FR2912908A1 - Composition, useful for coloring human keratinous fibers, preferably hair, comprises at least a cationic azo compound and at least an optionally siliconated cationic polymer with specific charge density - Google Patents

Abstract

Composition (I) for coloring human keratinous fibers, comprises: at least a cationic azo compound (a) and at least an optionally siliconated cationic polymer with specific charge density of less than 8 meq/g. Composition (I) for coloring human keratinous fibers, comprises: at least a cationic azo compound of formula (a) and at least an optionally siliconated cationic polymer with specific charge density of less than 8 meq/g. A : 3H-imidazol-1-ium group of formula (aa) or pyridinium group of formula (bb); R 1, R 21-4C 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

  FIELD OF THE INVENTION The present application relates to a composition for staining human keratinous fibers comprising at least one cationic azo dye with julolidine motif and at least one cationic polymer having a lower charge density. at 8 meq / g, 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 allows a rich palette of colors to be obtained.

  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 coloring molecules having an affinity for the fibers, to be allowed to pause in order to allow the colored molecules to penetrate, by diffusion, into the interior of the body. 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 to have stable dyes in solution allowing access to coloring areas different from those generally achieved in color 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 that induces risks of stains, as well as color change risks over time when we associate together dyes different respective tenacities.

  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 ): AN = N (I) in which A represents: R2 ~ N + X- (la) X- where R ,, R2, identical or not, represent a C1-C4, preferably C1-C2, alkyl radical; advantageously methyl; a represents the bond with the azo group; X- representing a cosmetically acceptable anion; at least one cationic polymer having a charge density of less than 8 meq / g. 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.

  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 containing julolidine unit used in the composition according to the invention corresponds to compounds of the following formula (I): ## STR2 ## in which A represents: R 2 X-X- with R, R 2, which may be identical or different, represent a C 1 -C 4, preferably C 1 -C 2, alkyl radical, advantageously methyl; X- represents a cosmetically acceptable anion chosen, for example, from methosulphate, tosylate, acetate, lactate, citrate, sulfate, carbonate or 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 - X representing a cosmetically acceptable anion. More particularly, X- represents a chloride or methosulphate ion. The dye 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 may 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, precursor non-cationic of A, has the following two formulas: CH3

  In the following, R 1 -HAL signifies a halogen group linked to the alkyl radical, preferably a chloro, bromo or iodo group, or a dialkylsulfato group, preferably dimethylsulfato or diethylsulfato group or else methylsulfonato group ( 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) 4BuNHZ 3 An The diazonium salt 2 of the heteroaromatic amine BNH 2 1 is prepared by classical 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 alkyl sulfate, alkyl halide, alkyl alkyl sulphonate or alkyl aryl sulphonate, to form the compound a cationic azo direct dye with a julolidine motif. 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 and oxidation of the compound 12 obtained to lead to the compound 13 (a cationic azo direct dye julolidine pattern). A. leaving group with leaving group = Cl, Br, I, etc. The reaction to form compound 12 can be carried out in a polar solvent, preferably an alcohol or DMF, at a temperature of 10 ° C. less than 150 ° C., in the presence, if any, of a less nucleophilic base 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 acid medium and at a temperature below 100 ° C. for less than twenty-four 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 cationic polymer with a charge density of less than 8 meq / g.

  The cationic charge density of a polymer corresponds to the number of moles of cationic charges per unit mass of polymer under the conditions where it is totally ionized. It can be determined by calculation if we know the structure of the polymer, that is to say the structure of the monomers constituting the polymer and their molar or weight proportion. It can also be determined experimentally by the Kjeldahl method. Preferably, the cationic polymer has a charge density of between 0.1 and 7.9, preferably between 3 and 7.5.

  This polymer may be silicone or not.

  The cationic polymers that may be used in the context of the invention may be associative cationic polymers or not, as long as they have a charge density of less than 8 meq / g. It is further recalled that in what follows, the term associative polymer, any polymer comprising at least one fatty chain C8-C30, more particularly C10-C30 and whose molecules are capable in the middle of the composition where they are present, to associate with each other or with molecules of other compounds. Among the non-silicone cationic polymers that can be used in the context of the present invention, mention may be made of the following polymers: (1) homopolymers or copolymers derived from acrylic or methacrylic esters or amides and comprising at least one of the units of formulas R3 R13 R3 ùCH2 ù ùCH4 Where ùCH C ùCH2 0 0 = 0 0 = C 0 = 0 0 = 0 0 NH NH XI IA-AAAN RùN + ùR N R4 R R6 / 44 / R2 R2 R1 R5 In which: R3, which may be identical or different, denote a hydrogen atom or a CH3 radical; A, which may be identical or different, represent a linear or branched alkyl group of 1 to 6 carbon atoms, preferably 2 or 3 carbon atoms or a hydroxyalkyl group of 1 to 4 carbon atoms; R4, R5, R6, which may be identical or different, represent an alkyl group having from 1 to 18 carbon atoms or a benzyl radical and preferably an alkyl group having from 1 to 6 carbon atoms; R 1 and R 2, which may be identical or different, represent hydrogen or an alkyl group having from 1 to 6 carbon atoms and preferably methyl or ethyl; X denotes an anion derived from a mineral or organic acid such as a methosulphate anion or a halide such as chloride or bromide.

  The copolymers of family (1) may also contain one or more units derived from monomers which may be chosen from the family of acrylamides, methacrylamides, diacetones acrylamides, acrylamides and methacrylamides substituted on the nitrogen by lower alkyls (C1-C4) , acrylic or methacrylic acids or their esters, vinyllactams such as vinylpyrrolidone or vinylcaprolactam, vinyl esters.

  Thus, among these copolymers of the family (1), mention may be made of: the copolymers of acrylamide and of dimethylaminoethyl methacrylate quaternized with dimethyl sulphate or with a dimethyl halide, such as that sold under the name HERCOFLOC by the company HERCULES the copolymers of acrylamide and of methacryloyloxyethyltrimethylammonium chloride described, for example, in the patent application EP-A-080976 and sold under the name BINA QUAT P 100 by the company CIBA GEIGY, 20-the copolymers of acrylamide and of methosulphate of methacryloyloxyethyltrimethylammonium sold under the name Reten by Hercules, - vinylpyrrolidone / dialkylaminoalkyl acrylate or methacrylate quaternized or otherwise quaternized copolymers. These polymers are described in detail in French Patents 2,077,143 and 2,393,573, the dimethylaminoethyl methacrylate / vinylcaprolactam / vinylpyrrolidone terpolymers, the vinylpyrrolidone / methacrylamidopropyl dimethylamine copolymers, and the quaternized vinylpyrrolidone / dimethylaminopropylmethacrylamide copolymers. . (2) Cationic polysaccharides, especially cationic celluloses and cationic galactomannans. Among the cationic polysaccharides, mention may be made more particularly of cellulose ether derivatives containing quaternary ammonium groups, cationic cellulose copolymers or cellulose derivatives grafted with a water-soluble quaternary ammonium monomer and cationic galactomannan gums.

