FR2912907A1 - Composition, useful for coloring human keratinous fibers, preferably hair, comprises a cationic azo compound and a non-cellulosic thickening polymer - Google Patents

Abstract

Composition (I) for coloring human keratinous fibers, comprises at least a cationic azo compound (a) and at least a non-cellulosic thickening polymer. Composition (I) for coloring human keratinous fibers, comprises at least a cationic azo compound of formula (a) and at least a non-cellulosic thickening polymer. A : 3H-imidazol-1-ium group of formula (aa) or pyridinium group of formula (bb); R 1, R 21-4C (preferably 1-2C) alkyl, preferably methyl; and X : anion group. Independent claims are included for: (1) a process of coloring human keratinous fiber comprising applying (I) on the keratinous fibers, leaving the fiber at rest and rinsing the fiber; and (2) a device with several compartments comprising a first compartment containing (I) and a second compartment containing (I) having an oxidizing agent. [Image].

Description

COLORING COMPOSITION COMPRISING AT LEAST ONE AZO COLORANT

  The present application relates to a composition for staining human keratinous fibers comprising at least one cationic azo dye with a julolidine motif and at least one non-cellulosic, associative thickening polymer. BACKGROUND OF THE INVENTION or not, a method of staining these fibers using such a composition and a device with appropriate compartment.

  It is known to dye human keratinous fibers, in particular the hair, with dyeing compositions comprising oxidation dye precursors, generally known as oxidation bases, such as ortho- or para-phenylenediamines, ortho- or para-phenylenediamines. aminophenols and heterocyclic compounds. These oxidation bases are colorless or weakly colored compounds which, combined with oxidizing products, make it possible to access colored species by a process of oxidative condensation with colored compounds.

  It is also known that the shades obtained with these oxidation bases can be varied by combining them with couplers, the latter being chosen in particular from aromatic meta-diamines, meta-aminophenols, meta-diphenols and certain compounds. heterocyclic compounds, such as indole compounds. The variety of molecules involved in the oxidation bases and couplers makes it possible to obtain a rich palette of colors. It is also known to dye keratinous fibers by a direct or semi-permanent coloring. The method conventionally used in direct dyeing consists in applying to the keratin fibers direct dyes which are colored and dyestuff molecules having an affinity for the fibers, to be allowed to pause in order to allow the colored molecules to penetrate, by diffusion, inside. hair, then rinse the fibers. In contrast to oxidation dyeing compositions, direct or semi-permanent dyeing compositions can be carried out without the obligatory presence of an oxidizing agent. These dyes can be performed repeatedly without degrading the keratin fiber. It is known, for example, to use nitrobenzene, anthraquinone, nitropyridine, azo, xanthene, acridine, azine or triarylmethane direct dyes. This results in often chromatic colorations which are, however, temporary or semi-permanent because of the nature of the bonds between the direct dyes and the keratin fiber. These interactions make the desorption of dyes from the surface and / or the core of the fiber relatively easy. Therefore, the colorations often have a relative poor resistance to washes or perspiration. Another disadvantage of the known direct coloration lies in the fact that certain shades are insufficiently accessible, such as in particular blues and chromatic violets. This is because not only relatively few direct dyes make it possible to obtain such colors, but also because some of these dyes are difficult to use because of their too low solubility limit or their insufficient stability in solution. which hinders their use in conventional dyeing compositions.

  There is a real need for dyes that make it possible to access dye areas that are different from those generally achieved in coloring while improving the homogeneity of the coloration obtained, whatever the state of sensitization of the treated fibers, but also the toughness of the color vis-à-vis external agents such as shampoos, while limiting disgorging which induces risks of stains, as well as risks of color change over time when we associate together chromatic colorants of tenacity respective ones.

  These and other objects are achieved by the present invention which therefore relates to a composition for the dyeing of human keratinous fibers, in particular the hair, comprising in a cosmetically acceptable medium, at least one azo cationic compound of formula (I ) where R 1, R 2, which may be identical or different, represent a C 1 -C 4, preferably C 1 -C 2, alkyl radical, advantageously methyl; a represents the bond with the azo group; X- representing a cosmetically acceptable anion; at least one non-cellulosic thickening polymer. It also relates to a process for staining human keratinous fibers, in particular the hair, wherein said composition is applied to said fibers, allowed to pause and then rinsed the fibers thus treated. (I) wherein A represents: R2 ~ N + X (la) X-The invention finally relates to a multi-compartment device comprising the dye composition according to the present invention.

  Other features, aspects, objects and advantages of the invention will emerge even more clearly on reading the description and examples which follow.

  It should be noted that in what follows, and unless otherwise indicated, the boundaries of a domain of values are included in this area.

  As indicated above, the azo cationic compound julolidine unit used in the composition according to the invention, corresponds to compounds of formula (I) below: AùN = N (I) wherein A represents: (la) R2 N a \ N + R 'N \\ X- with R ,, R2, identical or not, represent an alkyl radical C1-C4, preferably C1-C2, preferably methyl; X- represents a cosmetically acceptable anion chosen, for example, from methosulphate, tosylate, acetate, lactate, citrate, sulfate, carbonate, tartrate ions or halide ions such as the chloride ion. According to a particularly advantageous embodiment, the compound of formula (I) corresponds to the following compounds: ## STR1 ## and X- represents a cosmetically acceptable anion. More particularly, X- represents a chloride or methosulphate ion. The dyeing composition according to the present invention may comprise from 0.001 to 10%, preferably from 0.05 to 2% by weight of cationic azo direct dye of formula (I) relative to the total weight of the composition. These dyes can be obtained, for example, by four different synthetic routes, hereinafter referred to as A, B, C and D respectively: In the following diagrams, the definition of B, a non-cationic precursor of A, corresponds to the following two formulas: ## STR2 ## In the following, R 1 -HAL signifies a halogen group connected to the alkyl radical, preferably a chloro, bromo or iodo group, or a dialkylsulfato group, preferably dimethylsulfato or diethylsulfato or methylsulfonato (mesylate) or arylsulfonato (tosylate).

  1 / Synthetic route A The compound of formula (I) is obtained in three successive stages in accordance with the following scheme: HNO 2 (nitrosylsulphuric acid) 4BiNHZ 3 AiNN An 5 The diazonium salt 2 of the heteroaromatic amine BNH 2 is prepared 1 by conventional methods (H Zollinger, Color Chemistry, Wiley VCH Ed 2003 and The Chemistry of Synthetic Dyes, Academic Press, London, vol II, 1952). The diazonium salt 2 is then reacted with a compound 3 (a julolidine aromatic amine) to form compound 4. This type of coupling is well known in the literature cited above. The third step is to react the compound 4 with an alkylating reagent, such as an alkyl sulfate, an alkyl halide, an alkyl alkyl sulphonate or an alkyl aryl sulphonate, to form the compound 5: a cationic azo direct dye with julolidine pattern.

  The alkylation reaction is carried out for example in a halogenated solvent (dichloromethane) or ester (ethyl acetate), at a temperature below 150 ° C., preferably at reflux of the solvent. These conditions are notably described in the literature. With reference to this type of reaction, mention may be made, for example, of Advanced Organic Synthesis 5th Ed M. Smith and J. March John Wiley & Sons Ed, 2001 and International Application WO 03/060015.

  2 / Synthetic route B The compound of formula (I) can be obtained by diazotating the para-amine derivative of an aromatic amine with a julolidine 6 unit, and then coupling the obtained diazonium salt 7 with a heterocylate to yield compound 8, then alkylation of the heterocyclic function to give compound 9 (the joulolidine cationic direct azo dye) according to the following scheme: R 1 -HA A n N = N An 9 All the synthesis steps are described in the literature and references Track 1 are also applicable. More particularly, the second step consists in reacting the previously obtained diazonium salt 7 with a BH heterocycle (according to the above definition of B and H representing a hydrogen atom bonded to B on the position which will then be that of the azo group). .

