FR2920091A1 - Composition for coloring keratin fibers, preferably human hair, comprises amino pyrazolopyridine oxidation bases, couplers and polyols comprising hydrocarbon chain carrying two hydroxyl functions, where the chain is free from ether function - Google Patents

Abstract

Composition for coloring keratin fibers, comprises one or more amino pyrazolopyridine oxidation bases (I) and their acid or base addition salts, one or more couplers, and one or more 4-30C polyols comprising a hydrocarbon chain carrying at least two hydroxyl functions, where the chain is free from ether function, in a coloring medium. Composition for coloring keratin fibers, comprises one or more amino pyrazolopyridine oxidation bases of formula (I) and their acid or base addition salts, one or more couplers, and one or more 4-30C polyols comprising a hydrocarbon chain carrying at least two hydroxyl functions, where the chain is free from ether function, in a coloring medium. R 1-R 5H, halo, -NHSO 3H, OH, (1-4C)alkyl, (1-4C)alkoxy, (1-4C)alkylthio, mono(1-4C)alkylamino, di(1-4C)alkylamino (where the two alkyl groups are joined with N atom to form a cycle (interrupted by N, O or S)), heterocycle, NO 2, phenyl, carbonyl, alkoxy(1-4C)carbonyl, carboxamido, CN, amino, sulfonyl, -CO 2H, -SO 3H, - PO 3H 2, -PO 4H 2or hydrocarbon compound of formula (-Q-C(=R 1 c)-Y 1); R 1 cO or N; Q : O, NH or NH(1-4c)alkyl; and Y 1OH, amino, 1-4C alkyl, (1-4C)alkoxy, (1-4C)alkylamino or di(1-4C)alkylamino. Independent claims are included for: (1) a process for oxidation coloring of keratin fibers comprising applying the composition on the fibers in the presence of oxidizing agent; and (2) a device with several compartments comprising a first compartment containing a coloring composition and a second compartment containing an oxidizing agent. [Image].

Description

TINCTORIAL COMPOSITION COMPRISING AN OXIDATION BASE

  The subject of the invention is a dyeing composition comprising at least one aminopyrazolopyridine base, a coupler and a particular polyol. BACKGROUND OF THE INVENTION The subject of the invention is also the use of this composition for dyeing keratinous fibers as well as the dyeing process using this composition. It is known to dye keratinous fibers and in particular human hair with dye compositions containing oxidation dye precursors, generally known as oxidation bases, such as ortho or para-phenylenediamines, ortho or para-aminophenols and heterocyclic compounds. These oxidation bases are colorless or weakly colored compounds which, when combined with oxidizing products, can give rise to colored compounds by a process of oxidative condensation. It is also known that the shades obtained with these oxidation bases can be varied by combining them with couplers or color modifiers, the latter being chosen in particular from aromatic meta-diamines, meta-aminophenols, meta-diphenols and certain heterocyclic compounds such as than indolic compounds. The variety of molecules involved in oxidation bases and couplers, allows to obtain a rich palette of colors.

  The so-called "permanent" coloration obtained with these oxidation dyes must also meet a certain number of requirements. Thus, it must be harmless from the toxicological point of view, it must make it possible to obtain shades in the desired intensity and to have good resistance to external agents such as light, bad weather, washing, permanent undulations, sweating and friction.

  The dyes must also make it possible to cover the white hair, and finally be the least selective possible, that is to say, to obtain the lowest possible color differences throughout the same keratin fiber, which is in general differently sensitized (ie damaged) between its point and its root. It is already known to use aminopyrazolopyridine oxidation bases for dyeing keratin fibers, particularly in the patent application FR 2 801 308. These bases make it possible to obtain various shades. Furthermore, it is known to use, in the field of dyeing keratinous fibers, dyeing compositions using solvents of polyol type, in particular in document FR2886139.