  The cellulose ether derivatives comprising quaternary ammonium groups described in French Patent 1,492,597. These polymers are also defined in the CTFA dictionary as quaternary ammoniums of hydroxyethylcellulose having reacted with an epoxide substituted with a trimethylammonium group. Cationic cellulose copolymers or cellulose derivatives grafted with a water-soluble quaternary ammonium monomer, are described in particular in US Pat. No. 4 131 576, such as hydroxyalkyl celluloses, such as hydroxymethyl, hydroxyethyl or hydroxypropyl celluloses grafted in particular with a salt of methacryloylethyl trimethylammonium, methacrylmidopropyltrimethylammonium, dimethyl-diallylammonium.

  The cationic galactomannan gums are described more particularly in US Pat. Nos. 3,589,578 and 4,031,307, in particular guar gums containing cationic trialkylammonium groups. For example, guar gums modified with a salt (eg chloride) of 2,3-epoxypropyltrimethylammonium are used. (3) polymers consisting of piperazinyl units and straight or branched chain alkylene or hydroxyalkylene divalent radicals, optionally interrupted by oxygen, sulfur, nitrogen or aromatic or heterocyclic rings, as well as oxidation and / or quaternization of these polymers. Such polymers are in particular described in French Patents 2,162,025 and 2,280,361; (4) water-soluble polyaminoamides prepared in particular by polycondensation of an acidic compound with a polyamine; these polyaminoamides may be crosslinked by an epihalohydrin, a diepoxide, a dianhydride, an unsaturated dianhydride, a bis-unsaturated derivative, a bis-halohydrin, a bis-azetidinium, a bis-haloacyldiamine, a bis-alkyl halide or else by an oligomer resulting from the reaction of a bifunctional compound reactive with a bis-halohydrin, a bis-azetidinium, a bis-haloacyldiamine, a bis-alkyl halide, d epilhalohydrin, diepoxide or bis-unsaturated derivative; the crosslinking agent being used in proportions ranging from 0.025 to 0.35 moles per amine group of the polymaoamide; these polyaminoamides can be alkylated or if they contain one or more tertiary amine functional groups, quaternized. Such polymers are described in particular in French Patents 2,252,840 and 2,368,508;

  (5) polyamino amide derivatives resulting from the condensation of polyalkylene polyamines with polycarboxylic acids followed by alkylation with difunctional agents. Mention may be made, for example, of adipiquadioacylaminohydroxyalkyldialoylene triamine polymers in which the alkyl radical contains from 1 to 4 carbon atoms and preferably denotes methyl, ethyl or propyl. Such polymers are in particular described in French Patent 1,583,363.40. Among these derivatives, mention may be made more particularly of the adipic acid / dimethylaminohydroxypropyl / diethylenetriamine polymers sold under the name "CARTARETINE F, F4 or F8" by SANDOZ. (6) polymers obtained by reacting a polyalkylene polyamine comprising two primary amine groups and at least one secondary amine group with a dicarboxylic acid chosen from diglycolic acid and saturated aliphatic dicarboxylic acids having from 3 to 8 carbon atoms. The molar ratio between the polyalkylene polylamine and the dicarboxylic acid being between 0.8: 1 and 1.4: 1; the polyaminoamide resulting therefrom being reacted with epichlorohydrin in a molar ratio of epichlorohydrin relative to the secondary amine group of the polyaminoamide of between 0.5: 1 and 1.8: 1. Such polymers are described in particular in the patents US 3,227,615 and 2,961,347.

  Polymers of this type are in particular marketed under the name "HERCOSETT 57" by the company Hercules Inc. by the company HERCULES in the case of the adipic acid / epoxypropyl / diethylene-triamine copolymer.

  (7) cyclopolymers of alkyl diallyl amine or of dialkyl diallyl ammonium, such as homopolymers or copolymers comprising, as main constituent of the chain, units of formula (I) or (I '): (CH 2 CR 12 C (R 12) - Wherein k and t are 0 or 1, the sum of k + t being equal to 1, R 12 denotes a hydrogen atom or a methyl radical; R 10 and R 11 independently of the other, denote an alkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group in which the alkyl group preferably has 1 to 5 carbon atoms, a lower amidoalkyl group (C1-C4) or R10 and R 11 may denote, together with the nitrogen atom to which they are attached, heterocyclic groups, such as piperidinyl or morpholinyl; Y- is an anion such as bromide, chloride, acetate, borate, citrate, tartrate, bisulfate, bisulfite, sulfate These polymers are notammen t described in French Patent 2,080,759 and in its certificate of addition 2,190,406. - (CH 2) t - (I) Y - - (CH 2) t - CR C (R 12) - CH 2 - 12 (CH 2) k

  R10 and R11, independently of one another, preferably denote an alkyl group having 1 to 4 carbon atoms. Among the polymers defined above, mention may be made more particularly of the homopolymer of dimethyldiallylammonium chloride sold under the name "Merquat 100" by the company Nalco (and its counterparts of low average molecular weight masses) and the copolymers of sodium chloride. diallyldimethylammonium and acrylamide or (meth) acrylic acid. (8) quaternary diammonium polymers containing repeating units corresponding to the formula: ## STR2 ## wherein: R 13, R 14, R 15 and R 16, which are identical or different; different, represent aliphatic, alicyclic, or arylaliphatic radicals containing from 1 to 20 carbon atoms or lower hydroxyalkylaliphatic radicals, or R13, R14, R15 and R16, together or separately, together with the nitrogen atoms to which they are attached heterocycles optionally containing a second heteroatom other than nitrogen or R13, R14, R15 and R16 represent a linear or branched C1-C6 alkyl radical substituted with a nitrile, ester, acyl, amide or -CO-O-R17 group -D or -CO-NH-R17-D where R17 is alkylene and D is a quaternary ammonium group; Al and B1 represent polymethylene groups containing from 2 to 20 carbon atoms which may be linear or branched, saturated or unsaturated, and may contain, bound to or intercalated in the main chain, one or more aromatic rings, or one or more atoms of oxygen, sulfur or sulfoxide, sulfone, disulfide, amino, alkylamino, hydroxyl, quaternary ammonium, ureido, amide or ester groups, and X- denotes an anion derived from a mineral or organic acid; A1, R13 and R15 can form with the two nitrogen atoms to which they are

  attached a piperazine ring; in addition, if Al denotes a linear or branched, saturated or unsaturated alkylene or hydroxyalkylene radical, B1 may also denote a group (CH2), --CO-D-OC- (CH2) n- in which D denotes: a) a residue of glycol of formula: -OZO-, where Z denotes a linear or branched hydrocarbon radical or a group corresponding to one of the following formulas: - (CH 2 -CH 2 -O) x -CH 2 -CH 2 -; - [CH2-CH (CH3) -O] CH2-CH (CH3) - where x and y denote an integer from 1 to 4, representing a defined and unique degree of polymerization or any number from 1 to 4 representing a degree medium polymerization; b) a bis-secondary diamine residue such as a piperazine derivative; c) a bis-primary diamine residue of formula: -NH-Y-NH-, where Y denotes a linear or branched hydrocarbon radical, or alternatively the divalent radical -CH 2 -CH 2 -S-S-CH 2 -CH 2 -; d) a ureylene group of formula: -NH-CO-NH-; Preferably, X- is an anion such as chloride or bromide.