  3 / Synthetic Route C The compound of formula (I) can also be obtained in two synthesis steps: nucleophilic attack on a carbon atom of a cationic heterocycle [II] with a para-hydrazino compound of an aromatic amine julolidine unit 10 then oxidation of compound 12 obtained to lead to compound 13 (a cationic direct azo dye with julolidine motif) 6 A. leaving group with leaving group = Cl, Br, I, etc. HZN, NH AN HNH 12 13 The reaction for the compound 12 can be formed in a polar solvent, preferably an alcohol or DMF, at a temperature below 150 ° C., in the presence, if necessary, of a base which is less nucleophilic than the hydrazine chosen (J. Med. Chem., 1996, 39 (2), 570-581) The oxidation can be carried out using the usual oxidants: N-bromosuccinimide, ferric chloride, manganese oxide, chromium oxides, hydrogen peroxide, peracids, preferably in an acidic medium and at a temperature below 100 ° C. less than 24 hours 4 / Synthetic route D The compound of formula (I) can also be obtained by oxidative coupling. This pathway is described in the literature. With reference to this type of reaction, mention may be made, for example, of Angew. Chem. 1958, 70,215; Angew. Chem., Int. Ed., 1962, 1,640 and H Zollinger, Color Chemistry 3rd Ed, VCH Wiley, 2003. The pathway is exemplified according to the following scheme using to illustrate compound 14 to yield compound 17 (a joulolidine cationic direct azo dye): The starting reactants are commercially available or are obtained by methods known to those skilled in the art, preferably from commercially available compounds.

  The composition further comprises at least one non-cellulosic thickening polymer.

  For the purposes of the present invention, the term "thickening polymer" means any polymer which, at a concentration of 1% of active material, is introduced into the composition without thickening polymers, makes it possible to increase the viscosity of said composition by at least 100 cps at room temperature. 25 C and at a shear rate of 1 s -1.

  Preferably said thickening polymer has at the concentration of 1% of active material a viscosity in solution or in aqueous dispersion at pH7 of at least 100 cps at the temperature of 25 C and a shear rate of 1 s-1. These viscosities can be evaluated using a viscometer or rheometer cone / plane.

  The thickening polymer of the invention may be associative or not.

  It is first of all pointed out that for the purposes of the present invention, the non-associative thickening polymers are thickening polymers not containing a C8-C30 fatty chain. Moreover, the associative polymers comprise at least one fatty chain of C 8 -C 30 and preferably C 10 -C 30 and are capable, in the medium of the composition in which they are present, of associating with each other or with molecules of other compounds.

  Among the non-associative thickening polymers present in the composition according to the invention, mention may be made of crosslinked acrylic acid homopolymers, crosslinked homopolymers of 2-acrylamido-2-methylpropanesulphonic acid and their crosslinked copolymers of acrylamide, nonionic guar gums, biopolysaccharide gums of microbial origin, gums derived from plant exudates, pectins and alginates, alone or in mixtures.

  A first family of suitable nonassociative thickening polymers is represented by crosslinked acrylic acid homopolymers. Among the homopolymers of this type, mention may be made of those crosslinked with an allylic alcohol ether of the sugar series, such as, for example, the products sold under the names CARBOPOLS 980, 981, 954, 2984 and 5984 by the company NOVEON or the products sold under the names SYNTHALEN M and SYNTHALEN K by the company 3 VSA.

  The non-associative thickening polymers may also be chosen from cross-linked homopolymers of 2-acrylamido-2-methylpropanesulphonic acid and their crosslinked acrylamide copolymers. With regard to these homopolymers and copolymers, which may be partially or completely neutralized, mention may be made of polymers comprising from 90 to 99.9% by weight, relative to the total weight of the polymer, of units of formula (j) below: c 2 / C CH More particularly the cations are chosen from alkali metals (such as sodium, potassium), ammonium ions substituted or not by one to three identical or different alkyl radicals, comprising 1 to 6 carbon atoms, optionally carrying at least one hydroxyl radical, the cations derived from N-methylglucamine, basic amino acids such as arginine and lysine. Preferably, the cation is an ammonium or sodium ion.

  In addition, the polymer comprises from 0.01 to 10% by weight, relative to the total weight of the polymer, of crosslinking units originating from at least one monomer having at least two ethylenic unsaturation (carbon-carbon double bond). The crosslinking monomers having at least two ethylenic unsaturations are chosen for example from diallyl ether, triallyl cyanurate, diallyl maleate, allyl (meth) acrylate, dipropylene glycol diallyl ether, polyglycol diallyl ether, triethylene glycol divinyl ether, hydroquinone-diallyl ether, tetralyl-oxethanoyl, tetra- or di-ethylene glycol di (meth) acrylate, triallylamine, tetraallylethylenediamine, trimethylolpropane diallyl ether, trimethylolpropane triacrylate, methylenebis (meth) acrylamide or divinylbenzene, allyl ethers of alcohols of the series of sugars, or other allyl- or vinyl-ethers of polyfunctional alcohols, as well as the allyl esters of phosphoric and / or vinylphosphonic acid derivatives, or mixtures thereof. of these compounds. For more details about these polymers, reference can be made to EP 815828.

  Among the crosslinked copolymers of 2-acrylamido-2-methyl-propanesulfonic acid and of acrylamide partially or totally neutralized, mention may be made in particular of the product described in Example 1 of EP 503 853 and it will be possible to refer to this document for these polymers.

  The composition may also comprise nonionic guar gums, for example unmodified nonionic guar gums sold under the name VIDOGUM GH 175 by the company UNIPECTINE and under the name JAGUAR C by MEYHALL. The nonionic guar gums that may be used according to the invention are preferably modified with hydroxy-C 1 -C 6 groups. Among the groups H - H C CH 2 SO 3 X + 3 in which X + denotes a cation or a mixture of cations, or a proton. hydroxyalkyl, there may be mentioned by way of example, the hydroxymethyl, hydroxyethyl, hydroxypropyl and hydroxybutyl groups. These guar gums are well known in the state of the art and may for example be prepared by reacting corresponding alkene oxides, such as, for example, propylene oxides, with guar gum, so as to obtain guar gum modified with hydroxypropyl groups. The level of hydroxyalkylation, which corresponds to the number of alkylene oxide molecules consumed by the number of free hydroxyl functions present on the guar gum, preferably varies from 0.4 to 1.2.

  Such nonionic guar gums optionally modified with hydroxyalkyl groups are, for example, sold under the trade names Jaguar HP8, Jaguar HP60 and Jaguar HP120, Jaguar DC 293 and Jaguar HP 105 by the company Meyhall or under the name GALACTASOL 4H4FD2 by the company Aqualon.

  As suitable thickening polymers, mention may also be made of biopolysaccharide gums of microbial origin such as scleroglucan or xanthan gums. Also suitable are gums derived from plant exudates, such as gum arabic, Ghatti gums, Karaya and Tragacanthe gums; pectins and alginates. These polymers are well known to those skilled in the art and are described in particular in the book by Robert L. DAVIDSON entitled "Handbook of Water Soluble Gums and Resins" published by Mc Graw Hill Book Company (1980).

  As indicated above, the associative polymers are hydrophilic polymers capable, in an aqueous medium, to associate reversibly with each other or with other molecules. Their chemical structure more particularly comprises at least one hydrophilic zone and at least one hydrophobic zone. Hydrophobic group is understood to mean a radical or polymer with a hydrocarbon chain, saturated or unsaturated, linear or branched, comprising at least 8, preferably at least 10 carbon atoms, preferably from 10 to 30 carbon atoms, in particular from 12 to to 30 carbon atoms and more preferably from 18 to 30 carbon atoms. Preferably, the hydrocarbon group comes from a monofunctional compound. By way of example, the hydrophobic group may be derived from a fatty alcohol such as stearyl alcohol, dodecyl alcohol or decyl alcohol. It can also denote a hydrocarbon polymer such as for example polybutadiene.

  The composition may therefore comprise at least one associative polymer chosen from nonionic associative polyurethanes, polyunsaturated associative polyacids without urethane units, associative aminoplast-ethers, associative polymers or copolymers comprising at least one ethylenically unsaturated monomer containing a sulfonic group, alone. or in mixtures.