  The object of the present invention is to obtain a composition for hair dyeing which has enhanced dyeing properties in terms of power, selectivity and resistance to external agents. This object is achieved with the present invention which relates to a dyeing composition comprising, in a dyeing medium suitable for dyeing keratin fibers, one or more aminopyrazolopyridine oxidation bases of formula (I), R 2 NH R 1 ( In which: R 1, R 2, R 3, R 4 and R 5, which may be identical or different, represent a hydrogen or halogen atom; a radical -NHSO3H; a hydroxyl radical; a (C 1 -C 4) alkyl radical; a (C 1 -C 4) alkoxy radical; a (C 1 -C 4) alkylthio radical; mono (C 1 -C 4) alkylamino; a di (C 1 -C 4) alkylamino radical in which the two alkyl groups together with the nitrogen atom to which they are attached form a ring which can be interrupted by one or more nitrogen, oxygen or sulfur; a heterocycle; a nitro radical; a phenyl radical; a carbonyl radical; a (C 1 -C 4) alkoxycarbonyl radical; a carboxamido radical; a cyano radical; an amino radical; a sulfonyl radical; a radical -CO2H, a radical -SO3H; a radical -PO3H2; a radical -PO4H2; or a group: R "'QY in which R" "represents an oxygen or nitrogen atom, Q 20 represents an oxygen atom, an NH or NH (C 1 -C 4) alkyl group, and Y represents a hydroxyl, amino, C 1 -C 4 alkyl, (C 1 -C 4) alkoxy, (C 1 -C 4) alkylamino, or di (C 1 -C 4) alkylamino radical, and their addition salts with an acid or a base one or more couplers, and one or more C4-C30 polyols comprising a linear, branched or cyclic, saturated or unsaturated hydrocarbon-based chain carrying at least two hydroxyl functions, said chain being free of ether function.

