulas (VIII) and (IX) below:
dans lesquelles : - p peut prendre la valeur 0 ou 1 ; in which: - p can take the value 0 or 1;
- T1f T2, T3 et T4, indépendamment les uns des autres, représentent un atome d'oxygène ; un atome de soufre ; un atome d'azote non substitué ou substitué par un radical R14 ; ou un atome de carbone non substitué ou substitué par un ou deux radicaux R14, identiques ou différents ; - T5 représente un atome d'azote ; ou un atome de carbone non substitué ou substitué par un radical R14 ;- T 1f T 2 , T 3 and T 4 , independently of each other, represent an oxygen atom; a sulfur atom; a nitrogen atom unsubstituted or substituted by a radical R 14 ; or a carbon atom unsubstituted or substituted by one or two radicals R 14 , identical or different; - T 5 represents a nitrogen atom; or a carbon atom unsubstituted or substituted by a radical R 14 ;
- T6 peut prendre les mêmes significations que celles indiquées ci-dessous pour le radical R14, étant entendu que T6 est différent d'un atome d'hydrogène ; - T, ou T5 peuvent, en outre, former avec T6 un cycle saturé ou insaturé comportant de 5 à 7 chaînons, chaque chaînon étant non substitué ou substitué par un ou deux radicaux R14 identiques ou différents ;- T 6 can take the same meanings as those indicated below for the radical R 14 , it being understood that T 6 is different from a hydrogen atom; - T, or T 5 can, in addition, form with T 6 a saturated or unsaturated ring comprising from 5 to 7 links, each link being unsubstituted or substituted by one or two identical or different R 14 radicals;
- deux des radicaux adjacents T1t T2, T3, T4 et T5 peuvent en outre former un cycle comportant de 5 à 7 chaînons, chaque chaînon étant indépendamment représenté par un atome de carbone non substitué ou substitué par un ou deux radicaux R14 identiques ou différents, un atome d'azote substitué ou non substitué par un radical R14, un atome d'oxygène ou un atome de soufre ;- two of the adjacent radicals T 1t T 2 , T 3 , T 4 and T 5 can also form a ring comprising from 5 to 7 links, each link being independently represented by a carbon atom unsubstituted or substituted by one or two radicals R 14 identical or different, a nitrogen atom substituted or unsubstituted by a radical R 14 , an oxygen atom or a sulfur atom;
- R10. R11. R12. R13 e R14, identiques ou différents représentent un atome d'hydrogène ; une chaîne hydrocarbonée comportant de 1 à 10 atomes de carbone, linéaire ou ramifiée, éventuellement aromatiques, et dont un ou plusieurs atomes de carbone peuvent être remplacés par un atome d'oxygène, d'azote, de soufre, ou par un groupe SO2, et dont un ou plusieurs atomes de carbone peuvent, indépendamment les uns des autres, être substitués par un ou plusieurs atomes d'halogène ; ledit radical ne comportant pas de liaison peroxyde ni de radicaux diazo, nitro ou nitroso ; - R10, Rn et R12 peuvent également former, deux à deux avec l'atome d'azote quaternaire auquel ils sont rattachés, un ou plusieurs cycles saturés comportant de 5 à 7 chaînons, chaque chaînon étant indépendamment représenté par un atome de carbone non substitué ou substitué par un ou deux radicaux R14 identiques ou différents, un atome d'azote non substitué ou substitué par un radical R14 , un atome d'oxygène , ou un atome de soufre,- R 10 . R 11 . R 12 . R 13 e R 14 , identical or different, represent a hydrogen atom; a hydrocarbon chain comprising from 1 to 10 carbon atoms, linear or branched, optionally aromatic, and one or more carbon atoms of which may be replaced by one atom oxygen, nitrogen, sulfur, or by an SO 2 group, and one or more carbon atoms of which may, independently of one another, be substituted by one or more halogen atoms; said radical not comprising a peroxide bond or diazo, nitro or nitroso radicals; - R 10 , Rn and R 12 can also form, two by two with the quaternary nitrogen atom to which they are attached, one or more saturated rings comprising from 5 to 7 links, each link being independently represented by a carbon atom unsubstituted or substituted by one or two identical or different R 14 radicals, a nitrogen atom unsubstituted or substituted by an R 14 radical, an oxygen atom, or a sulfur atom,