  Among the associative thickening polymers, mention may be made of associative polyurethane derivatives, such as those obtained by polymerization: about 20% to 70% by weight of a carboxylic acid with α, β-monoethylenic unsaturation, about 20 to 80% by weight of a non-surfactant a, 13-monoethylenic unsaturated monomer different from the foregoing, - about 0.5 to 60% by weight of a nonionic mono-urethane which is the reaction product of a monohydroxy surfactant with a monoethylenically unsaturated monoisocyanate, such are especially described in EP 173109 and more particularly in Example 3. More specifically, this polymer is a terpolymer methacrylic acid / methyl acrylate / dimethyl metaisopropenyl benzyl isocyanate alcohol ethoxylated behenate (400E This product is available under the reference VISCOPHOBE DB1000 by the company AMERCHOL.

  The associative polyurethane derivatives of the invention may advantageously be chosen from nonionic polyether polyurethanes. More particularly, said polymers contain in their chain both hydrophilic sequences of a most often polyoxyethylenated nature and hydrophobic sequences which may be aliphatic chains alone and / or cycloaliphatic and / or aromatic chains.

  Preferably, these polyurethane polyethers comprise at least two hydrocarbon-based lipophilic chains having from 6 to 30 carbon atoms, separated by a hydrophilic sequence, the hydrocarbon chains possibly being pendant chains or chains at the end of the hydrophilic sequence. In particular, it is possible that one or more pendant chains are provided. In addition, the polymer may comprise a hydrocarbon chain at one end or at both ends of a hydrophilic block. The polyether polyurethanes may be multiblocked, in particular in the form of a triblock. The hydrophobic sequences may be at each end of the chain (for example: hydrophilic central block triblock copolymer) or distributed at both the ends and in the chain (multiblock copolymer for example). These same polymers may also be graft or star. The fatty-chain nonionic polyurethane polyethers may be triblock copolymers whose hydrophilic sequence is a polyoxyethylenated chain containing from 50 to 1000 oxyethylenated groups. The nonionic polyurethane polyethers comprise a urethane bond between the hydrophilic blocks, hence the origin by name. By extension also appear among the nonionic polyurethane polyethers with a hydrophobic chain, those whose hydrophilic sequences are linked to the hydrophobic blocks by other chemical bonds.

  By way of examples of nonionic polyurethane polyethers with a hydrophobic chain which can be used in the invention, it is also possible to use the urea-functional Rheolate 205 sold by Rheox or the Rheolates 208, 204 or 212 and the Acrysol RM. 184. Mention may also be made of the product ELFACOS T210 with a C12-C14 alkyl chain and the product ELFACOS T212 with an O18 alkyl chain from AKZO. The product DW 1206B from ROHM & HAAS with a C20 alkyl chain and a urethane bond, proposed at 20% solids content in water, can also be used.

  It is also possible to use solutions or dispersions of these polymers, especially in water or in an aqueous-alcoholic medium. By way of examples, such polymers include, for example, Rheolate 255, Rheolate 278 and Rheolate 244 sold by Rheox. It is also possible to use the product DW 1206F and the DW 1206J proposed by the company Rohm & Haas.

  The usable polyurethane polyethers described above can also be chosen from those described in the article by G. Fonnum, J. Bakke and Fk. Hansen - Colloid Polym. Sci 271, 380, 389 (1993).

  More particularly still, according to the invention, it is preferred to use a polyether polyurethane obtainable by polycondensation of at least three compounds comprising (i) at least one polyethylene glycol comprising from 150 to 180 moles of ethylene oxide, ( ii) stearyl alcohol or decyl alcohol and (iii) at least one diisocyanate. Such polyether polyurethanes are sold in particular by Rohm & Haas under the names Aculyn 46 and Aculyn 44. Aculyn 46 is a polycondensate of polyethylene glycol containing 150 or 180 moles of ethylene oxide, stearyl alcohol and methylene. bis (4-cyclohexyl-isocyanate) (SMDI), 15% by weight in a matrix of maltodextrin (4%) and water (81%); ACULYN 44 is a polycondensate of polyethylene glycol with 150 or 180 moles of ethylene oxide, decyl alcohol and methylenebis (4-cyclohexylisocyanate) (SMDI), at 35% by weight in a propylene glycol mixture (39). %) and water (26%)].

  Among the associative unsaturated polyacid derivatives without urethane units, mention may be made of those comprising at least one hydrophilic unit of the olefinic unsaturated carboxylic acid type, and at least one hydrophobic unit of the unsaturated carboxylic acid (C 10 -C 30) alkyl ester type.

  These polymers are especially chosen from those whose hydrophilic unit of olefinic unsaturated carboxylic acid type corresponds to the monomer of formula (e) below: ## STR2 ##

R1 O (e)

  in which, R 1 denotes H or CH 3 or C 2 H 5, that is to say acrylic acid, methacrylic acid or ethacrylic acid units, and whose hydrophobic unit of alkyl ester (C 10 -C 30) unsaturated carboxylic acid type; corresponds to the monomer of the following formula (f): ## STR2 ## where

  in which, R2 denotes H or CH3 or C2H5 (that is to say acrylate, methacrylate or ethacrylate units) and preferably H (acrylate units) or CH3 (methacrylate units), R3 denotes a C10-C30 alkyl radical; and preferably C12-C22. (C 10 -C 30) alkyl esters of unsaturated carboxylic acids include, for example, lauryl acrylate, stearyl acrylate, decyl acrylate, isodecyl acrylate, dodecyl acrylate, and corresponding methacrylates, lauryl methacrylate, stearyl methacrylate, decyl methacrylate, isodecyl methacrylate, and dodecyl methacrylate. Anionic polymers of this type are, for example, described and prepared according to US Pat. Nos. 3,915,921 and 4,509,949.

  In this type of anionic associative polymers, polymers formed from a monomer mixture comprising: (i) essentially acrylic acid, (ii) an ester of formula (f) described above and wherein R2 denotes H or CH3, R3 denotes an alkyl radical having from 12 to 22 carbon atoms, (iii) and a crosslinking agent, which is a well-known copolymerizable polyethylenic unsaturated monomer, such as diallyl phthalate, (meth) allyl acrylate, divinylbenzene, (poly) ethylene glycol dimethacrylate, and methylene-bis-acrylamide.

  Among this type of anionic associative polymers, those consisting of 95 to 60% by weight of acrylic acid (hydrophilic unit), of 4 to 40% by weight of C 10 -C 30 alkyl acrylate (hydrophobic unit), are preferred. and from 0 to 6% by weight of crosslinking polymerizable monomer, or those consisting of 98 to 96% by weight of acrylic acid (hydrophilic unit), of 1 to 4% by weight of C10-C30 alkyl acrylate (Hydrophobic unit), and from 0.1 to 0.6% by weight of crosslinking polymerizable monomer such as those described above.

  Among said polymers above, the products sold by the company Goodrich under the trade names Pemulen TR1, Pemulen TR2, Carbopol 1382, and even more preferentially Pemulen TR1, and the product sold by the company S.E.P.P.I.C., are particularly preferred. under the name COATEX SX.

  Among the associative unsaturated polyacid derivatives without urethane units, mention may also be made of those comprising among their monomers an α, β-monoethylenically unsaturated carboxylic acid and an α, β-monoethylenically unsaturated carboxylic acid ester and an oxyalkylenated fatty alcohol. .

  Preferentially, these compounds also comprise, as monomer, a carboxylic acid ester containing α, β-monoethylenic unsaturation and of C 1 -C 4 alcohol. By way of examples of this type of compounds, mention may be made of Aculyn 22 sold by Rohm and Haas, which is a methacrylic acid / ethyl acrylate / stearyl methacrylate oxyalkylenated terpolymer.

  As regards the thickening polymers of the aminoplast-ether type, any product resulting from the condensation of aldehyde with an amine or an amide, as well as any structural unit formed of an aminoplast residue and a divalent hydrocarbon residue, is meant. bound to the aminoplast residue by an ether linkage.