  These polymers have a number-average molecular weight generally between 1000 and 100,000.

  Polymers of this type are described in French patents 2,320,330, 2,270,846, 2,316,271, 2,336,434 and 2,413,907 and US Patents 2,273,780, 2,375,853, 2,388,614 and 2,454,547. , 3,206,462, 2,261,002, 2,271,378, 3,874,870, 4,001,432, 3,929,990, 3,966,904, 4,005,193, 4,025,617, 4,025,627, 4,025,653, 4,026,945 and 4,027 .020.

  Polymers which consist of repeating units having the formula: ## STR1 ## in which R 1, R 2, R 3 and R 4, which are identical or different, may be used more particularly. denote an alkyl or hydroxyalkyl radical having from 1 to about 4 carbon atoms, n and p are integers ranging from about 2 to about 20, and X- is an anion derived from an inorganic or organic acid.

  A compound of formula (a) which is particularly preferred is that for which R 1, R 2, R 3 and R 4 represent a methyl radical and n = 3, p = 6 and X = Cl, called Hexadimethrine chloride according to the INCI nomenclature (CTFA). (9) quaternary polyammonium polymers comprising units of formula R1 ## STR1 ## wherein R1 is a group of formula (II): ## STR2 ## in which: R18i R19i R20 and R21i are identical or different, represent a hydrogen atom or a methyl, ethyl, propyl, 13-hydroxyethyl, 13-hydroxypropyl or -CH2CH2 (OCH2CH2) POH radical, where p is 0 or to an integer between 1 and 6, with the proviso that R18i R19i R20 and R21 do not simultaneously represent a hydrogen atom, r and s, which may be identical or different, are integers between 1 and 6, q is equal to Or at an integer from 1 to 34, X- is an anion such as a halide, A is a radical of a dihalide or is preferably -CH2-CH2-O-CH2-CH2-.

  Such compounds are described in particular in patent application EP-A-122 324.

  For example, the products "Mirapol A 15", "Mirapol AD1", "Mirapol AZ1" and "Mirapol 175" sold by the company Miranol can be mentioned among them.

  (10) Quaternary polymers of vinylpyrrolidone and vinylimidazole such as, for example, the products sold under the names Luviquat FC 905, FC 550 and FC 370 by the company B.A.S.F.

  (11) Crosslinked polymers of methacryloyloxyalkyl (C1-C4) trialkyl (C1-C4) ammonium salts such as polymers obtained by homopolymerization of dimethylaminoethyl methacrylate quaternized with methyl chloride, or by copolymerization of acrylamide with dimethylaminoethyl methacrylate quaternized by the methyl chloride, homo or copolymerization being followed by crosslinking with an olefinically unsaturated compound, in particular methylenebisacrylamide.

  Other cationic polymers which may be used in the context of the invention are cationic proteins or hydrolysates of cationic proteins, polymers containing vinylpyridine or vinylpyridinium units, condensates of polyamines and of epichlorohydrin, quaternary polyureylenes and derivatives of chitin, especially chitosans or their salts (the usable salts are in particular acetate, lactate, glutamate, gluconate or pyrrolidone carboxylate chitosan). Among these compounds, mention may be made of chitosan having a degree of deacetylation of 90% by weight, the chitosan pyrrolidonecarboxylate sold under the name KYTAMER PC by the company Amerchol.

  Among the cationic polymers that may be used in the context of the invention, mention may also be made of cationic derivatives of associative polyurethanes, such as those whose family has been described in patent application FR 0009609. It may be represented more particularly by the general formula (A). ): RX- (P), - [L- (Y) m] r-L '- (P') P-X'-R '(A) in which: R and R', which are identical or different, represent a hydrophobic group or a hydrogen atom; X and X ', which are identical or different, represent a group comprising an amine functional group which may or may not carry a hydrophobic group, or the group L ", L', L 'and L", which may be identical or different, represent a group derived from a diisocyanate; P and P ', which may be identical or different, represent a group comprising an amine functional group which may or may not carry a hydrophobic group; Y represents a hydrophilic group; r is an integer from 1 to 100, preferably from 1 to 50 and in particular from 1 to 25; n, m, and p are each independently from 0 to 1000; the molecule containing at least one protonated or quaternized amine function and at least one hydrophobic group.

  In a very advantageous embodiment, the only hydrophobic groups of these polyurethanes are the groups R and R 'located at the chain ends.

  According to a first preferred embodiment, the associative polyurethane corresponds to the formula (A) in which R and R 'both independently represent a hydrophobic group; X, X 'each represents a group L "; n and p are between 1 and 1000 and L, L', L", P, P ', Y and m have the meaning indicated in formula (A).

  According to another preferred embodiment of the invention, the associative polyurethane corresponds to the formula (A) in which R and R 'both independently represent a hydrophobic group, X, X' each represent a group L ", n and p is 0, and L, L ', L ", Y and m have the meaning as in formula (A) indicated before.

  The fact that n and p are 0 means that these polymers do not contain units derived from an amine-functional monomer incorporated in the polymer during the polycondensation. The protonated amine functions of these polyurethanes result from the hydrolysis of isocyanate functional groups, in excess, at the end of the chain, followed by the alkylation of the primary amine functions formed by alkylation agents with a hydrophobic group, that is to say ie compounds of the type RQ or R'Q, in which R and R 'are as defined above and Q is a leaving group such as a halide, a sulfate, etc.

  According to another preferred embodiment of the invention, the associative polyurethane corresponds to the formula (A) in which R and R 'both independently represent a hydrophobic group; X and X 'are each independently a group having a quaternary amine; n and p are zero, and L, L ', Y and m have the meaning indicated in formula (A).