-lorsque n'" = 0, alors le groupement de formule (IX) peut être relié au composé de formule (V) et (VI) directement par l'atome d'azote de l'ammonium quaternaire, R13 représentant dans ce cas une simple liaison, - V représente un anion organique ou minéral,-when n '"= 0, then the group of formula (IX) can be linked to the compound of formula (V) and (VI) directly by the nitrogen atom of the quaternary ammonium, R 13 representing in this case a single bond, - V represents an organic or mineral anion,
• Z2 représente une chaîne hydrocarbonée en d-C10, linéaire ou ramifiée pouvant former un cycle carboné ayant de 5 à 7 chaînons, éventuellement aromatique ; un ou plusieurs atomes de carbone pouvant être remplacés par un ou plusieurs atomes d'oxygène, d'azote, de soufre ou par un groupement SO2. ledit radical Z2 ne comportant pas de liaison peroxyde, ni de radicaux diazo, nitro ou nitroso ; un groupe cationique Z3 tel que défini ci-dessus, avec la réserve que Z2 n'est pas cationique lorsque R7, R9, R7' ou R9' est cationique, • A2 représente un radical de formule (X) correspondant à un radical aromatique carboné, pyridinique ou pyridazinique substitué par un radical hétéroaromatique cationique à 5 chaînons, éventuellement substitué par un ou plusieurs radicaux R19 de même définition que R2 ; un radical de formule (XI) :• Z 2 represents a dC 10 hydrocarbon chain, linear or branched, which can form a carbon ring having 5 to 7 members, optionally aromatic; one or more carbon atoms which can be replaced by one or more oxygen, nitrogen, sulfur atoms or by an SO 2 group. said radical Z 2 not comprising a peroxide bond, nor of diazo, nitro or nitroso radicals; a cationic group Z 3 as defined above, with the proviso that Z 2 is not cationic when R 7 , R 9 , R 7 'or R 9 ' is cationic, • A 2 represents a radical of formula (X ) corresponding to a carbon, pyridine or pyridazine aromatic radical substituted by a 5-membered cationic heteroaromatic radical, optionally substituted by one or more radicals R 19 of the same definition as R 2 ; a radical of formula (XI):
dans lesquelles r est un entier égal à 0 ou 1 , - q est un entier égal à 0, 1 , 2 ou 3, s est un entier égal à 0, 1 , 2, 3, 4 ou 5, t est un entier égal à 0, 1 ou 2. Y3=Y4 représente C=C, C=N ou N=N, si r = 0 alors X représente O, S, NR18 CR20, - si r = 1 alors X représente CR20, in which r is an integer equal to 0 or 1, - q is an integer equal to 0, 1, 2 or 3, s is an integer equal to 0, 1, 2, 3, 4 or 5, t is an equal integer at 0, 1 or 2. Y 3 = Y 4 represents C = C, C = N or N = N, if r = 0 then X represents O, S, NR 18 CR 20 , - if r = 1 then X represents CR 20
R15 et R18 ont la même définition que R, définie ci-dessus,R 15 and R 18 have the same definition as R, defined above,
R16 R17, R19, R20et R21ont la même définition que R2 définie ci-dessus,R 16 R 17 , R 19 , R 20 and R 21 have the same definition as R 2 defined above,
V" représente un anion organique ou minéral,V "represents an organic or mineral anion,
avec la condition que dans la formule (I) un des groupes A1f Z2 et A3 est un groupe cationique.with the proviso that in formula (I) one of the groups A 1f Z 2 and A 3 is a cationic group.