  The polymers having an aminoplast-ether backbone are preferably chosen from those containing at least one unit of the following structure (g): (RO) AMP-RO, (g) in which: AMP is an aminoplast residue with alkylene units (or divalent alkyl), -R denotes a hydrogen atom, a C1-C4 alkyl radical or a C1-C4 acyl radical, -RO, is a divalent alkylene-oxy residue, -p denotes a positive integer, -the or the OR groups being linked to the alkylene units of the AMP residue.

  Preferably, the polymers having an aminoplast-ether backbone are chosen from those containing at least one unit with the following structure (h): (RO) / (RO 2) q AMP RO RO, (h) in which: -AMP, R, RO , and p have the same meaning as before, - R02 is a different group of AMP-linked RO with a heteroatom and comprising at least two carbon atoms, and, -q is a positive integer. More preferably still, the polymers correspond to the following formulas (III) and (III) bis: (Ro) (ROI - (RO2) q * C AMPUROB (i) R2 AMPuRO, R3 (ibis) R2 R3 aa in which: -AMP, R, RO ,, R02, p and q have the same meaning as previously, -R2 or R3 , identical or different, represent a terminal group which can designate a hydrogen atom, a group RO, H, a group RO2H, a group AMP (OR) p or any monofunctional group such as alkyl, cycloalkyl, aryl, aralkyl, alkylaryl, alkyloxyalkyl , aryloxyalkyl, cycloalkoxyalkyl, -a being a number greater than 1 and preferably greater than 2. Preferably, the aminoplast residue (s) carrying their OR groups are chosen from those of structure (13) below: OO NO (13) ` Where R, p, and x have the same meanings as above The divalent alkyleneoxy residues are preferably those corresponding to the diols of the following general formula (14): ## STR2 ## (Z0) (Z1 (Z20) w), - (Z'O) y'-Z3OH (14), -y and y 'being numbers ranging from 0 to 1000, and where w is a number from 0 to 10, -Z, Z ', Z2 and Z3 are C2-04 alkylene radicals and preferably -CH2-CH (Z4) -and -CH2-CH (Z4) radicals; ) -CH2-, -Z, being a linear or cyclic radical, branched or unbranched, aromatic or not, with or without one or more heteroatoms and having 1 to 40 carbon atoms, -Z4 denoting a hydrogen atom or a C1-C4 alkyl radical or a C1-C3 acyl radical, it being understood that at least one of the radicals Z4 of the radicals Z, Z ', Z2 and Z3 is different from an acyl radical. Z4 preferably denotes a hydrogen atom or a methyl radical. Even more preferentially, t = 0 and Z, Z 'and Z3 denote -CH2CH2-, and at least one of y or y' is different from O. The compounds of formula (14) are then polyethylene glycols.

  The aminoplast ether polymers of formula (g) are in particular described in US Pat. No. 5,914,373 to which reference may be made for more details. As aminoplast-ether skeletal polymers of formula (g), mention may be made in particular of Pure-Thix L products [PEG-180 / Octoxynol-40 / TMMG Copolymer (INCI name)], Pure-Thix M [PEG-180 / Laureth-50 / TMMG Copolymer (INCI name)], Pure-Thix HH [Polyether1 (INCI name)]; Pure Thix TX-1442 [PEG-18 / dodoxynol-5 copolymer / PEG25 tristyrylphenol / tetramethoxy methyl glycolurile] proposed by the company Süd-Chemie.

  The thickening polymers entering as an ingredient in the composition according to the invention may also be chosen from associative polymers comprising at least one ethylenically unsaturated monomer containing a sulphonic group, in free form or partially or totally neutralized and comprising at least one hydrophobic part.

  Preferably, said polymers are partially or completely neutralized with a mineral base (sodium hydroxide, potassium hydroxide, ammonia) or an organic base such as mono-, di- or tri-ethanolamine, aminomethylpropanediol, N-methylglucamine, amino acids basics such as arginine and lysine, and mixtures of these compounds.

  These associative polymers may or may not be crosslinked, and preferably are crosslinked polymers. In this case, the crosslinking agents from at least one monomer having at least two ethylenic unsaturation (carbon-carbon double bond).

  The crosslinking monomers having at least two ethylenic unsaturations are chosen for example from diallyl ether, triallyl cyanurate, diallyl maleate, allyl (meth) acrylate, dipropylene glycol diallyl ether, polyglycol diallyl ether, triethylene glycol divinyl ether, hydroquinone-diallyl ether, tetraallyl-oxethanoyl, tetra- or di-ethylene glycol di (meth) acrylate, triallylamine, tetraallylethylenediamine, trimethylolpropane diallyl ether, trimethylolpropane triacrylate, methylenebis (meth) acrylamide or divinylbenzene allyl ethers of alcohols of the series of sugars, or other allyl- or vinyl-ethers of polyfunctional alcohols, and the allylic esters of phosphoric and / or vinylphosphonic acid derivatives, or mixtures thereof. compounds.

  Methylenebisacrylamide, allyl methacrylate or trimethylol propane triacrylate are more particularly used. The degree of crosslinking generally varies from 0.01 to 10 mol%, relative to the polymer. The ethylenically unsaturated monomers containing a sulfonic group are chosen in particular from vinylsulfonic acid, styrenesulphonic acid, (meth) acrylamido (C1-C22) alkylsulphonic acids and N- (C1-C22) alkyl (meth) acrylamido acids ( C1-C22) alkylsulfonic acids such as undecyl-acrylamido-methanesulfonic acid and their partially or totally neutralized forms. More particularly, it is possible to use (meth) acrylamido (C1-C22) alkylsulphonic acids such as, for example, acrylamido-methanesulfonic acid, acrylamido-ethanesulfonic acid, acrylamido-propanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, methacrylamido-2-methylpropanesulfonic acid, 2-acrylamido-n-butanesulfonic acid, 2-acrylamido-2,4,4-trimethylpentane acid sulphonic acid, 2-methacrylamido-dodecyl-sulphonic acid, 2-acrylamido-2,6-dimethyl-3-heptanesulfonic acid and their partially or completely neutralized forms. 2-Acrylamido-2-methylpropanesulfonic acid (AMPS) is preferably used as well as its partially or completely neutralized forms.

  The amphiphilic polymers present in the composition according to the invention may be chosen from AMPS random amphiphilic polymers modified by reaction with a n-monoalkylamine or a C6-C22 di-n-alkylamine, and such as those described in the application W000 / 31154.

  The hydrophobic monomers which constitute the hydrophobic part of the polymer are nevertheless preferably chosen from acrylates or acrylamides of the following formula (k): Y [CH 2 -CH (R 3) -OR 2 x

  in which R1 and R3, which may be identical or different, denote a hydrogen atom or a linear or branched C1-C6 alkyl radical (preferably methyl); Y is O or NH; R2 denotes a hydrophobic hydrocarbon radical as defined previously; x denotes a number of moles of alkylene oxide and ranges from 0 to 100. The radical R2 is advantageously chosen from linear C6-C18 alkyl radicals (for example n-hexyl, n-octyl, n-decyl, n -hexadecyl, n-dodecyl), branched or cyclic (for example cyclododecane (C12) or adamantane (C10)); perfluorinated C 6 -C 18 alkyl radicals (for example the group of formula û (CH 2) 2 (CF 2) 9-CF 3); the cholesteryl radical (C27) or a cholesteryl ester residue such as the cholesteryl oxyhexanoate group; polycyclic aromatic groups such as naphthalene or pyrene. Among these radicals, linear alkyl radicals, and more particularly the n-dodecyl radical, are more particularly preferred.

  According to one particular form of the invention, the monomer of formula (k) comprises at least one alkylene oxide unit (x> 1) and preferably a polyoxyalkylene chain. The polyoxyalkylene chain is preferably composed of ethylene oxide units and / or propylene oxide units and even more particularly ethylene oxide units. The number of oxyalkylenated units generally varies from 3 to 100 and more preferably from 3 to 50 and even more preferably from 7 to 25.