  The number average molecular weight of the cationic associative polyurethanes is usually between 400 and 500,000, in particular between 1000 and 400000 and ideally between 1000 and 300000 g / mol. When X and / or X 'denote a group containing a tertiary or quaternary amine, X and / or X' may represent one of the following formulas: R3 where N1R2 is N1 R2 or R2 or R2 for X R1 R1 A R1 Embedded image in which: R 2 represents an alkylene radical having from 1 to 20 carbon atoms, linear or branched, with or without R 1, R 1 a saturated or unsaturated ring, or an arylene group, one or more of the carbon atoms that can be replaced by a heteroatom selected from N, S, O, P; R 3 and R 3, which may be identical or different, denote a linear or branched C 1 -C 30 alkyl or alkenyl radical, an aryl radical, at least one of the carbon atoms may be replaced by a heteroatom chosen from N, S, O, P; A- is a physiologically acceptable counterion. The groups L, L 'and L "represent a group of the formula: wherein Z represents -O-, -S- or -NH-, and R4 represents an alkylene radical having from 1 to 20 carbon atoms. , linear or branched, with or without a saturated or unsaturated ring, an arylene radical, one or more of the carbon atoms may be replaced by a heteroatom selected from N, S, O and P. Where The groups P and P ', comprising an amine function, may represent at least one of the following formulas: ## STR5 ## where R 6 R 6. Wherein R5 and R7 have the same meanings as R8 N or R5CHUR7 R8 ùR5uN + R7 where R6A or R5Ci R7iR6iN + R9A R8iR5iCiR7iR1R6iNiR9AiR6iR8N10a or R5iCH11R8R8; R2 defined previously; R6, R8 and R9 have the same meanings as R1 and R3 defined above; Rio represents an alkylene group, linear or branched, optionally unsaturated and may contain one or more heteroatoms selected from N, O, S and P; A- is a cosmetically acceptable counterion.

  As regards the meaning of Y, the term "hydrophilic group" means a water-soluble polymeric group or not. By way of example, non-polymers include ethylene glycol, diethylene glycol and propylene glycol.

  When it comes, according to a preferred embodiment, a hydrophilic polymer, there may be mentioned by way of example polyethers, sulfonated polyesters, sulfonated polyamides, or a mixture of these polymers. Preferably, the hydrophilic compound is a polyether and especially a poly (ethylene oxide) or poly (propylene oxide).

  The associative polyurethanes of formula (A) are formed from diisocyanates and various compounds having functions with a labile hydrogen. The functions with a labile hydrogen can be alcohol, primary or secondary amine or thiol functions giving, after reaction with the diisocyanate functions, respectively polyurethanes, polyureas and polythioureas. The term "polyurethanes" of the present invention includes these three types of polymers namely polyurethanes themselves, polyureas and polythioureas as well as copolymers thereof.

  A first type of compound used in the preparation of the polyurethane of formula (A) is a compound comprising at least one amine-functional unit. This compound may be multifunctional, but preferentially the compound is difunctional, that is to say that according to a preferred embodiment, this compound comprises two labile hydrogen atoms carried for example by a hydroxyl function, primary amine, secondary amine or thiol. It is also possible to use a mixture of multifunctional and difunctional compounds in which the percentage of multifunctional compounds is low.

  As indicated above, this compound may comprise more than one amine-functional unit. It is then a polymer bearing a repetition of the amine functional unit. This type of compounds can be represented by one of the following formulas: HZ- (P), - ZH, or HZ- (P ') P-ZH in which Z, P, P', n and p are as defined upper. As examples of an amine-functional compound, mention may be made of N-methyldiethanolamine, N-tert-butyl diethanolamine and N-sulfoethyldiethanolamine.

  The second compound used in the preparation of the polyurethane of formula (A) is a diisocyanate corresponding to the formula O = C = N-R 4 -N = C = O, in which R 4 is defined above. Mention may in particular be made of methylenediphenyl diisocyanate, methylene cyclohexane diisocyanate, isophorone diisocyanate, toluene diisocyanate, naphthalene diisocyanate, butane diisocyanate and hexane diisocyanate.

  A third compound used in the preparation of the polyurethane of formula (A) is a hydrophobic compound intended to form the terminal hydrophobic groups of the polymer of formula (A). This compound consists of a hydrophobic group and a function with labile hydrogen, for example a hydroxyl function, primary or secondary amine, or thiol. By way of example, this compound may be a fatty alcohol, such as in particular stearyl alcohol, dodecyl alcohol or decyl alcohol. When this compound comprises a polymer chain, it may be, for example, hydrogenated polybutadiene-hydroxyl. The hydrophobic group of the polyurethane of formula (A) can also result from the quaternization reaction of the tertiary amine of the compound having at least one tertiary amine unit. Thus, the hydrophobic group is introduced by the quaternizing agent. This quaternizing agent is a compound of the type RQ or R'Q, in which R and R 'are as defined above and Q denotes a leaving group such as a halide, a sulphate, etc.

  The cationic associative polyurethane may further comprise a hydrophilic block. This sequence is provided by a fourth type of compound used in the preparation of the polymer. This compound can be multifunctional. It is preferably difunctional. One can also have a mixture where the percentage of multifunctional compound is low.

  The functions with a labile hydrogen are alcohol, primary or secondary amine or thiol functions. This compound may be a polymer terminated at the chain ends by one of these functions with labile hydrogen.

  By way of examples, non-polymers include ethylene glycol, diethylene glycol and propylene glycol. When it is a hydrophilic polymer, mention may be made by way of example of polyethers, sulphonated polyesters, sulphonated polyamides, or a mixture of these polymers. Preferably, the hydrophilic compound is a polyether and especially a poly (ethylene oxide) or poly (propylene oxide).

  The hydrophilic group Y in formula (A) is optional. Indeed, the quaternary or protonated amine functional units may be sufficient to provide the solubility or hydrodispersibility necessary for this type of polymer in an aqueous solution.

  Although the presence of a hydrophilic Y group is optional, cationic associative polyurethanes having such a group are preferred.

  The cationic polymers may also be chosen from cationic associative polyvinyllactams, which may be mentioned, for example, the polymers especially described in FR 0101106. Said polymers are more particularly cationic polymers and comprise: -a) at least one vinyl lactam or alkylvinyllactam type monomer ; b) at least one monomer with the following structures (a) or (b): R3 + CHFC (R), where X (Y) p (CH2-CH2-O) m (CH2-CH (R2) -O) n ( Y,) q Nr R4 (a)

  CHFC (R 1) -CHiXu (Y) p (CH 2 -CH 2 -O) m (CH 2 -CH (R 2) -O) n (Y 1) q (b) in which: X denotes an oxygen atom or a radical NR6, R, and R6 denote, independently of one another, a hydrogen atom or a linear or branched C1-C5 alkyl radical, R2 denotes a linear or branched C1-C4i alkyl radical Z-R5 R3 R 4 and R 5 denote, independently of one another, a hydrogen atom, a linear or branched C 1 -C 30 alkyl radical or a radical of formula (IV): ## STR2 ## R7) -O) R8 (c) Y, Y, and Y2 denote, independently of one another, a linear or branched C2-C16 alkylene radical, R7 denotes a hydrogen atom, or a linear alkyl radical; or branched C1-C4 or a linear or branched hydroxyalkyl radical C1-C4i R8 denotes a hydrogen atom or a linear or branched alkyl radical C, -030, p, q and r designate, independently one of the other, either the zero value or the value 1, m and n designate, independently of the other, an integer ranging from 0 to 100, x denotes an integer ranging from 1 to 100, Z denotes an organic or mineral acid anion, provided that: - at least one of the substituents R3i R4, R5 or R8 denotes a linear or branched C9-C30 alkyl radical, - if m or n is other than zero, then q is equal to 1, - if m or n are equal to zero, then p or q is equal to 0 .