2. Composition selon la revendication 1 dans laquelle les radicaux R R3 et R5 sont choisis parmi un radical alkyle ou alcényle en C C4 pouvant être substitué par un ou plusieurs substituants hydroxy, amino éventuellement substitué, carboxyl ; un radical phényle pouvant être substitué par un ou plusieurs atomes d'halogènes, un ou plusieurs groupes alkyle en C1-C4, aikoxy en d-C4, amino, hydroxy, trifluorométhyle, alkylamino en CrC4, carboxy ou sulfonyle ; un radical benzyle pouvant être substitué par un ou plusieurs atomes d'halogènes, un ou plusieurs groupes alkyle en d-C4, aikoxy en d-C4l amino, trifluorométhyle ; un hétérocycle choisi parmi l'imidazole, le thiazole, la pyridine ou la pyrimidine ; un radical (CH2)p-T-(CH2)q-V1R' où p et q sont entiers, identiques ou différents, compris entre 1 et 3, R' représente H ou méthyle et T et V, désignent indépendamment un atome d'oxygène ou un radical NR" avec R" désignant un hydrogène ou un méthyle. 2. Composition according to claim 1 in which the radicals RR 3 and R 5 are chosen from a CC 4 alkyl or alkenyl radical which can be substituted with one or more hydroxy, optionally substituted amino, carboxyl substituents; a phenyl radical which may be substituted by one or more halogen atoms, one or more C 1 -C 4 alkyl, dC 4 aikoxy, amino, hydroxy, trifluoromethyl, C r C 4 alkylamino, carboxy or sulfonyl; benzyl which may be substituted by one or more halogen atoms, one or more alkyl groups dC 4 aikoxy in dC 4l amino, trifluoromethyl; a heterocycle chosen from imidazole, thiazole, pyridine or pyrimidine; a radical (CH2) p -T- (CH2) q -V 1 R 'where p and q are whole, identical or different, between 1 and 3, R' represents H or methyl and T and V, independently denote an atom of oxygen or a radical NR "with R" denoting a hydrogen or a methyl.
3. Composition selon la revendication 2 dans laquelle R1 t R3 et R5 sont choisis parmi les radicaux méthyle ; éthyle ; hydroxyéthyle ; aminoéthyle ; carboxyméthyle ; carboxyéthyle ; phényle ; benzyle ; les hétérocycles choisis parmi pyridyle, imidazolyle, pyrimidinyle. 3. Composition according to claim 2 in which R 1 t R 3 and R 5 are chosen from methyl radicals; ethyl; hydroxyethyl; aminoethyl; carboxymethyl; carboxyethyl; phenyl; benzyl; heterocycles chosen from pyridyle, imidazolyle, pyrimidinyle.
4. Composition selon l'une quelconque des revendications 1 à 3 dans laquelle R, et R3 sont choisis parmi les groupes méthyle ; éthyle ; phényle ; hydroxyéthyle ; aminoéthyle ; carboxyméthyl ; carboxyéthyle.4. Composition according to any one of claims 1 to 3 in which R 1 and R 3 are chosen from methyl groups; ethyl; phenyl; hydroxyethyl; aminoethyl; carboxymethyl; carboxyethyl.
5. Composition selon l'une quelconque des revendications 1 à 4 dans laquelle les radicaux R2, R4 et R6 sont choisis parmi un atome d'hydrogène ; un radical alkyle ; un radical alkyle substitué par un ou plusieurs hydroxy, amino ou un halogène ; un radical phényle pouvant être substitué par un ou plusieurs substituants choisis parmi les radicaux alkyle, hydroxy, amino, alcoxy, carboxyle, trifluorométhyle, sulfonique ; les radicaux benzyle ;les radicaux benzyles substitués par un alcoxy, hydroxy ; un hétérocycle choisi parmi N-pyrrolidinyle, N-pipéridinyle, N-morpholine, N- pipérazinyle ou N-imidazolyle ; un radical alcoxy ; un radical phosphonyle ; un radical siloxy ; un radical amino ; un radical (di)alkylamino en d-C4 ; un radical acyle ; un radical acylamino ; un radical sulfonamide ; un radical uréido ; un radical sulfonylamino.5. Composition according to any one of claims 1 to 4 in which the radicals R 2 , R 4 and R 6 are chosen from a hydrogen atom; an alkyl radical; an alkyl radical substituted by one or more hydroxy, amino or halogen; a phenyl radical which may be substituted by one or more substituents chosen from alkyl, hydroxy, amino, alkoxy, carboxyl, trifluoromethyl, sulfonic radicals; benzyl radicals, benzyl radicals substituted by alkoxy, hydroxy; a heterocycle chosen from N-pyrrolidinyl, N-piperidinyl, N-morpholine, N-piperazinyl or N-imidazolyl; an alkoxy radical; a phosphonyl radical; a siloxy radical; an amino radical; a (di) alkylamino radical at dC 4 ; an acyl radical; an acylamino radical; a sulfonamide radical; a ureido radical; a sulfonylamino radical.