  The copolymers may also contain other hydrophilic ethylenically unsaturated monomers chosen, for example, from (meth) acrylic acids, their R-substituted alkyl derivatives or their esters obtained with monoalcohols or mono or polyalkylene glycols, the (meth) acrylamides vinylpyrrolidone, maleic anhydride, itaconic acid or maleic acid or mixtures of these compounds.

  These copolymers are described in particular in the documents EP750899, US 5089578, the following Yotaro Morishima publications: Self-assembling amphiphilic polyelectrolytes and their nanostructures - Chinese Journal of Polymer Science Vol. 18, No. 40, (2000), 323-336. ; Miscellanous formation of random copolymers of 2- (acrylamido) -2-methylpropanesulfonate and a non-ionic surfactant macromonomer in water as studied by fluorescence and dynamic light scattering (Macromolecules 2000, Vol. 33, N-3694-3704; Solution properties of miscellence formed by non-ionic moieties covalently bound to a polyelectrolyte: known effects on rheological behavior-Langmuir, 2000, Vol.16, N 12, 5324-5332; Stimuli responsive amphiphilic copolymers of sodium 2- (acrylamido) -2-methylpropanesulfonate and associative macromonomers -Polym. Preprint, Div. Polym. Chem. 1999, 40 (2), 220-221.

  The distribution of the monomers in the copolymer can be statistical or block.

  Among these polymers of this type, mention may be made more specifically of: - crosslinked or non-crosslinked copolymers, neutralized or not, comprising from 15 to 60% by weight of AMPS units and from 40 to 85% by weight of (C8-C16) units ) alkyl (meth) acrylamide or (C 8 -C 16) alkyl (meth) acrylate units with respect to the polymer, such as those described in application EP-A-750 899; terpolymers comprising from 10 to 90 mol% of acrylamide units, from 0.1 to 10 mol% of AMPS units and from 5 to 80 mol% of n- (C6-C18) alkylacrylamide units, such as those described in US-5089578. copolymers of completely neutralized AMPS and of dodecyl methacrylate, as well as copolymers of AMPS and n-dodecylmethacrylamide which are non-crosslinked and crosslinked, such as those described in the Morishima articles cited above.

  More particularly, the copolymers consisting of AMPS units of formula (I) below: ## STR2 ## in which X + has the same definition as above, and of units of formula (I) below: ## EQU1 ##

0 [CH2-CH2-O R4 x

  in which x denotes an integer ranging from 3 to 100, preferably from 5 to 80 and more preferably from 7 to 25; R, has the same meaning as that indicated above in formula (j) and R4 denotes a linear or branched C6-C22 and more preferably C10-C22 alkyl.

15

  Particularly preferred polymers are those wherein x = 25, R 1 is methyl and R 4 is n-dodecyl; they are described in the articles of Morishima mentioned above.

  Polymers for which X + denotes sodium or ammonium are more particularly preferred.

  The polymers of the Genapol range of Hoechst / Clariant can be used in the composition according to the invention. Preferably, the content of non-cellulosic thickening polymer is from 0.01 to 20% by weight and preferably from 0.1 to 5% by weight, relative to the total weight of the dyeing composition. The composition may also comprise at least one oxidation base.

  By way of example, the oxidation bases are chosen from para-phenylenediamines, bis-phenylalkylenediamines, para-aminophenols, ortho-phenylenediamines and

  aminophenols, heterocyclic bases and their addition salts.

  Among the paraphenylenediamines, para-phenylenediamine, paratoluylenediamine, 2-chloro-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine 2,5-dimethyl-para-phenylenediamine, N, N-dimethyl-para-phenylenediamine, N, N-diethyl-para-phenylenediamine, N, N-dipropyl-para-phenylenediamine, 4-amino-N, N-diethyl-3-methylaniline, N, N- bis- (13-hydroxyethyl) paraphenylenediamine, 4-N, N-bis- (13-hydroxyethyl) amino-2-methylaniline, 4-N, N-bis- (13-hydroxyethyl) amino-2-chloroaniline, 2-13-hydroxyethyl paraphenylenediamine, 2-fluoro-para-phenylenediamine, 2-isopropyl-para-phenylenediamine, N- (13-hydroxypropyl) para-phenylenediamine, 2-hydroxymethyl-para-phenylenediamine, N, N-dimethyl-3-methyl-para-phenylenediamine, N, N - (ethyl, 13-hydroxyethyl) paraphenylenediamine, N- (13, y-dihydroxypropy) (1) para-phenylenediamine, N- (4'-aminophenyl) paraphenylenediamine, N-phenyl-para-phenylenediamine, 2-hydroxy-hydroxyethyloxy-para-phenylenediamine, 2- (13-acetylaminoethyloxy) paraphenylenediamine, N- (13-methoxyethyl) para-phenylenediamine, 4-aminophenylpyrrolidine, 2-thienyl paraphenylenediamine, 2-hydroxyethylamino-5-amino toluene, 3-hydroxy-1- (4'-aminophenyl) pyrrolidine and their addition salts with an acid. Of the paraphenylenediamines mentioned above, paraphenylenediamine, paratoluylenediamine, 2-isopropyl paraphenylenediamine, 2-hydroxy-3-hydroxyethyl paraphenylenediamine, 2-hydroxy-hydroxyethyloxy-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6 ethyl paraphenylenediamine, 2,3-dimethyl paraphenylenediamine, N, N-bis- (13-hydroxyethyl) paraphenylenediamine, 2-chloro-para-phenylenediamine, 2-13-acetylaminoethyloxy-para-phenylenediamine, and their addition salts with an acid are particularly preferred. Among the bis-phenylalkylenediamines, mention may be made, by way of example, of N, N'-bis- (13-hydroxyethyl) N, N'-bis- (4'-aminophenyl) 1,3-diamino propanol, N N, N'-bis- (13-hydroxyethyl) N, N'-bis- (4'-aminophenyl) ethylenediamine, N, N'-bis- (4-aminophenyl) tetramethylenediamine, N, N'-bis- ( 13-hydroxyethyl) N, N'-bis (4-aminophenyl) tetramethylenediamine, N, N'-bis- (4-methylaminophenyl) 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. Among para-aminophenols, para-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluoro phenol, 4-amino-3-chlorophenol, 4- amino 3-hydroxymethyl phenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol, 4-amino-2- hydroxyethyl aminomethyl) phenol, 4-amino-2-fluoro phenol, and their addition salts with an acid. Among the ortho-aminophenols, mention may be made, for example, of 2-amino phenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol and 5-acetamido-2-aminophenol, and their addition salts.

  Among the heterocyclic bases that may be mentioned by way of example are pyridine derivatives, pyrimidine derivatives and pyrazole derivatives.

  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, 3,4-diamino pyridine, and their addition salts. Other pyridinic oxidation bases useful in the present invention are the 3-amino pyrazolo [1,5-a] pyridines oxidation bases or their addition salts described for example in the patent application FR 2801308. By way of example, mention may be made of pyrazolo [1,5-a] pyridin-3-ylamine; 2-acetylamino pyrazolo [1,5-a] pyridin-3-ylamine; 2-morpholin-4-yl-pyrazolo [1,5-a] pyridin-3-ylamine; 3-amino-pyrazolo [1,5-a] pyridin-2-carboxylic acid; 2-methoxy-pyrazolo [1,5-a] pyridin-3-ylamino; (3-amino-pyrazolo [1,5-a] pyridin-7-yl) -methanol; 2- (3-Amino-pyrazolo [1,5-a] pyridin-5-yl) -ethanol; 2- (3-Amino-pyrazolo [1,5-a] pyridin-7-yl) -ethanol; (3-Amino-pyrazolo [1,5-a] pyridin-2-yl) -methanol; 3,6-diamino-pyrazolo [1,5-a] pyridine; 3,4-diamino-pyrazolo [1,5-a] pyridine; pyrazolo [1,5-a] pyridine-3,7-diamine; 7-morpholin-4-yl-pyrazolo [1,5-a] pyridin-3-ylamine; pyrazolo [1,5-a] pyridine-3,5-diamine; 5-morpholin-4-yl-pyrazolo [1,5-a] pyridin-3-ylamine; 2 - [(3-amino-pyrazolo [1,5-a] pyridin-5-yl) - (2-hydroxyethyl) amino] ethanol; 2 - [(3-Amino-pyrazolo [1,5-a] pyridin-7-yl) - (2-hydroxyethyl) amino] ethanol; 3-amino-pyrazolo [1,5-a] pyridin-5-ol; 3-amino-pyrazolo [1,5-a] pyridin-4-ol; 3-amino-pyrazolo [1,5-a] pyridin-6-ol; 3-amino-pyrazolo [1,5-a] pyridin-7-ol; as well as their addition salts.