  The invention also relates to a dyeing process using this composition. Another subject of the invention is the use of the composition of the present invention for dyeing keratinous fibers, in particular human keratinous fibers such as the hair. The composition of the present invention makes it possible in particular to obtain a keratinous fiber coloring composition which is suitable for use in oxidation dyeing and makes it possible to obtain a coloration with varied shades, powerful, aesthetic, not very selective and resistant well to various attacks that hair can suffer such as shampoos, light, sweat and permanent deformities. It should be noted that in what follows, and unless otherwise indicated, the boundaries of a domain of values are included in this area. In the compounds of formula (I) above, the alkyl expression used for the alkyl radicals as well as for the groups comprising an alkyl part, signifies a carbon chain, linear or branched, containing from 1 to 4 carbon atoms, substituted or unsubstituted by one or more heterocycles, or by one or more phenyl groups or by one or more groups selected from halogen atoms such as chlorine, bromine, iodine and fluorine; hydroxyl, alkoxyl, amino, carbonyl, carboxamido, sulphonyl, -CO2H, -SO3H, -PO3H2, -PO4H2, -NHSO3H, sulphonamide, (C1-C4) alkylamino, trialkyl (C1-C4) ammonium radicals, or moreover, by a (C 1 -C 4) -alkylamino radical in which the two alkyl groups can form, together with the nitrogen atom of said (C 1 -C 4) -alkylamino group to which they are bonded, a cycle which can be interrupted by one or more atoms of nitrogen, oxygen or sulfur. Similarly, according to the invention, the alkoxy expression used for the alkoxy radicals as well as for the groups comprising an alkoxy part, signifies a linear or branched O-carbon chain containing from 1 to 4 carbon, substituted or unsubstituted by one or more groups selected from heterocycles; halogen atoms such as chlorine, bromine, iodine and fluorine; hydroxyl, amino, carbonyl, carboxamido, sulfonyl, -CO2H, -SO3H, -PO3H2, -PO4H2, -NHSO3H, sulfonamide, (C1-C4) alkylamino, trialkyl (C1-C4) ammonium radicals, or else by a dialkyl (C 1 -C 4) amino radical in which the two alkyl groups can form, together with the nitrogen atom of said dialkyl (C 1 -C 4) amino group to which they are attached, a ring which can be interrupted by a or several atoms of nitrogen, oxygen or sulfur. According to the invention, the term "heterocycle" means an aromatic or non-aromatic ring containing 5, 6, 7 or 8 vertices, and from 1 to 3 heteroatoms chosen from nitrogen, sulfur and oxygen atoms. These heterocycles may be fused to other heterocycles or to a phenyl group. They may be substituted by a halogen atom; a (C 1 -C 4) alkyl radical; a (C 1 -C 4) alkoxy radical; a hydroxyl radical; an amino radical; a (C 1 -C 4) alkylamino radical; di (C 1 -C 4) alkylamino wherein the two alkyl groups together with the nitrogen atom to which they are attached form a ring which can be interrupted by one or more nitrogen, oxygen or sulfur atoms. These heterocycles may, in addition, be quaternized with a (C 1 -C 4) alkyl radical. Among these optionally fused heterocycles, there may be mentioned by way of example the rings: thiadiazole, triazole, isoxazole, oxazole, azaphosphole, thiazole, isothiazole, imidazole, pyrazole, triazine, thiazine, pyrazine, pyridazine, pyrimidine, pyridine, diazepine, oxazepine, benzotriazole, benzoxazole, benzimidazole, benzothiazole, morpholine, piperidine, piperazine, azetidine, pyrrolidine, aziridine, 3- (2-hydroxyethyl) benzothiazol-3-ium, and 1- (2-hydroxyethyl) pyridinium. According to the invention, phenyl is understood to mean a phenyl radical which is unsubstituted or substituted with one or more cyano, carbonyl, carboxamido, sulphonyl, -CO2H, -SO3H, -PO3H2, -PO4H2, hydroxyl, amino or monoalkyl (C -C4) amino, or dialkyl (C1-C4) amino wherein the two alkyl groups can form, together with the nitrogen atom of said dialkyl (C 1 -C 4) amino group to which they are attached, a ring which can be interrupted by one or more atoms of nitrogen, oxygen or sulfur. Among the QY groups, there may be mentioned the acetamide, dimethylurea, 