6. Composition selon la revendication 5 dans laquelle R2, R4 et R6 sont l'hydrogène ; un radical alkyle choisi parmi méthyle, éthyle ; un radical alkyle substitué choisi parmi trifluorométhyle; hydroxyméthyle, hydroxyéthyle, aminométhyle, aminoéthyle ; un benzyle ; un phényl éventuellement substitué par un ou plusieurs radicaux choisis parmi les radicaux méthyle, hydroxy, amino, méthoxy ; 2- méthoxybenzyle ; 4-méthoxybenzyle ; 2-hydroxybenzyle ; 4-hydroxybenzyle ; un hétérocycle choisi parmi pyrrolidinyle, pipéridinyle ; un radical méthoxy ; un radical acyle ; un radical amino ; un radical (di)alkylamino en CrC4 6. Composition according to claim 5 in which R 2 , R 4 and R 6 are hydrogen; an alkyl radical chosen from methyl, ethyl; a substituted alkyl radical chosen from trifluoromethyl; hydroxymethyl, hydroxyethyl, aminomethyl, aminoethyl; benzyl; a phenyl optionally substituted by one or more radicals chosen from methyl, hydroxy, amino and methoxy radicals; 2- methoxybenzyl; 4-methoxybenzyl; 2-hydroxybenzyl; 4-hydroxybenzyl; a heterocycle chosen from pyrrolidinyl, piperidinyl; a methoxy radical; an acyl radical; an amino radical; a C r C 4 (di) alkylamino radical
7. Composition selon la revendication 6 dans laquelle R2ι R4 et R6 sont choisis parmi l'hydrogène ; méthyle ; éthyle ; trifluorométhyle ; phényle ; pyrrolidinyle ; méthoxy ; amino. 7. Composition according to claim 6 in which R 2ι R 4 and R 6 are chosen from hydrogen; methyl; ethyl; trifluoromethyl; phenyl; pyrrolidinyl; methoxy; amino.
8. Composition selon l'une quelconque des revendications précédentes dans laquelle R8 et R8' sont choisis parmi un radical alkyle ou alcényle en d-C4 pouvant être substitué par un ou plusieurs substituants hydroxy, amino éventuellement substitué, carboxyl ; un radical phényle pouvant être substitué par un ou plusieurs atomes d'halogènes, un ou plusieurs groupes alkyle en d-C4, aikoxy en d-C4, amino, hydroxy, trifluorométhyle, alkylamino en d-C4, carboxy ou sulfonyle ; un hétérocycle choisi parmi l'imidazole, le thiazole, la pyridine ou la pyrimidine ; un radical (CH2)P-T- (CH2)q-V1R' où p et q sont entiers, identiques ou différents, compris entre 1 et 3, R' représente H ou méthyle et T et V, désignent indépendamment un atome d'oxygène ou un radical NR" avec R" désignant un hydrogène ou un méthyle.8. Composition according to any one of the preceding claims, in which R 8 and R 8 ′ are chosen from a dC 4 alkyl or alkenyl radical which may be substituted by one or more hydroxy or amino substituents, optionally substituted, carboxyl; a phenyl radical which may be substituted by one or more halogen atoms, one or more alkyl groups -C 4, -C 4 aikoxy, amino, hydroxy, trifluoromethyl, -C 4 alkylamino, carboxy or sulfonyl; a heterocycle chosen from imidazole, thiazole, pyridine or pyrimidine; a radical (CH2) P -T- (CH2) q -V 1 R 'where p and q are whole, identical or different, between 1 and 3, R' represents H or methyl and T and V, independently denote an atom of oxygen or a radical NR "with R" denoting a hydrogen or a methyl.