  The poly (vinyllactam) polymers may be crosslinked or uncrosslinked and may also be block polymers.

  Preferably, the Z-counterion of the monomers of formula (b) is chosen from halide ions, phosphate ions, methosulphate ion and tosylate ion.

  Preferably R 3, R 4 and R 5 denote, independently of one another, a hydrogen atom or a linear or branched C 1 -C 0 alkyl radical. More preferably, the monomer b) is a monomer of formula (b) for which, even more preferably, m and n are equal to zero.

  The vinyllactam or alkylvinyllactam monomer is preferably a compound of structure (d): CH (R9) = C (R10) - = O (d) (CH2) S wherein s denotes an integer ranging from 3 to 6 R 9 denotes a hydrogen atom or a C 1 -C 5 alkyl radical, R 10 denotes a hydrogen atom or a C 1 -C 5 alkyl radical, with the proviso that at least one of the radicals R 9 and R 10 denotes a hydrogen atom.

  Even more preferentially, the monomer (d) is vinylpyrrolidone.

  Poly (vinyllactam) polymers may also contain one or more additional monomers, preferably cationic or nonionic.

  As more particularly preferred compounds according to the invention, mention may be made of the following terpolymers comprising at least: a) a monomer of formula (d), b) -a monomer of formula (a) in which p = 1, q R3 and R4 denote, independently of one another, a hydrogen atom or a C1-C5 alkyl radical and R5 denotes an alkyl radical at 09-024 and c) a monomer of formula ( b) in which R3 and R4 denote, independently of one another, a hydrogen atom or a C1-C5 alkyl radical.

  Even more preferentially, terpolymers comprising, by weight, 40 to 95% of monomer (d), 0.1 to 55% of monomer (b) and 0.25 to 50% of monomer (b) are used. Such polymers are described in particular in patent application WO 00/68282, the content of which forms an integral part of the invention. 20 As poly (vinyllactam), in particular using the vinylpyrrolidone / dimethylaminopropylmethacrylamide / dodecyl tosylate diméthylméthacrylamidopropylammonium, vinylpyrrolidone / dimethyl aminopropylmethacrylamide / tosylate cocoyldiméthylméthacrylamido propyl ammonium 25, the vinylpyrrolidone / dimethylaminopropylmethacrylamide / tosylate or chloride lauryldiméthylméthacrylamidopropylammonium. The vinylpyrrolidone / dimethylaminopropyl methacrylamide / lauryl dimethylmethacrylamidopropylammonium terpolymer is proposed in 20% water by ISP under the name STYLEZE W20. The composition may likewise comprise polymers derived from associative celluloses such as: quaternized cationic celluloses modified with groups comprising at least one fatty chain comprising at least 8 carbon atoms, or mixtures thereof, quaternized cationic hydroxyethylcelluloses modified with groups comprising at least one hydrophobic chain, such as alkyl, arylalkyl or alkylaryl groups containing at least 8 carbon atoms, or mixtures thereof. The alkyl radicals carried by the above quaternized celluloses or hydroxyethylcelluloses preferably have from 10 to 30 carbon atoms.

  Examples of C8-C30 hydrophobic chain quaternized alkylhydroxyethylcelluloses are QUATRISOFT LM 200, QUATRISOFT LM-X 529-18-A, QUATRISOFT LM-X 529-18B (C12alkyl) and QUATRISOFT LM-X. 529-8 (C18 alkyl) marketed by the company AMERCHOL and the products CRODACEL QM, CRODACEL QL (C12 alkyl) and CRODACEL QS (C18 alkyl) marketed by the company CRODA.

  It is also possible to use silicone cationic polymers preferably chosen from (i) the compounds corresponding to the following formula (VII): (R 1) a (T) 3-a-Si [OSi (T) 2] n - [OSi ( T) b (R 1) 2-barium-OSi (T) 3-a - (R 1) wherein, T is a hydrogen atom, or a phenyl, or OH, or C 1 -C 8 alkyl radical, and preferably methyl, or C1-C8 alkoxy, and preferably methoxy. a denotes the number 0 or an integer from 1 to 3, and preferably 0, b denotes 0 or 1, and in particular 1, m and n are numbers such that the sum (n + m) may vary in particular from 1 at 2,000 and in particular from 50 to 150, n being able to designate a number from 0 to 1,999 and in particular from 49 to 149 and m being able to designate a number from 1 to 2,000, and especially from 1 to 10; R1 is a monovalent radical of formula -CgH2gL in which q is a number from 2 to 8 and L is an optionally quaternized amino group selected from the groups: -N (R 2) -CH 2 -CH 2 -N (R 2) 2 -N ( R2) 2 -N (R 2) 3 Q- -N (R 2) (H) 2 Q- -N (R 2) 2H Q-N (R 2) -CH 2 -CH 2 -N (R 2) (H) 2 Q- in which R 2 can denote hydrogen, phenyl, benzyl, or a monovalent saturated hydrocarbon radical, for example an alkyl radical having from 1 to 20 carbon atoms and Q - represents a halide ion such as, for example, fluoride, chloride, bromide or iodide .

  A product corresponding to this definition is the polymer referred to in the CTFA dictionary "trimethylsilylamodimethicone", corresponding to the following formula (VIII): CH 3 SiO Si (CH 3) 3 CH 2 CHCH 3 CH 2 NH m CH 2 CH 2 NH 2 in which n and m have the meanings given above [see formula (VII)].

  Such compounds are described, for example, in patent application EP-A-95238; a compound of formula (VIII) is for example sold under the name Q2-8220 by the company OSI. Other products corresponding to this definition are in particular the compounds referred to in the CTFA dictionary, "amodimethicone" and corresponding to the following formula (VI): (CH 3) 3 SiO CH 3 SiO 1 CH 3 n R y 'in which R denotes the radical CH3 or OH, and x 'and y' are molecular weight dependent integers, generally such that said number molecular weight is from about 5,000 to about 500,000; (ii) the compounds corresponding to the following formula (IX): ## STR5 ## wherein R 3 represents a monovalent hydrocarbon radical having from 1 to 18 carbon atoms; carbon atoms, and in particular a C 1 -C 18 alkyl radical, or C 2 -C 18 alkenyl radical R 4 represents a divalent hydrocarbon radical, especially a C 1 -C 18 alkylene radical or a C 1 -C 18 alkyleneoxy radical, and example in Cl-C8; Q- is a halide ion, especially chloride; r represents an average statistical value of 2 to 20 and in particular 2 to 8; s represents a mean statistical value of 20 to 200 and in particular of 20 to 50. Such compounds are described more particularly in US Pat. No. 4,185,087. A compound in this class is that sold by Union Carbide under the name US Pat. denomination "Ucar Silicone ALE 56". (iii) the compounds of the following formula (X): ## STR2 ## in which R 7 R 7 R 7 R 7 R 7 R 7 -N-CH 2 CH 2 R 7 R 7 R 7 R 7 R 7 R 7 R 7 R 7 R6 represents a divalent hydrocarbon radical, in particular a C1-C18 alkylene radical or a divalent C1-C18 alkyleneoxy radical connected to Si by an SiC bond; the radicals R7, which may be identical or different, represent a monovalent hydrocarbon radical having 1 to 18 carbon atoms, a C2-C18 alkenyl radical or a ring comprising 5 or 6 carbon atoms; the radicals R8, which may be identical or different, represent a hydrogen atom, a monovalent hydrocarbon radical having from 1 to 18 carbon atoms, a C2-20 018 alkenyl radical, a -R6-NHCOR7 radical; r represents an average statistical value of 2 to 200; X- is an anion such as a halide ion, especially chloride, or an organic acid salt (acetate). The cationic silicones of formula (X) are for example described in the application EP-A-0530974. this class are the silicones marketed by GOLDSCHMIDT under the names ABIL QUAT 3270, ABIL QUAT 3272, ABIL QUAT 3474.