0-methylcarbamate, methylcarbonate, N-dimethylcarbamate and the esters groups. Among the compounds of formula (I) above, 3-amino pyrazolo is preferred. [1,5-a] pyridines corresponding to the following sub-formula, and their addition salts with an acid or with a base: in which: R 1, R 2, R 3, which may be identical or different, represent a hydrogen atom; hydrogen, halogen, a hydroxyl radical, a (C 1 -C 4) alkyl radical, a (C 1 -C 4) alkylthio radical, a (C 1 -C 4) alkoxy radical, a -NHSO 3 H radical or an amino radical; a (C 1 -C 4) alkylamino radical; a di (C 1 -C 4) alkylamino radical in which the two alkyl groups may together with the nitrogen atom to which they are attached form a ring which may be interrupted by one or more nitrogen, oxygen or sulfur atoms, a heterocycle as defined above, a sulfonamide radical, a carbonyl radical, a radical (C 1 -C 4) alkoxycarbonyl, a carboxamido radical, or a group of formula: R "QY in which R" 'represents an oxygen or nitrogen atom, Q represents an oxygen atom, an NH group, or NH (C 1 -C 4) alkyl, and Y is hydroxyl, amino, C 1 -C 4 alkyl, (C 1 -C 4) alkoxy, (C 1 -C 4) alkylamino, or di (C 1 -C 4) alkylamino . Among the 3-amino pyrazolo [1,5-a] pyridines of formula (I), which can be used as oxidation bases in the dyeing compositions in accordance with the invention, mention may be made in particular 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-amino acid 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] pyridine-5-ol - 3-amino-pyrazolo [1,5-a] pyridine-4-ol - 3-amino-pyrazolo [1,5-a] a] pyridine-6-ol; 3-amino-pyrazolo [1,5-a] pyridine-7-ol - 2-methoxy-6,7-dimethylpyrazolo [1,5-a] pyridin-3-amine; 2 - [(3-aminopyrazolo [1,5-a] pyridin-2-yl) oxy] ethanol; 4-ethyl-2-methoxy-7-methylpyrazolo [1,5-a] pyridin-3-amine hydrochloride; 1- (3-aminopyrazolo [1,5-a] pyridin-2-yl) pyrrolidin-3-ol; 2,2 '- [(3-aminopyrazolo [1,5-a] pyridin-2-yl) imino] diethanol; 2 - [(3-aminopyrazolo [1,5-a] pyridin-2-yl) amino] ethanol; N2- (2-pyridin-3-ylethyl) pyrazolo [1,5-a] pyridine-2,3-diamine; and their addition salts with an acid or with a base. For the most part, the 3-amino pyrazolo [1,5-a] pyridines of formula (I) are compounds known in the pharmaceutical field, and are described in particular in US Patent 5,457,200. These compounds can be prepared according to synthetic methods well known in the literature and as described, for example, in US Pat. No. 5,457,200. The oxidation base (s) of the invention are generally present each in an amount of between 0.001 to 10% by weight approximately of the total weight of the dyeing composition, preferably between 0.005 and 6%. The dye composition according to the invention contains one or more couplers conventionally used for dyeing keratinous fibers. Among these couplers, there may be mentioned meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalenic couplers, heterocyclic couplers and their addition salts. By way of example of a coupler, there may be mentioned 2-methyl-5-aminophenol, 5-N- (3-hydroxyethyl) amino-2-methylphenol, 6-chloro-2-methyl-5-aminophenol, 3 amino phenol, 2,4-dichloro-3-aminophenol, 5-amino-4-chloro-o-cresol, 1,3-dihydroxy benzene, 1,3-dihydroxy-2-methyl benzene, 4-chloro 1 , 3-dihydroxy benzene, 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-B-hydroxyethylamino-3,4-methylenedioxybenzene, α-naphthol, 2-methyl 1-naphthol, 1,5-dihydroxy naphthalene, 2,7-naphthalenediol, 1-acetoxy-2-methylnaphthalene, 6-hydroxyindole, 4-hydroxyindole, 4-hydroxy N-methylindole, 2-amino-3-hydroxy-pyridine, 6-hydroxybenzomorpholine, 3,5-diamino-2,6-dimethoxypyridine, 2,6-dihydroxy-3-4-dimethylpyridine, 3-amino-2-methyl amino-6-methoxypyridine, 1-N- (β-hydroxyethyl) amino-3,4-methylene dioxybenzene, 2,6-bis- (β-hydroxyethylamino) toluene, 3-methyl-1-phenyl-5- pyrazolone phenyl methyl pyrazolone and their addition salts with an acid. In the composition of the present invention, the coupler or couplers generally represent an amount of between 0.001 and 10% by weight of the total weight of the dyeing composition, preferably between 0.005 and 6%. In the context of the invention, in the definition of the polyol, a chain is understood to mean