9. Composition selon la revendication 8 dans laquelle R8 et R'8 sont choisis parmi les radicaux Hydrogène ; méthyle ; éthyle ; hydroxyéthyle ; aminoéthyle ; carboxyméthyle ; carboxyéthyle ; phényle ; les hétérocycles choisis parmi pyridynyle, imidazolyle, pyrimidinyle, de préférence parmi l'hydrogène ; méthyle ; éthyle ; phényle ; hydroxyéthyle ; aminoéthyle ; carboxyméthyl ; carboxyéthyle.9. Composition according to claim 8 in which R 8 and R ′ 8 are chosen from the hydrogen radicals; methyl; ethyl; hydroxyethyl; aminoethyl; carboxymethyl; carboxyethyl; phenyl; heterocycles chosen from pyridynyl, imidazolyl, pyrimidinyl, preferably from hydrogen; methyl; ethyl; phenyl; hydroxyethyl; aminoethyl; carboxymethyl; carboxyethyl.
10. Composition selon l'une quelconque des revendications précédentes dans laquelle B est choisi parmi un radical alkyle éventuellement substitué choisi parmi méthyle, éthyle, propyle ; hydroxyméthyle, hydroxyéthyle, aminométhyle, aminoéthyle ; un méthoxybenzyle ; un hétérocycle choisi parmi pipérazinyle, de préférence parmi un radical méthyle ; éthyle ; propyle ; phényle ; pypérazinyle ; triazine.10. Composition according to any one of the preceding claims, in which B is chosen from an optionally substituted alkyl radical chosen from methyl, ethyl and propyl; hydroxymethyl, hydroxyethyl, aminomethyl, aminoethyl; methoxybenzyl; a heterocycle chosen from piperazinyl, preferably from a methyl radical; ethyl; propyl; phenyl; piperazinyl; triazine.
11. Composition selon l'une quelconque des revendications précédentes dans laquelle R10, R,,, R12, R13 et R14 sont choisis parmi un hydrogène ; un radical alkyle ou alcényle en d-C4 pouvant être substitué par un substituant hydroxy, amino éventuellement substitué; un radical phényle pouvant être substitué par un ou plusieurs atomes d'halogènes, un ou plusieurs groupes alkyle en 0,-04, aikoxy en C,- C4, amino, hydroxy, trifluorométhyle, alkylamino en 0,-04, carboxy ou sulfonyle ; un radical benzyle pouvant être substitué par un ou plusieurs atomes d'halogènes, un ou plusieurs groupes alkyle en 0,-04, aikoxy en C1-C4, amino, trifluorométhyle ; un radical (poly)aminoalkyl en CrC4 ; un radical (CH2)p-T-(CH2)q-V1R' où p et q sont entiers, identiques ou différents, compris entre 1 et 3, R' représente H ou méthyle et T et V, désignent indépendamment un atome d'oxygène ou un radical NR" avec R" désignant un hydrogène ou un méthyle, un radical sulfonyl. 11. Composition according to any one of the preceding claims, in which R 10 , R ,,, R 12 , R 13 and R 14 are chosen from hydrogen; a dC 4 alkyl or alkenyl radical which may be substituted with a hydroxy or optionally substituted amino substituent; a phenyl radical which can be substituted by one or more halogen atoms, one or more alkyl groups at 0, -0 4 , aikoxy at C, - C 4 , amino, hydroxy, trifluoromethyl, alkylamino at 0, -0 4 , carboxy or sulfonyl; a benzyl radical which can be substituted by one or more halogen atoms, one or more alkyl groups in O, -0 4 , aikoxy in C 1 -C 4 , amino, trifluoromethyl; a C r C 4 (poly) aminoalkyl radical; a radical (CH2) p -T- (CH2) q -V 1 R 'where p and q are whole, identical or different, between 1 and 3, R' represents H or methyl and T and V, independently denote an atom of oxygen or a radical NR "with R" denoting a hydrogen or a methyl, a radical sulfonyl.
12. Composition selon la revendication 11 dans laquelle R10, Rn, R,2, Rι3 et12. Composition according to claim 11 in which R 10 , Rn, R, 2 , Rι 3 and
R14 sont choisis parmi les radicaux méthyle ; éthyle ; isopropyle ; hydroxyéthyle ; aminoéthyle ; phényle ; benzyle ; les hétérocycles choisis parmi pyridynyle, imidazolyle, pyrimidinyle, de préférence parmi les radicaux méthyle ; éthyle ; phényle ; hydroxyéthyle ; aminoéthyle ; carboxyméthyl ; carboxyéthyle.R 14 are chosen from methyl radicals; ethyl; isopropyl; hydroxyethyl; aminoethyl; phenyl; benzyl; heterocycles chosen from pyridynyl, imidazolyl, pyrimidinyl, preferably from methyl radicals; ethyl; phenyl; hydroxyethyl; aminoethyl; carboxymethyl; carboxyethyl.