  When these amino silicones are used, a particularly advantageous embodiment is their use together with cationic and / or nonionic surfactants. By way of example, it is possible to use the product sold under the name "Cationic Emulsion DC 939" by Dow Corning, which comprises, in addition to amodimethicone, a cationic surfactant which is trimethylketylammonium chloride and an agent nonionic surface of formula: C13H27- (OC2H4) 12-OH, known under the name CTFA "trideceth-12".

  Another commercial product that can be used according to the invention is the product sold under the name "Dow Corning Q2 7224" by the company Dow Corning, comprising in combination the trimethylsilylamodimethicone of formula (VIII) described above, a nonionic surfactant of formula: C8H17-C6H4- (OCH2CH2) 40-OH, known under the name CTFA "octoxynol-40", a second nonionic surfactant of the formula: C12H25- (OCH2-CH2) 6-OH, known under the name CTFA "isolaureth-6", and propylene glycol.

  Preferably the cationic polymer is non-silicone, that is to say that it does not contain silicon atoms in its structure. Preferably, the cationic polymer does not contain a C8-C30 fatty chain in its structure.

  Among all the cationic polymers that may be used in the context of the present invention, it is preferred to use quaternary cellulose ether derivatives such as the products sold under the name JR 400 by the company Union Carbide Corporation, cyclopolymers , in particular homopolymers of diallyldimethylammonium salt and copolymers of diallyldimethylammonium salt and of acrylamide, in particular chlorides, sold under the names Merquat 550 and Merquat S by the company Merck, cationic polysaccharides and more particularly modified guar gums by 2,3-epoxypropyltrimethylammonium chloride, sold for example under the name Jaguar C13S by the company Meyhall, homopolymers and optionally crosslinked copolymers of (meth) acryloyloxyethyltrimethylammonium salt sold by the company Allied Colloids in solution. n at 50% in mineral oil under the trade names SALCARE SC92 (crosslinked copolymer of methacryloyloxyethyltrimethylammonium chloride and acrylamide) and SALCARE SC95 (crosslinked homopolymer of methacryloyloxyethyltrimethylammonium chloride), the quaternary copolymers of vinylpyrrolidone and of salt imidazole vinyl such as the products sold by BASF under the names Luviquat FC 370, Lucquat FC 550, Luviquat FC 905 and Luviquat HM-552.

  Preferably, the content of cationic polymer represents 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-aminophenols, heterocyclic bases and their addition salts.

  Among the paraphenylenediamines, there may be mentioned, for example, para-phenylenediamine, paratoluylenediamine, 2-chloro-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, 2,6-dimethyl paraphenylenediamine, 2,6-diethyl paraphenylenediamine, 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, γ-dihydroxypropyl) paraphenylenediamine, N- (4'-aminophenyl) paraphenylenediamine, N-phenyl paraphenylenediamine, 2-13-hydroxyethyloxy paraphenylenediamine, 2-13-acetylaminoethyloxy para-phenylenediamine, N- (13-methoxyethyl) paraphenylenediamine, 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- (R) 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-diaminopyridine, 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-aminopyrazolo [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] pyridine-4-01; 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, 2 , 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 1 - ([3-hydroxyethyl) 3-methylpyrazole, 4,5-diamino-1-ethyl-3-methylpyrazole, 4,5-diamino-1-ethyl-3- (4'-methoxyphenyl) pyrazole, 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 - ([3-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-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- (13-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] -1, 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-B-hydroxyethylamino-2-nitro-4-bis (13-hydroxyethylamino) -1-B-hydroxyethylamino-2-nitro-4-aminobenzene -1-13-hydroxyethylamino-2-nitro-4- (ethyl) (B-hydroxyethyl) -aminobenzene -1-amino-3-methyl-4- benzene 13-hydroxyethylamino-6-nitrobenzene -1-amino-2-nitro-4-13-hydroxyethylamino-5-chlorobenzene -1,2-Diamino-4-nitrobenzene 1-amino-2-13-hydroxyethylamino-5-nitrobenzene 1, 2-Bis- (13-hydroxyethylamino) -4-nitrobenzene -1-amino-2-tris (hydroxymethyl) methylamino-5-nitrobenzene -1-hydroxy-2-amino-5-nitrobenzene-1-hydroxy-2-hydroxy amino-4-nitrobenzene -1-Hydroxy-3-nitro-4-aminobenzene-1-Hydroxy-2-amino-4,6-dinitrobenzene -1-13-hydroxyethyloxy-2-13-hydro 1-Methoxy-2-13-hydroxyethylamino-5-nitrobenzene -1-13-hydroxyethyloxy-3-methylamino-4-nitrobenzene -1,3-dihydroxypropyloxy-3-methylamino-4-nitrobenzene -1-methyl-5-amino-5-nitrobenzene 1-hydroxyethylamino-4- (3-yl) dihydroxypropyloxy-2-nitrobenzene-1,3-yl dihydroxypropylamino-4-trifluoromethyl-2-nitrobenzene -1-13-hydroxyethylamino-4-trifluoromethyl-2-nitrobenzene -1- 13-Hydroxyethylamino-3-methyl-2-nitrobenzene -1-13-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- (13-hydroxyethyl) -amino-3-nitrobenzene -1-13-hydroxyethylamino-2-nitrobenzene -1-hydroxy-4-13-hydroxyethylamino-3- nitrobenzene. Among the azo, azomethine and merino direct dyes that may be used according to the invention, mention may be made of the cationic dyes described in 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-03-hydroxyethyl) aminobenzene and 4-hydroxy-3- (2-methoxyphenylazo) -1-naphthalene sulfonic acid. Among the quinone direct dyes, the following dyes may be mentioned: Disperse Red 15 25 - Solvent Violet 13 - Acid Violet 43 - Disperse Violet 1 - Disperse Violet 4 - Disperse Blue 1 30 - Disperse Violet 8 - Disperse Blue 3 - Disperse Red 11 - Acid Blue 62 - Disperse Blue 7 35 - Basic Blue 22 - Disperse Violet 15 - Basic Blue 99 and the following compounds: -1-N-methylmorpholiniumpropylamino-4-hydroxyanthraquinone 40 -1-Aminopropylamino-4-methylaminoanthraquinone -1-Aminopropylaminoanthraquinone - 5-13-hydroxyethyl-1,4-diaminoanthraquinone -2-amino-amino-aminoanthraquinone -1,4-bis (13, -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 The indoamino 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: ## STR1 ## ## STR1 ## N N + N N N N N N N N NN N N N N N N N N N N N N N N N N N N N NNNNNNNNNNNNNNNNNNNN NNN OH NNN OH NN Among the natural direct dyes that can be used according to the invention, mention may be made of lawsone, juglone, alizarin, purpurin, carminic acid, kermesic acid, purpurogalline, protocatechaldehyde, 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 as perborates and persulfates, peracids and oxidase enzymes among which we may mention 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 dye composition, and even more preferably between 5 and 30% by weight approximately.