  -OCOC- free of ether function, a chain which contains no motif In the polyols useful in the present invention, the chain and / or its branches may be substituted by one or more other substituents, especially the substituents chosen from carboxy groups, amino, halogen, C6-C30 aryl. As examples of the C 4 -C 30 polyol, mention may be made of branched or unbranched diols, such as 1,4-butanediol; 1,5-pentanediol; 1,6-hexanediol; neopentyl glycol (or 2,3-dimethyl-1,3-propanediol); 2,5-hexanediol; amylene glycol (or 2,4-pentanediol); hexylene glycol (or 2-methyl-2,4-pentanediol); isoprene glycol (or 3-methyl-1,3-butanediol); pinacol (or 2,3-dimethyl-2,3-butanediol); triols, branched or unbranched, such as 1,2,4-butanetriol and 1,2,6-hexanetriol.

  According to a particular embodiment of the invention, the polyol (s) are (C4-C15). Preferably, they are chosen from hexylene glycol; neopentyl glycol; isoprene. The polyol (s) are present in the composition according to the present invention in proportions generally of between 0.1 and 40% by weight, and even more particularly between 0.5 and 20% by weight of the total weight of the composition.

  The dye composition of the invention may optionally comprise one or more additional oxidation bases conventionally used for dyeing keratinous fibers, different from the oxidation bases of formula (I). By way of example, these additional oxidation bases may be chosen from para-phenylenediamines, bis-phenylalkylenediamines, para-aminophenols, bis-para-aminophenols, ortho-aminophenols, heterocyclic bases other than oxidation of formula (I) and their addition salts.