13. Composition selon l'une quelconque des revendications 1 à 12 dans laquelle Z1 est choisi parmi les radicaux imidazolinium , triazolinium, pyridinium, pyridazinium éventuellement substitué sur les atomes de carbone du cycle par un méthyle, un méthoxy, un carboxy, un amino, un phényle, une pyrrolidine et sur l'atome d'azote par un méthyl, un 2-hydroxyethyl, un carboxyméthyl, un carboxyethyl.13. Composition according to any one of claims 1 to 12 in which Z1 is chosen from the imidazolinium, triazolinium, pyridinium, pyridazinium radicals optionally substituted on the ring carbon atoms by a methyl, a methoxy, a carboxy, an amino, a phenyl, a pyrrolidine and on the nitrogen atom by a methyl, a 2-hydroxyethyl, a carboxymethyl, a carboxyethyl.
14. Composition selon l'une quelconque des revendications précédentes dans laquelle Z2 est choisi parmi radicaux imidazolium, pyridinium, pyridazinium, pyrimidinium, pyrazinium14. Composition according to any one of the preceding claims, in which Z 2 is chosen from imidazolium, pyridinium, pyridazinium, pyrimidinium, pyrazinium radicals
15. .Composition selon l'une quelconque des revendications 1 à 14 dans laquelle A2 est choisi parmi les radicaux pyrazolyle, pyrrolyle, imidazolyle, triazolyle, thiadiazolyle, éventuellement substitué.15.. A composition according to any one of claims 1 to 14 in which A 2 is chosen from the pyrazolyl, pyrrolyl, imidazolyl, triazolyl, thiadiazolyl radicals, optionally substituted.
16. Composition selon l'une quelconque des revendications 1 à 15 dans laquelle A,, A3 représentent indépendamment l'un de l'autre un radical aniline, aminopyridinyle, aminopyridazinyle éventuellement substitué par un atome d'hydrogène, par un radical méthyle, éthyle, hydroxyméthyle, hydroxyéthyle, 1 ,2- di hydroxyéthyle, 1 ,2-dihydroxypropyle, 2,3-dihydroxypropyle, aminométhyle, aminoéthyle, aminopropyle ; par un radical trifluorométhyle ; par un hétérocycle choisi parmi N-pyrrolidinyle, N-pipéridinyle, N-morpholine, N-pipérazinyle ou N-imidazolyle, par un radical alcoxy, par un radical phosphonyle, par un radical siloxy, par un radical 1 ,2-diaminoéthyle, par un radical 2,3-diaminopropyle, par un radical acyle, par un radical acylamino, par un radical sulfonamide, par un radical uréido, par un radical sulfonylamino. 16. Composition according to any one of claims 1 to 15 in which A ,, A 3 independently of one another represent an aniline, aminopyridinyl, aminopyridazinyl radical optionally substituted by a hydrogen atom, by a methyl radical, ethyl, hydroxymethyl, hydroxyethyl, 1,2-di hydroxyethyl, 1,2-dihydroxypropyl, 2,3-dihydroxypropyl, aminomethyl, aminoethyl, aminopropyl; with a trifluoromethyl radical; by a heterocycle chosen from N-pyrrolidinyl, N-piperidinyl, N-morpholine, N-piperazinyl or N-imidazolyl, by an alkoxy radical, by a phosphonyl radical, by a siloxy radical, by a 1,2-diaminoethyl radical, by a 2,3-diaminopropyl radical, an acyl radical, an acylamino radical, a sulfonamide radical, a ureido radical, a sulfonylamino radical.
17. Composition selon la revendication 16 dans laquelle A,, A3 sont choisis parmi les couples (A,, A3) suivants (radical aniline, radical aniline), (radical aniline, radical aminopyridinyle), (radical aminopyridinyle, radical aniline).17. Composition according to claim 16 in which A ,, A 3 are chosen from the following pairs (A ,, A 3 ) (aniline radical, aniline radical), (aniline radical, aminopyridinyl radical), (aminopyridinyl radical, aniline radical) .