  Among the pyrimidine derivatives, mention may be made of the compounds described, for example, in DE 2359399; JP 88-169571; JP 05-63124; EP 0770375 or patent application WO 96/15765 such as 2,4,5,6-tetraaminopyrimidine, 4-hydroxy 2,5,6-triaminopyrimidine, 2-hydroxy 4,5,6-triaminopyrimidine, , 4-dihydroxy-5,6-diaminopyrimidine, 2,5,6-triaminopyrimidine and their addition salts and tautomeric forms, when tautomeric equilibrium exists. Among the pyrazole derivatives, mention may be made of the compounds described in DE 3843892, DE 4133957 and patent applications WO 94/08969, WO 94/08970, FR-A-2 733 749 and DE 195 43 988 as the 4.5 1-methyl pyrazole, 4,5-diamino-1-yl-hydroxyethyl) pyrazole, 3,4-diamino pyrazole, 4,5-diamino-1- (4'-chlorobenzyl) pyrazole, diamino 1,3-dimethyl pyrazole, 4,5-diamino-3-methyl-1-phenyl pyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 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 amino-1- (13-hydroxyethyl) 3-methylpyrazole, 4,5-diamino-1-ethyl-3-methylpyrazole, 4,5-diamino-1-ethyl-3- (4'-methoxyphenyl) pyrazole, 4, 5-diamino-1-ethyl-3-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-yl-hydroxyethyl) amino-1-methyl pyrazole, and their addition salts. It is also possible to use 4-5-diamino-1-methoxyethyl pyrazole.

  The oxidation base (s) present in the composition of the invention are generally present in an amount ranging from 0.001% to 20% by weight of the total weight of the dyeing composition, preferably ranging from 0.005% to 6%. If the composition contains at least one oxidation base, the composition according to the invention preferably contains one or more couplers conventionally used for dyeing keratinous fibers. Among these couplers, there may be mentioned meta-phenylenediamines, meta-aminphenols, meta-diphenols, naphthalenic couplers, heterocyclic couplers and their addition salts. By way of example, mention may be made of 1,3-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene, 4-chloro-1,3-dihydroxybenzene and 2,4-diamino-1- (B- hydroxyethyloxy) benzene, 2-amino 4- (B-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-naphthol, 6-hydroxyindole, 4-hydroxyindole, 4-hydroxy N-methylindole, 2-amino-3-hydroxypyridine, 6-hydroxybenzomorpholine 3,5-diamino-2,6-dimethoxypyridine, 1-N- (B-hydroxyethyl) amino-3 , 4-methylene dioxybenzene, 2,6-bis- (β-hydroxyethylamino) toluene, 6-hydroxy indoline, 2,6-dihydroxy 4-methyl pyridine, 1-H 3 -methyl pyrazole 5-one, 1-phenyl-3-methyl-pyrazole-5-one, 2,6-dimethyl-pyrazolo [1,5-b] -1,2,4-triazole, 2,6-dimethyl [3,2-c] -l, 2,4-triazole, 6-methyl pyrazolo [1,5 -a] -benzimidazole, their addition salts with an acid, and mixtures thereof. In the composition of the present invention, the coupler or couplers are generally present in an amount ranging from 0.001 to 20% by weight of the total weight of the dyeing composition, preferably ranging from 0.005 to 6%.

  In general, the addition salts of the oxidation bases and couplers that can be used in the context of the invention are chosen especially from the addition salts with an acid such as hydrochlorides, hydrobromides, sulphates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates.

  The dyeing composition in accordance with the invention may also contain one or more additional direct dyes other than the cationic azo direct dyes of formula (I) according to the invention, which may especially be chosen from nitro dyes of the neutral, acidic benzene series. or cationic, neutral, acidic or cationic azo, azomethine or methine direct dyes, neutral, acidic or cationic quinone and, in particular, anthraquinone, naphthoquinone or benzoquinone direct dyes, azine direct dyes, triarylmethane direct dyes, direct dyes indoamines tetraazapentamethine dyes, phenotiazine indigo, xanthene, phenanthridine, phthalocyanine dyes and natural direct dyes, alone or in mixtures.

  Among the benzene direct dyes that may be used according to the invention, the following compounds may be mentioned in a nonlimiting manner: -1,4-diamino-2-nitrobenzene, 1-amino-2-nitro-4-B-hydroxyethylaminobenzene-1-amino -2-nitro-4-bis ((3-hydroxyethyl) -aminobenzene-1,4-bis (3-hydroxyethylamino) -2-nitrobenzene -1-β-hydroxyethylamino-2-nitro-4-bis (β-hydroxyethyl) amino ) -benzene -1-β-hydroxyethylamino-2-nitro-4-aminobenzene -1- [3-hydroxyethylamino-2-nitro-4- (ethyl) (β-hydroxyethyl) -aminobenzene -1-amino-3-methyl- 4- [3-Hydroxyethylamino-6-nitrobenzene -1-amino-2-nitro-4- [3-hydroxyethylamino-5-chlorobenzene -1,2-Diamino-4-nitrobenzene 1-amino-2- [3-hydroxyethylamino] -benzylamino) 5-nitrobenzene 1,2-Bis - ([3-hydroxyethylamino) -4-nitrobenzene -1-amino-2-tris (hydroxymethyl) methylamino-5-nitrobenzene -1-hydroxy-2-amino-5-nitrobenzene 1-Hydroxy-2-amino-4-nitrobenzene -1-hydroxy-3-nitro-4-aminobenzene-1-hydroxy-2-amino-4,6-dinitrobenzene -1- [3-hydroxyethyloxy-2- [3- hyd roxyethylamino-5-nitrobenzene -1-methoxy-2- [3-hydroxyethylamino-5-nitrobenzene -1- [3-hydroxyethyloxy-3-methylamino-4-nitrobenzene 1- [3, y-dihydroxypropyloxy-3-methylamino-4- nitrobenzene -1- [3-hydroxyethylamino-4- (3-yl) dihydroxypropyloxy-2-nitrobenzene -1- [3, y-dihydroxypropylamino-4-trifluoromethyl-2-nitrobenzene -1- [3-hydroxyethylamino-4-trifluoromethyl]; 2-nitrobenzene -1- [3-hydroxyethylamino-3-methyl-2-nitrobenzene -1- [3-aminoethylamino-5-methoxy-2-nitrobenzene -1-hydroxy-2-chloro-6-ethylamino-4-nitrobenzene] 1-Hydroxy-2-chloro-6-amino-4-nitrobenzene -1-hydroxy-6-bis - (3-hydroxyethyl) -amino-3-nitrobenzene -1- [3-hydroxyethylamino-2-nitrobenzene -1- hydroxy-4- [3-hydroxyethylamino-3-nitrobenzene.