  Among the para-phenylenediamines, there may be mentioned, for example, para-phenylenediamine, para-toluenediamine, 2-chloro-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine and 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) para-phenylenediamine, 4-N, N-bis (13-hydroxyethyl) amino-2-methylaniline, 4-N, N-bis- (13-hydroxyethyl) amino 2-chloroaniline, 2-13-hydroxyethyl-para-phenylenediamine, 2-fluoro para-phenylenediamine, 2-isopropyl para-phenylenediamine, N- (13-hydroxyethyl) -2- hydroxypropyl) para-phenylenediamine, 2-hydroxymethyl-para-phenylenediamine, N, N-dimethyl-3-methyl-para-phenylenediamine, N, N- (ethyl, 13-hydroxyethyl) para-phenylenediamine, N- (13, yd) hydroxypropyl) para-phenylenediamine, N- (4'-aminophenyl) para-phenylenediamine, N-phenyl para-phenylenediamine, 2-13-hydroxyethyloxy para-phenylenediamine, 2-13-acetylaminoethyloxy para-phenylenediamine, N- (13 methoxyethyl) para-phenylenediamine, 4-aminophenylpyrrolidine, 2-thienyl para-phenylenediamine, 2-hydroxyethylamino-5-amino toluene, 3-hydroxy-1- (4'-aminophenyl) pyrrolidine and their salts. addition with an acid. Among the para-phenylenediamines mentioned above, para-phenylenediamine, para-toluenediamine, 2-isopropyl para-phenylenediamine, 2-13-hydroxyethyl para-phenylenediamine, 2-13-hydroxyethyloxy para-phenylenediamine, 2 , 6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, N, N-bis- (13-hydroxyethyl) para-phenylenediamine, 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 with an acid. Among the para-aminophenols, para-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluoro phenol, 4-amino-3-hydroxymethylphenol, 4- amino 2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol, 4-amino-2 - ([3-hydroxyethylaminomethyl) phenol, 4 amino-2-fluoro phenol, 1-hydroxy-4-methylamino-benzene, 2-2'-methylenebis-4-amino phenol and their addition salts with an acid. Among the ortho-aminophenols, there may be mentioned by way of example, 2-amino phenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol, 5-acetamido-2-amino phenol, and their addition salts with an acid. 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, 2,3-diamino-6-methoxy pyridine, 2 - ([3-methoxyethyl) amino-3-amino-6-methoxy pyridine, 3,4-diamino pyridine, and their addition salts with an acid. Among the pyrimidine derivatives, mention may be made of the compounds described, for example, in 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 pyrazolopyrimidine derivatives such as those mentioned in the patent application FR-A-2750048 and among which mention may be made of pyrazolo [1, 5-a] -pyrimidine-3,7-diamine; 2,5-dimethyl pyrazolo [1,5-a] pyrimidine-3,7-diamine; pyrazolo [1,5-a] pyrimidine-3,5-diamine; 2,7-dimethyl pyrazolo [1,5-a] pyrimidine-3,5-diamine; 3-amino pyrazolo [1,5-a] pyrimidin-7-ol; 3-amino pyrazolo [1,5-a] pyrimidin-5-ol; 2- (3-amino pyrazolo [1,5-a] pyrimidin-7-ylamino) ethanol, 2- (7-amino pyrazolo [1,5-a] pyrimidin-3-ylamino) - ethanol, 2 - [(3-amino-pyrazolo [1,5-a] pyrimidin-7-yl) - (2-hydroxyethyl) amino] ethanol, 2 - [(7-amino-pyrazolo [ 1,5-a] pyrimidin-3-yl) - (2-hydroxyethyl) amino] ethanol, 5,6-dimethyl pyrazolo [1,5-a] pyrimidine-3,7-diamine, 2,6-dimethyl pyrazolo [1,5-a] pyrimidine-3,7-diamine, 2,5-N, 7-N-7-tetramethyl-pyrazolo [1,5-a] -pyrimidine-3, 7-diamine, 3-amino-5-methyl-7-imidazolylpropylamino pyrazolo [1,5-a] pyrimidine and their acid addition salts and their 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 - ([3-hydroxyethyl) pyrazole, 3,4-diamino pyrazole, 4,5-diamino 1- (4'-chlorobenzyl) pyrazole, 4, 5-diamino 1,3-dimethyl pyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole, 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-diamino-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-meth 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- (13-hydroxyethyl) amino-1-methyl pyrazole, and their addition salts with an acid. There may also be mentioned diaminopyrazolinones described in patent application FR2886137 and in particular 2,3-diamino-6,7-dihydro-1H, 5H-pyrazol-1-one and its salts. 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 and addition salts with a base such as sodium hydroxide, potassium hydroxide, ammonia, amines or alkanolamines. The dye composition in accordance with the invention may also contain one or more direct dyes that may be chosen in particular from nitro dyes of the benzene series, azo direct dyes and methine direct dyes. These direct dyes may be nonionic, anionic or cationic in nature. The medium suitable for dyeing keratinous fibers, in particular human fibers such as the hair, also called dyeing support, generally comprises water or a mixture of water and at least one organic solvent other than the polyols which are useful in the present invention to solubilize compounds that would not be sufficiently soluble in water. As organic solvent, there may be mentioned for example lower alkanols C1-C4, such as ethanol and isopropanol; polyols and polyol ethers such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and monomethyl ether, polyethylene glycols, as well as aromatic alcohols such as benzyl alcohol or phenoxyethanol, and mixtures thereof. 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 compositions for dyeing hair, such as anionic, cationic, amphoteric and nonionic surfactants, anionic, cationic, nonionic, amphoteric and zwitterionic polymers. or mixtures thereof, inorganic or organic thickeners, and in particular anionic, cationic, nonionic and amphoteric polymeric associative thickeners, antioxidants, penetrating agents, sequestering agents, perfumes, buffers, dispersing agents, volatile or non-volatile silicones, modified or unmodified, film-forming agents, ceramides, preserving agents, 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 such that the advantageous properties intrinsically attached to the oxidation dyeing composition according to the invention are not, or not substantially impaired by the addition or additions envisaged. The pH of the dye composition according to the invention is generally between 3 and 12 approximately, and preferably between 5 and 11 approximately. It can be adjusted to the desired value by means of acidifying or 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, by way of example, are ammonia, alkaline carbonates, alkanolamines such as mono-, di- and triethanolamines and their derivatives, sodium or potassium hydroxides and wherein W is a propylene residue optionally substituted with a hydroxyl group or a C1-C4 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 keratinous fibers, and especially human 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 the fibers in the presence of an oxidizing agent for a time sufficient to develop the desired coloration. The color can be revealed at acidic, neutral or alkaline pH and the oxidizing agent can be added to the composition of the invention just at the time of use or it can be used from an oxidizing composition containing it applied simultaneously or sequentially to the composition of the invention. The revelation at acidic pH may be particularly interesting. According to a particular embodiment, the composition according to the present invention is mixed, preferably at the time of use, with a composition containing, in a medium suitable for dyeing, at least one oxidizing agent, this oxidizing agent being present in an amount sufficient to develop a coloration. The mixture obtained is then applied to the keratinous fibers. After a residence time of about 3 to 50 minutes, preferably about 5 to 30 minutes, the keratinous fibers are rinsed, washed with shampoo, rinsed again and then dried. The oxidizing agents conventionally used for the oxidation dyeing of keratin fibers are, for example, hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulfates, peracids and oxidase enzymes. among which there may be mentioned peroxidases, 2-electron oxidoreductases such as uricases and 4-electron oxygenases such as laccases. Hydrogen peroxide is particularly preferred.