18. Composition selon la revendication 17 dans laquelle le couple (A,, A3) est le couple (radical aniline, radical aniline) éventuellement subtitué par un radical méthyle, éthyle ou par un radical hydroxyméthyle, 1 ,2-dihydroxyéthyle, aminométhyle, 2-aminoéthyle, 1 ,2-diaminoéthyle, 2,3-diaminopropyle ou par un radical pyrrolidinyle, pipéridinyle, ou par un radical méthoxy ; amino ; méthylamino ; dimethylamino ; 2- hydroxyethylamino.18. Composition according to Claim 17, in which the pair (A ,, A 3 ) is the pair (aniline radical, aniline radical) optionally substituted by a methyl or ethyl radical or by a hydroxymethyl, 1,2-dihydroxyethyl or aminomethyl radical, 2-aminoethyl, 1,2-diaminoethyl, 2,3-diaminopropyl or by a pyrrolidinyl radical, piperidinyl, or by a methoxy radical; amino; methylamino; dimethylamino; 2- hydroxyethylamino.
19. Composition selon l'une quelconque des revendications 1 à 18 dans laquelle le colorant azoique correspond à la formule (I) dans laquelle Z1 est un groupe imidazolium, n est égal à 1, le couple A1.A3 est un couple (radical aniline, radical aniline) et Z2 est choisi parmi les radicaux imidazolium, pyridinium, pyridazinium, pyrimidinium, pyrazinium, de préférence pyridinium ou pyrimidinium.19. Composition according to any one of claims 1 to 18 in which the azo dye corresponds to formula (I) in which Z1 is an imidazolium group, n is equal to 1, the pair A1.A3 is a pair (aniline radical , aniline radical) and Z 2 is chosen from the imidazolium, pyridinium, pyridazinium, pyrimidinium, pyrazinium radicals, preferably pyridinium or pyrimidinium.
20. Composition selon l'une quelconque des revendications 1 à 19 dans laquelle le colorant azoique de formule (I) est choisi parmi20. Composition according to any one of claims 1 to 19 in which the azo dye of formula (I) is chosen from
21. Composition selon la revendication 20 dans laquelle le colorant azoique de formule (I) est choisi parmi : 21. Composition according to claim 20 in which the azo dye of formula (I) is chosen from:
22. Composition selon l'une quelconque des revendications 1 à 21 comprenant de plus une base d'oxydation.22. Composition according to any one of claims 1 to 21 further comprising an oxidation base.
23. Composition selon la revendication 22 dans laquelle la base d'oxydation est choisie parmi les paraphénylènediamines, les bis- phénylalkylènediamines, les para-aminophénols, les ortho-aminophénols, les bases hétérocycliques, et leurs sels d'addition avec un acide.23. The composition as claimed in claim 22 in which the oxidation base is chosen from paraphenylenediamines, bisphenylalkylenediamines, para-aminophenols, ortho-aminophenols, heterocyclic bases, and their addition salts with an acid.
24. Composition selon l'une quelconque des revendications 22 ou 23 dans laquelle la ou les bases d'oxydation sont présentes en quantité comprise entre 0,001 et 10 %, de préférence entre 0,005 et 6 %. 24. Composition according to any one of claims 22 or 23 in which the oxidation base or bases are present in an amount between 0.001 and 10%, preferably between 0.005 and 6%.
25. Composition selon l'une quelconque des revendications 1 à 24 comprenant au moins un coupleur.25. Composition according to any one of claims 1 to 24 comprising at least one coupler.
26. Composition selon la revendication 25 dans laquelle le coupleur est choisi parmi métaphénylènediamines, les méta-aminophénols, les metadiphenols, les coupleurs naphtaléniques et les coupleurs hétérocycliques et leur sel d'addition avec un acide.26. The composition as claimed in claim 25 in which the coupler is chosen from metaphenylenediamines, meta-aminophenols, metadiphenols, naphthalene couplers and heterocyclic couplers and their addition salt with an acid.