  Among the azo, azmethine and methine direct dyes that may be used according to the invention, mention may be made of the cationic dyes described in the patent applications WO 95/15144, WO 95/01772 and EP 714954, the content of which forms an integral part of the invention. Among these compounds, mention may be made in particular of the following dyes: 1,3-dimethyl-2 - [[4- (dimethylamino) phenyl] azo] -1H-imidazolium chloride, 1,3-dimethylchloride 2 - [(4-Aminophenyl) azo] -1H-Imidazolium, - 1-methyl-4 - [(methylphenylhydrazono) methyl] -pyridinium methylsulfate. The following dyes, described in the COLOR INDEX INTERNATIONAL 3rd edition, may also be mentioned among the azo direct dyes: - Disperse Red 17 - Acid Yellow 9 - Acid Black 1 - Basic Red 22 - Basic Red 76 - Basic Yellow 57 -Basic Brown 16 - Acid Yellow 36 - Acid Orange 7 - Acid Red 33 - Acid Red 35 - Basic Brown 17 - Acid Yellow 23 - Acid Orange 24 - Disperse Black 9. Mention may also be made of 1- (4'-aminodiphenylazo) -2-methyl -4bis- (13-hydroxyethyl) aminobenzene and 4-hydroxy-3- (2-methoxyphenylazo) -1-naphthalenesulfonic acid. Among the quinone direct dyes that may be mentioned are the following dyes: - Disperse Red 15 - Solvent Violet 13 - Acid Violet 43 - Disperse Violet 1 - Disperse Violet 4 - Disperse Blue 1 - Disperse Violet 8 - Disperse Blue 3 - Disperse Red 11 - Acid Blue 62 - Disperse Blue 7 - Blue Basic 22 -Disperse Violet 15 - Basic Blue 99 and the following compounds: -1-N-methylmorpholiniumpropylamino-4-hydroxyanthraquinone -1-Aminopropylamino-4-methylaminoanthraquinone -1-Aminopropylaminoanthraquinone -5-13 1-hydroxy-1,4-diaminoanthraquinone -2-aminoethylaminoanthraquinone -1,4-bis - ([3, y-dihydroxypropylamino) -anthraquinone. Among the azine dyes, mention may be made of the following compounds: - Basic Blue 17 - Basic Red 2.

  Among the triarylmethane dyes that can be used according to the invention, mention may be made of the following compounds: - Basic Green 1 - Acid Blue 9 - Basic Violet 3 - Basic Violet 14 - Basic Blue 7 - Acid Violet 49 - Basic Blue 26 - Acid Blue 7 the indoamine dyes that can be used according to the invention include the following compounds: -2- [3-hydroxyethlyamino-5- [bis- ([3-4'-hydroxyethyl) amino] anilino-1,4-benzoquinone -2- [3-hydroxyethylamino-5- (2'-methoxy-4'-amino) anilino-1,4-benzoquinone-3-N (2'-chloro-4'-hydroxy) phenyl-acetylamino-6-methoxy-1, 4-Benzoquinone imine-3-N (3'-Chloro-4'-methylamino) phenyl-ureido-6-methyl-1,4-benzoquinone imine -3- [4'-N- (ethyl, carbamylmethyl) amino] phenyl-ureido-6-methyl-1,4-benzoquinone imine. Among the tetraazapentamethine-type dyes that can be used according to the invention, mention may be made of the following compounds appearing in the table below, An being defined as above: ~ NN ~ NNN \ + '~ N ~ N' NN ~ NAN.NN 1 OMeOMeOMeOMeOMe I NN ~ N ~ 1, N 1 Year 1 Year NN ~ N ~ N, NN OH Year NN ~ N1 \ 1.NN OH Year NN1 \ 1 NNN '1 \ 1, Aq, Year An OH NN'NNN OH Among the natural direct dyes that may be used according to the invention, lawsone, juglone, alizarin, purpurin, carminic acid, kermesic acid, purpurogallin, protocatechaldehyde may be mentioned. indigo, isatin, curcumin, spinulosin, apigenidine. It is also possible to use the extracts or decoctions containing these natural dyes, and in particular poultices or extracts made from henna. The additional direct dye or dyes different from those of formula (I) preferably represent from 0.001 to 20% by weight approximately of the total weight of the composition, and still more preferably from 0.005 to 10% by weight approximately. The composition according to the invention may also comprise at least one oxidizing agent conventionally used for the oxidation dyeing of keratin fibers, such as, for example, hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulfates, peracids and oxidase enzymes, among which mention may be made of peroxidases, 2-electron oxidoreductases such as uricases and 4-electron oxygenases such as laccases. Hydrogen peroxide is particularly preferred.

  The medium suitable for dyeing, also known as a dyeing medium, is a cosmetic medium generally consisting of water or a mixture of water and at least one organic solvent for solubilizing compounds that are not sufficiently soluble in water. water. As organic solvent, there may be mentioned, for example lower alkanols in C 1 -C 4, such as ethanol and isopropanol; polyols and polyol ethers different from the previously described polyols, such as 2-butoxyethanol, propylene glycol, glycerol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and monomethyl ether, and aromatic alcohols such as benzyl alcohol or phenoxyethanol , and their mixtures. The solvents are preferably present in proportions preferably of between 1 and 40% by weight approximately relative to the total weight of the dyeing composition, and even more preferably between 5 and 30% by weight approximately. The dyeing composition complies with the invention may also contain various adjuvants conventionally used in compositions for dyeing hair, such as anionic, cationic, nonionic, amphoteric, zwitterionic surfactants or mixtures thereof, cationic anionic polymers other than those detailed previously, nonionic, amphoteric, zwitterionic or mixtures thereof, inorganic or organic thickeners different from the thickening polymers of the invention, antioxidants, penetrating agents, sequestering agents, perfumes, buffers, dispersing agents, agents such as for example silicones vola non-volatile, modified or unmodified, film-forming agents, ceramides, preservatives and opacifying agents. The adjuvants above are generally present in an amount for each of them between 0.01 and 20% by weight relative to the weight of the composition.

  Of course, one 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 dyeing composition according to the invention are not, or not substantially, impaired by the or the additions envisaged. The pH of the dye composition in accordance with the invention is generally between 2 and 12, preferably between 5 and 11, and even more particularly between 6 and 10.5. It can be adjusted to the desired value by means of acidifying or alkalizing agents usually used for dyeing keratin fibers or else using conventional buffer systems. Among the acidifying agents, mention may be made, by way of example, of mineral or organic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid, lactic acid, sulphonic acids. Among the alkalinizing agents that may be mentioned, for example, ammonia, alkaline carbonates, alkanolamines, such as mono-, di- and triethanolamines and their derivatives, sodium or potassium hydroxides and compounds of formula (II): Ra Rb i NW-NRR d (II) wherein W is a propylene residue optionally substituted with a hydroxyl group or a C1-C4 alkyl radical; Ra, Rb, Rd and Rd, which may be identical or different, represent a hydrogen atom, a C1-C4 alkyl radical or a C1-C4 hydroxyalkyl radical. The dye composition according to the invention may be in various forms, such as in the form of liquids, creams, gels, or in any other form suitable for dyeing human keratinous fibers, and especially the hair.

  The process of the present invention is a process in which the composition according to the present invention as defined above is applied to said dry or wet fibers, said pausing being allowed to proceed and then rinsing said fibers. According to a particular embodiment, the composition of the invention is applied to the keratinous fibers in the presence of an oxidizing agent. The oxidizing agent can be added to the composition of the invention just at the time of use (the so-called resultant composition, ready-to-use composition) or it can be used from a composition oxidizing the container, applied simultaneously or sequentially to the composition of the invention. Preferably, in this particular embodiment, the composition of the invention contains at least one oxidation base.

  The compositions with or without an oxidant are applied to the keratin materials and after a pause of 1 minute to 1 hour, preferably 10 minutes to 30 minutes, the keratinous fibers are rinsed with water, washed with shampoo, rinsed again with water and then dried.

  The oxidizing composition may also contain various adjuvants conventionally used in compositions for dyeing hair and as defined above. The pH of the oxidizing composition containing the oxidizing agent is such that, after mixing with the dyeing composition, the pH of the ready-to-use composition applied to the keratinous fibers preferably varies between 3 and 12 approximately, even more preferably between 5 and 11 and even more particularly between 6 and 10.5. The pH can be adjusted to the desired value by means of acidifying or alkalinizing agents usually used for coloring keratinous fibers and as defined above.

  The ready-to-use composition which is finally applied to the keratin fibers may be in various forms, such as in the form of liquids, creams, gels or in any other form suitable for dyeing keratinous fibers, and including human hair.

  The invention also relates to a multi-compartment device or "kit" of coloring, wherein a first compartment contains the dye composition according to the invention and a second compartment contains an oxidizing agent. This device may be equipped with means for delivering the desired mixture onto the hair, such as the devices described in patent FR-2,586,913.