  The dyeing composition in accordance with the invention may also contain various adjuvants conventionally used in hair dyeing compositions, such as anionic, cationic, nonionic, amphoteric or zwitterionic surfactants or mixtures thereof, anionic and nonionic polymers, amphoteric, zwitterionic or mixtures thereof, inorganic or organic thickeners, and in particular anionic, nonionic and amphoteric associative thickeners, antioxidants, penetrating 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 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 \ R b NW-NR ~ Rd (II) wherein W is a propylene residue optionally substituted by a hydroxyl group or a C 1 -C 4 alkyl radical; Ra, Rb, R, 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 with water. again to the 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, more preferably 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 basifying agents usually used for coloring the 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 coloring the keratinous fibers, and especially 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 the yarn compound: HNO 2 (nitrosylsulfuric acid) NH 2 (A) [I]

  To 200 g of 40% w / v solution of nitrosylsulphuric acid in sulfuric acid is added 100 ml of anhydrous acetic acid and 500 ml of anhydrous propionic acid, and the mixture is then brought to a temperature of less than 5. C., 50 g of 4-aminopyridine are gradually introduced. 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. Use of Compound [i] The following dyeing composition was prepared (contents expressed in grams of active material): Dyestuff obtained above 0.1 Homopolymer of diallyldimethyl-ammonium chloride sold under the name Merquat 100 Hydroxyethylcellulose (MM 720.00) 0.72 Decylpolyglucoside 9.00 Benzyl alcohol 4.00 Preservatives 0.06 Demineralised 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 [11 HNO 2 (nitrosylsulfuric acid)] HN NN IIi To 13.21 g of aminoimidazole suspension in 100 ml of water, 30 ml of 35% hydrochloric acid are added and the mixture is cooled to - 5 g, then a solution of 7 g of sodium nitrite in 10 ml of water is added dropwise, keeping an N-ion exchange resin at a temperature below 0 ° C. 5 g of sulphanilic acid and then the mixture is poured on an acid solution of julolidine obtained beforehand by mixing 8.75 g of julolidine, 175 ml of water and 225 ml of acetic acid and 40 g of sodium acetate and kept at 0 ° C. After 2 h at 5 ° C., the reaction mixture is diluted, brought to pH 8 with sodium hydroxide, the precipitated product (B) is filtered and washed with water. 50 ml of dichloromethane are successively added: 5 ml of dimethylsulphate and 1.53 g of sodium acetate are added successively After stirring for 2 hours, the mixture is concentrated under vacuum, taken up in 100 mL of methyl ethyl ketone and then 100 mL of heptane is 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

  The following dyeing composition (contents expressed in grams of active material) was prepared: Dye obtained above 0.1 Hexadimethrin chloride known under the name 3 Mexomere PO at 60% in water Hydroxyethylcellulose (MW of 720.00) 0.72 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 with 90% white, on the other hand on locks of gray hair permed 90% white, for 30 minutes at room temperature (20 C).

  After the break time, the locks were rinsed, shampooed and then rinsed and dried. They were dyed in a very chromatic violet shade and selectively. 20

Claims (18)