27. Composition selon l'une quelconque des revendications 1 à 26 comprenant de plus un agent oxydant, de préférence le peroxyde d'hydrogène.27. Composition according to any one of claims 1 to 26 further comprising an oxidizing agent, preferably hydrogen peroxide.
28. Procédé de teinture d'oxydation des fibres kératiniques et en particulier des fibres kératiniques humaines telles que les cheveux, caractérisé en ce qu'on applique sur les fibres au moins une composition tinctoriale telle que définie à l'une quelconque des revendications 1 à 21.28. Process for the oxidation dyeing of keratin fibers and in particular human keratin fibers such as the hair, characterized in that at least one dye composition as defined in any one of claims 1 is applied to the fibers. 21.
29. Procédé selon la revendication 28 dans lequel la composition tinctoriale contient un agent oxydant.29. The method of claim 28 wherein the dye composition contains an oxidizing agent.
30. Procédé selon la revendication 28 dans lequel l'agent oxydant est mélangé au moment de l'emploi à la composition tinctoriale.30. The method of claim 28 wherein the oxidizing agent is mixed at the time of use with the dye composition.
31. Procédé selon l'une quelconque des revendications 29 ou 30 dans lequel l'agent oxydant est appliqué sur les fibres sous forme de composition oxydante simultanément ou séquentiellement à la composition tinctoriale.31. A method according to any one of claims 29 or 30 in which the oxidizing agent is applied to the fibers in the form of an oxidizing composition simultaneously or sequentially with the dye composition.
32. Procédé de teinture d'oxydation des fibres kératiniques et en particulier des fibres kératiniques humaines telles que les cheveux, caractérisé en ce qu'on applique sur les fibres au moins une composition tinctoriale telle que définie selon l'une quelconque des revendications 1 à 21 , comprenant de plus au moins une base d'oxydation et optionnellement au moins un coupleur en présence d'un agent-oxydant.32. Process for the oxidation dyeing of keratin fibers and in particular human keratin fibers such as the hair, characterized in that at least one dye composition as defined according to any one of claims 1 is applied 21, further comprising at least one oxidation base and optionally at least one coupler in the presence of an oxidizing agent.
33. Procédé selon la revendication 32 dans lequel l'agent oxydant est mélangé au moment de l'emploi à la composition tinctoriale. 33. The method of claim 32 wherein the oxidizing agent is mixed at the time of use with the dye composition.
34. Procédé selon la revendication 32 dans lequel l'agent oxydant est appliqué sur les fibres sous forme de composition oxydante simultanément ou séquentiellement à la composition tinctoriale.34. The method of claim 32 wherein the oxidizing agent is applied to the fibers in the form of an oxidizing composition simultaneously or sequentially with the dye composition.
35. Dispositif à plusieurs compartiments ou "kit" de teinture à plusieurs compartiments, dans lequel un premier compartiment contient une composition telle que définie à l'une quelconque des revendications 1 à 26 et un deuxième compartiment contient une composition oxydante.35. Multi-compartment device or multi-compartment dye "kit", in which a first compartment contains a composition as defined in any one of claims 1 to 26 and a second compartment contains an oxidizing composition.
36. Composés monoazoïques dicationiques de formule (I) ou (II) telle que définie selon l'une quelconque des revendications 1 à 21 et R8 est l'hydrogène. 36. Dicationic monoazo compounds of formula (I) or (II) as defined according to any one of claims 1 to 21 and R 8 is hydrogen.
EP02759813A 2001-04-03 2002-04-03 Novel dyeing composition for dyeing keratinous fibres comprising a particular dicationic monoazo dye Withdrawn EP1408919A2 (en)

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FR0104537A FR2822698B1 (en) 2001-04-03 2001-04-03 NEW DYE COMPOSITION FOR DYEING KERATIN FIBERS COMPRISING A DICATIONIC MONOAZO DYE
FR0104537 2001-04-03
PCT/FR2002/001153 WO2002080869A2 (en) 2001-04-03 2002-04-03 Novel dyeing composition for dyeing keratinous fibres comprising a particular dicationic monoazo dye

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FR2822698B1 (en) 2006-04-21
JP2005504726A (en) 2005-02-17
US7060110B2 (en) 2006-06-13
FR2822698A1 (en) 2002-10-04

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