  The following examples serve to illustrate the invention without being limiting in nature.

EXAMPLE 1

  1. Preparation of compound [i]: N III (nitrosylsulfuric acid) NN HNO 2 NH 2 (A) [I] To 200 g of 40% w / v solution of nitrosylsulfuric acid in sulfuric acid, 100 ml of anhydrous acetic acid and 500 ml of anhydrous propionic acid, and then the mixture is brought to a temperature below 5 C, is gradually introduced into 50 g of 4-aminopyridine. The mixture thus obtained is diluted by addition of 200 ml of propionic acid and 40 ml of acetic acid, and then a solution of 50 g of julolidine in 200 ml of toluene is added dropwise, while maintaining the temperature below 10 ° C. methanol. The reaction mixture is neutralized after 16 hours of reaction at a temperature below 5 C by introduction of 500 mL of water, 300 g of ice and 500 mL of 30% sodium hydroxide. The product (A) is extracted with ethyl acetate and purified by chromatography on silica gel. To 5 g of pure product (A), diluted in 50 ml of dichloromethane, 5 ml of dimethylsulphate are added, and the reaction mixture is then stirred for 2 hours. The medium is concentrated by vacuum distillation of the solvents, and the residue obtained is purified by solubilization in methyl ethyl ketone followed by precipitation with heptane. 7.12 g of a blue powder are thus obtained. The analyzes indicate that it complies with the expected [i].

2. Using the compound wire

  The following dyeing composition (contents expressed in grams of active material) was prepared: Dye obtained above 0.2 Acrylamide / acrylamido-2-methyl propane 4,5-sulfonate copolymer in 40% inverse emulsion in isoparaffin / water; sold by the company Seppic Décylpolyglucoside 9.00 Benzyl alcohol 4.00 Preservatives 0.06 Demineralized water qs 100 The composition was applied on the one hand to locks of natural gray hair with 90% white, on the other hand on strands of gray hair permed 90% white, for 30 minutes at room temperature (20 C).

  After the break time, the locks were rinsed, shampooed and rinsed and dried. They have been dyed in a very aesthetic blue shade

EXAMPLE 2

  1. Preparation of the compound HNO2 (nitrosylsulfuric acid) N

  13.21 g of aminoimidazole suspension in 100 ml of water are added, 30 ml of 35% hydrochloric acid are added, the mixture is cooled to -5 ° C. and then a solution of 7 g of nitrite is added dropwise. of sodium in 10 ml of water, maintaining a temperature below 0 C. 5 g of sulphanilic acid are then added and the mixture is then poured into an acid solution of julolidine obtained beforehand by mixing 8.75 g of julolidine ion exchange, 175 ml of water and 225 ml of acetic acid and 40 g of sodium acetate and maintained at 0 ° C. After 2 h at 5 ° C., the reaction mixture is diluted, brought back to pH 8 by soda. The product (B), precipitated, is filtered and washed with water. (B) are solubilized in 50 mL of dichloromethane; 5 ml of dimethylsulphate and 1.53 g of sodium acetate are successively added. After stirring for 2 h, the mixture is concentrated under vacuum, taken up in 100 ml of methyl ethyl ketone and 100 ml of heptane are then added. The precipitate obtained is washed with heptane and 4.5 g of black violet powder are collected. Resin ion exchange is then carried out to obtain the expected product [ii] in hydrochloride form (2.56 g). The analyzes indicate that it complies with the expected [ii].

2. Use of the compound [iil

  The following dyeing composition (contents expressed in grams of active material) was prepared: Dye obtained above 0.1 Acrylamide / acrylamido-2-methylpropane-3-sulfonate copolymer in 40% inverse emulsion in isoparaffin / water; sold by the company Seppic Decylpolyglucoside 9.00 Benzyl alcohol 4.00 Preservatives 0.06 Demineralized water qs 100 Preservatives qs pH agent qs 7 0.5 Demineralized water qs 100 The composition was applied on the one hand to locks of natural gray hair 90% white, secondly on strands of gray hair 20 permed 90% white, for 30 minutes at room temperature (20 C).

  After the break time, the locks were rinsed, shampooed and rinsed and dried. They were dyed in a very chromatic and unselective violet shade.

Claims (17)

  1. Composition for dyeing human keratin fibers, comprising in a cosmetically acceptable medium, at least one azo cationic compound of formula (I) below: A n N (N) wherein A represents: R2 a N + X-R ' Wherein R 1, R 2, which may be identical or different, represent a C 1 -C 4, preferably C 1 -C 2, alkyl radical, advantageously methyl; a represents the bond with the azo group; X- representing a cosmetically acceptable anion; at least one non-cellulosic thickening polymer.   2. Composition according to the preceding claim, characterized in that the compound of formula (I) corresponds to the following compounds: ## STR1 ## and X- representing a cosmetically acceptable anion.   3. Composition according to any one of claims 1 or 2, characterized in that the thickening polymer is a non-associative polymer.   4. Composition according to claim 3, characterized in that the non-associative thickening polymer is chosen from crosslinked acrylic acid homopolymers, crosslinked homopolymers of 2-acrylamido-2-methyl-propane sulfonic acid and their crosslinked acrylamide copolymers. homopolymers of ammonium acrylate or copolymers of acrylate and ammonium acrylate, nonionic guar gums, biopolysaccharide gums of microbial origin, gums derived from plant exudates, pectins and alginates, alone or in mixtures. X   5. Composition according to any one of claims 1 or 2, characterized in that the thickening polymer is an associative polymer.   6. Composition according to claim 5, characterized in that the associative thickening polymer is chosen from associative polyurethanes, more particularly cationic or nonionic, associative vinyllactams, polyunsaturated associative polyacids, aminoplast-associative ethers, cross-linked homopolymers. 2-acrylamido-2-methylpropanesulphonic acid and their crosslinked acrylamide copolymers, the associative polymers or copolymers comprising at least one ethylenically unsaturated monomer containing a sulfonic group, alone or in mixtures.   7. Composition according to any one of the preceding claims, characterized in that it comprises from 0.001 to 10%, preferably from 0.05 to 2% of direct dye (s) of formula (I) relative to to the total weight of the composition.   8. Composition according to any one of the preceding claims, characterized in that it comprises from 0.01 to 20% by weight and preferably from 0.1 to 5% by weight of thickening polymer, relative to the total weight of the composition.   9. Composition according to any one of the preceding claims, characterized in that it comprises at least one oxidation base chosen from para-phenylenediamines, bis-phenylalkylenediamines, para-aminophenols, ortho-aminophenols, heterocyclic bases and their addition salts.   10. Composition according to the preceding claim, characterized in that it comprises an amount of between 0.001 to 20% by weight and preferably between 0.005 and 6% by weight of base (s) oxidation relative to the total weight of the composition.   11. Composition according to any one of the preceding claims, characterized in that it comprises at least one coupler chosen from meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalenic couplers, heterocyclic couplers and their salts. addition.   12. Composition according to the preceding claim, characterized in that the coupler or couplers are present in an amount of between 0.001 and 20%, preferably between 0.005 and 6% by weight relative to the total weight of the composition. 25 30 35   13. Composition according to any one of the preceding claims, characterized in that it comprises one or more additional direct dyes different from the compounds of formula (I).   14. Composition according to the preceding claim, characterized in that the additional direct dye or dyes are present in an amount of between 0.001 to 20% by weight and preferably between 0.005 and 10% by weight relative to the total weight of the composition.   15. Composition according to any one of the preceding claims, characterized in that it comprises at least one oxidizing agent chosen from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts, peracids and oxidase enzymes, and preferably hydrogen peroxide.   16. A method for dyeing human keratinous fibers, characterized in that the following steps are carried out: the dyeing composition according to one of claims 1 to 15 is applied to the keratin fibers, it is allowed to pause, the fibers are rinsed.   17. Multi-compartment device, characterized in that it comprises a first compartment containing a composition as defined according to one of claims 1 to 14 and a second compartment containing a composition comprising an oxidizing agent.