  1. Composition for dyeing human keratinous fibers, comprising in a cosmetically acceptable medium, at least one azo cationic compound of formula (I) below: ## STR1 ## wherein A represents: R2 a ~ N + X X- (la) (Ib) where R ,, R2, identical or not, represent a C1-C4 alkyl radical, preferably C1-C2, advantageously methyl; a represents the bond with the azo group; X- representing a cosmetically acceptable anion; At least one cationic polymer, silicone or not, with a charge density of less than 8 meq / g.   2. Composition according to the preceding claim, characterized in that the compound of formula (I) corresponds to the following compounds: ## STR2 ## X and X- representing a cosmetically acceptable anion.   3. Composition according to any one of claims 1 or 2, characterized in that the cationic polymer has a charge density of between 0.1 and 7.9, preferably between 3 and 7.5.   4. Composition according to any one of the preceding claims, characterized in that the cationic polymer is chosen from non-silicone polymers. 30   5. Composition according to the preceding claim, characterized in that the cationic polymer is chosen from the following non-silicone polymers: (1) homopolymers or copolymers derived from acrylic or methacrylic esters or amides and comprising at least one of the following units of formula: in which: R3, which may be identical or different, denote a hydrogen atom or a CH3 radical; A, which may be identical or different, represent a linear or branched alkyl group of 1 to 6 carbon atoms, preferably 2 or 3 carbon atoms or a hydroxyalkyl group of 1 to 4 carbon atoms; R4, R5, R6, which may be identical or different, represent an alkyl group having from 1 to 18 carbon atoms or a benzyl radical and preferably an alkyl group having from 1 to 6 carbon atoms; R 1 and R 2, which are identical or different, represent hydrogen or an alkyl group having from 1 to 6 carbon atoms and preferably methyl or ethyl; X denotes an anion derived from a mineral or organic acid such as a methosulphate anion or a halide such as chloride or bromide; (2) cationic polysaccharides; (3) polymers consisting of piperazinyl units and straight or branched chain alkylene or hydroxyalkylene divalent radicals, optionally interrupted by oxygen, sulfur, nitrogen or aromatic or heterocyclic rings, as well as oxidation and / or quaternization of these polymers; (4) water-soluble polyaminoamides prepared in particular by polycondensation of an acidic compound with a polyamine; (5) polyamino amide derivatives resulting from the condensation of polyalkylene polyamines with polycarboxylic acids followed by alkylation with difunctional agents; Embedded image The polymers obtained by reaction of a polyalkylene polyamine containing two primary amine groups and at least one amine group are defined as follows: ## STR2 ## secondary with a dicarboxylic acid; (7) cyclopolymers of alkyl diallyl amine or of dialkyl diallyl ammonium (8) quaternary diammonium polymers containing recurring units corresponding to the formula: ## STR2 ## formula (II) in which: R13, R14, R15 and R16i, which are identical or different, represent aliphatic, alicyclic or arylaliphatic radicals containing from 1 to 20 carbon atoms or lower hydroxyalkylaliphatic radicals, or R13, R14, R15 and R16i together or separately , together with the nitrogen atoms to which they are attached, are heterocyclic rings optionally containing a second heteroatom other than nitrogen or R13i Rio, Ri5 and R16 represent a linear or branched C1-C6 alkyl radical substituted with a nitrile or ester group; acyl, amide or -CO-O-R17-D or -CO-NH-R17-D wherein R17 is alkylene and D is a quaternary ammonium group; Al and B1 represent polymethylene groups containing from 2 to 20 carbon atoms which may be linear or branched, saturated or unsaturated, and may contain, bound to or intercalated in the main chain, one or more aromatic rings, or one or more atoms of oxygen, sulfur or sulfoxide, sulfone, disulfide, amino, alkylamino, hydroxyl, quaternary ammonium, ureido, amide or ester groups, and X- denotes an anion derived from a mineral or organic acid; A1, R13 and R15 can form with the two nitrogen atoms to which they are attached a piperazine ring; in addition, if Al denotes a linear or branched, saturated or unsaturated alkylene or hydroxyalkylene radical, B1 may also denote a group (CH2), --CO-D-OC- (CH2) n- in which D denotes: a) a residue of glycol of formula: -OZO-, where Z denotes a linear or branched hydrocarbon radical or a group corresponding to one of the following formulas: - (CH 2 -CH 2 -O) X CH 2 -CH 2 - - [CH 2 -CH (CH 3) -O] CH 2 -CH (CH 3) -where x and y denote an integer of 1 to 4, representing a defined and unique degree of polymerization or any number of 1 to 4 representing an average degree of polymerization; b) a bis-secondary diamine residue such as a piperazine derivative; c) a bis-primary diamine residue of formula: -NH-Y-NH-, where Y denotes a linear or branched hydrocarbon radical, or alternatively the divalent radical -CH 2 -CH 2 -S-S-CH 2 -CH 2 -; d) a ureylene group of formula: -NH-CO-NH-; (9) quaternary polyammonium polymers comprising units of formula (III): R 18 R 20 --N (CH 2) n -NH-CO- (CH 2) q CO-NH- (CH 2) sN A X-1 R 19 (III) in which: R18, R19, R20 and R21, which may be identical or different, represent a hydrogen atom or a methyl, ethyl, propyl, 13-hydroxyethyl, 13-hydroxypropyl or -CH2CH2 (OCH2CH2) POH radical, where p is equal to at 0 or an integer between 1 and 6, with the proviso that R18, R19, R20 and R21 do not simultaneously represent a hydrogen atom, r and s, which may be identical or different, are integers between 1 and 6 q is 0 or an integer from 1 to 34, X- is an anion such as a halide, A is a radical of a dihalide, or is preferably -CH2-CH2-O-CH2-CH2 -; (10) Quaternary polymers of vinylpyrrolidone and vinylimidazole; (11) crosslinked polymers of methacryloyloxyalkyl (C1-C4) trialkyl (C1-C4) ammonium salts; (12) cationic proteins or cationic protein hydrolysates, polyalkyleneimines, polymers containing vinylpyridine or vinylpyridinium units, condensates of polyamines and epichlorohydrin, quaternary polyureylenes and chitin derivatives.   6. Composition according to any one of the preceding claims, characterized in that the cationic polymer is chosen from silicone cationic polymers. x- R21   7. Composition according to the preceding claim, characterized in that the cationic polymer is chosen from: (i) the compounds corresponding to the following formula (VII): (R1) a (T) 3-a-Si [OSi (T) 2] n - [Osi (T) b (R 1) 2-b] m -OS 1 (T) 3-a - (R 1) wherein, T is a hydrogen atom, or a phenyl radical, or OH, or C1-C8alkyl or C1-C8alkoxy a is the number 0 or an integer of 1 to 3; b is 0 or 1; m and n are numbers such that the sum (n + m) may vary in particular from 1 to 2000, n being able to designate a number from 0 to 1,999 and m being able to designate a number from 1 to 2,000; R1 is a monovalent radical of formula -CgH2gL in which q is a number from 2 to 8 and L is an optionally quaternized amino group selected from the groups: -N (R 2) -CH 2 -CH 2 -N (R 2) 2 -N ( R2) 2 -N (R2) 3 Q- -N (R2) (H) 2 Q- -N (R2) 2H Q- -N (R2) -CH2-CH2-N (R2) (H) 2 Q- wherein R2 may be hydrogen, phenyl, benzyl, or a monovalent saturated hydrocarbon radical and Q- is a halide ion; (ii) the compounds corresponding to the following formula (IX): ## STR2 ## wherein R 3 represents a hydrocarbon radical; R 3 R 3 R 3 R 4 RCH 2 CHOH N / R 3 R 3 R 3 monovalent having from 1 to 18 carbon atoms; R4 represents a divalent hydrocarbon radical, especially a C1-C18 alkylene radical or a divalent C1-C18 alkyleneoxy radical; Q- is a halide ion; r represents an average statistical value of 2 to 20; 35 s represents an average statistical value of 20 to 200. (iii) compounds of the following formula (X): ## STR2 ## R 7 R 8 -N -CH CHOH-CH 2 -R 6 R 7 R 7 R 7 Si-R 6 CH 2 -CHOH-CH 2 Nt R 8 R 7 Wherein: R6 represents a divalent hydrocarbon radical, especially a C1-C18 alkylene radical or a divalent C1-C18 alkyleneoxy radical connected to Si by an SiC bond; the radicals R7, which are identical or different, represent a monovalent hydrocarbon radical; having from 1 to 18 carbon atoms, a C 2 -C 18 alkenyl radical or a ring containing 5 or 6 carbon atoms; the radicals R8, which may be identical or different, represent a hydrogen atom, a monovalent hydrocarbon radical having 1 to 18 carbon atoms, a C2-C18 alkenyl radical or a -R6-NHCOR7 radical; r represents an average statistical value of 2 to 200; X- is an anion.   8. 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.   9. 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 cationic polymer, relative to the total weight of the composition.   10. 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.   11. 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 oxidation base (s) relative to the total weight of the composition.   12. 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.   13. 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.   14. 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).   15. 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.   16. 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.   17. A method for staining human keratinous fibers, characterized in that the following steps are carried out: the dyeing composition according to one of claims 1 to 16 is applied to the keratinous fibers, it is allowed to pausing, the fibers are rinsed.   18. Multi-compartment device, characterized in that it comprises a first compartment containing a composition as defined according to one of claims 1 to 15 and a second compartment containing a composition comprising an oxidizing agent.