  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 resulting composition applied to the keratinous fibers preferably varies between 3 and 12 approximately, and even more preferably between 5 and 11. It can be adjusted to the desired value by means of acidifying or basifying agents usually used for dyeing 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 dyeing in which a first compartment contains the dye composition of the present invention defined above and a second compartment contains an oxidizing agent. This device may be equipped with means for delivering the desired mixture to the hair, such as the devices described in patent FR-2 586 913 in the name of the applicant. From this device, it is possible to dye the keratinous fibers from a process which comprises mixing a dyeing composition comprising one or more oxidation bases of formula (I), one or more couplers and one or more several polyols according to the invention with an oxidizing agent, and the application of the mixture obtained on the keratinous fibers for a time sufficient to develop the desired coloration. The examples which follow serve to illustrate the invention without, however, being limiting in nature.

  Examples Composition 1 Composition 1 comprises the following dyes: 2 - [(3-aminopyrazolo [1,5-a] pyridin-2-yl) oxy] ethanol hydrochloride 0.005 mole per 100 g 2-Methyl 5-beta-hydroxyethylamino phenol 0.005 moles per 100 g introduced into the following medium:

  This coloring composition was introduced into the following support:

  Mixture of C18 to C24 linear alcohols [C18 / C20 / C22 / C24: 7/58/30/6 with alcohol content> 95%] Mixture of linear C18 to C24 alcohols [C18 / 020/022/024 7/58/30/6 - alcohol content> 95%] oxyethylenated (30 EO) stearyl alcohol oxyethylenated (20E) Stearyl alcohol oxyethylenated (21 0E) Crosslinked polyacrylic acid (Carbopol 980 from GOODRICH) Aculyn 44 oleic acid sold by ROHM & HAAS Monoisopropanolamide of coconut acids Cationic polymer MEXOMERE PO proposed by the company CHIMEX Neopentyl glycol Sodium metabisulfite EDTA (Ethylenediamine tetraacetic acid) Ter-butyl hydroquinone Monoethanolamine Ammonia at 20% NH3 Perfume qs Demineralized water q.s.p 3g 1g

  4.5 g 1.75 g 0.6 g 2.6 g 1.4 g M.A. 3g 4 g M.A. 6g 0.71 g 0.2 g 0.3 g 1 g 11 g

  100 g Method of application This composition is diluted extemporaneously with 1.5 times its weight of oxygenated water at 20 volumes and whose pH is 3.

  The mixture thus produced is applied to natural gray hair at 90% white, at the rate of 30 g for 3 g of hair for 30 minutes at room temperature (22 C 3 C). The hair is then rinsed, washed with a standard shampoo and dried.

  Result Capillary staining is evaluated visually. Height of tone Reflection Composition 1 Dark Blonde Red This coloring is stubborn and uniform.

Claims (17)

  1. Dyeing composition comprising, in a dyeing medium suitable for dyeing keratinous fibers, one or more aminopyrazolopyridine oxidation bases of formula (I) wherein R 2 in which: R 1 R2, R3, R4 and R5, which may be identical or different, represent a hydrogen or halogen atom; a radical -NHSO3H; a hydroxyl radical; a (C 1 -C 4) alkyl radical; a (C 1 -C 4) alkoxy radical; a (C 1 -C 4) alkylthio radical; mono (C 1 -C 4) alkylamino; a di (C 1 -C 4) alkylamino radical in which the two alkyl groups can, together with the nitrogen atom to which they are bonded, form a ring which can be interrupted by one or more nitrogen, oxygen or sulfur; a heterocycle; a nitro radical; a phenyl radical; a carbonyl radical; a (C 1 -C 4) alkoxycarbonyl radical; a carboxamido radical; a cyano radical; an amino radical; a sulfonyl radical; a radical -CO2H, a radical -SO3H; a radical -PO3H2; a radical -PO4H2; or a group: wherein R "" represents an oxygen or nitrogen atom, Q represents an oxygen atom, an NH or NH (C 1 -C 4) alkyl group, and Y represents a hydroxyl, amino, C 1 -C 4 alkyl, (C 1 -C 4) alkoxy, (C 1 -C 4) alkylamino, or di (C 1 -C 4) alkylamino radical, and their addition salts with an acid or a base • one or more couplers, and • one or more one or more C4-C30 polyols comprising a linear, branched or cyclic hydrocarbon chain, saturated or unsaturated, bearing at least two hydroxyl functions, said chain being functionally free ether.   2. Composition according to claim 1 characterized in that the compounds of formula (I) are the   3-amino pyrazolo [1,5-a] pyridines corresponding to the following sub-formula, and their addition salts with an acid or with a base: R 3 in which: R 1, R 2, R 3, which are identical or different , represent a hydrogen or halogen atom; a hydroxyl radical; a (C1-C4) alkyl radical; a (C 1 -C 4) alkylthio radical; a (C 1 -C 4) alkoxy radical; a radical -NHSO3H; an amino radical; a (C 1 -C 4) alkylamino radical; a di (C 1 -C 4) alkylamino radical in which the two alkyl groups can, together with the nitrogen atom to which they are bonded, form a ring which can be interrupted by one or more nitrogen, oxygen or sulfur; a heterocycle; a sulphonamide radical, a carbonyl radical, a (C1-C4) alkoxycarbonyl radical or a carboxamido radical, or a group of formula: ## STR2 ## in which R "'represents an oxygen or nitrogen atom , Q represents an oxygen atom, an NH or NH (C1-C4) alkyl group, and Y represents a hydroxyl, amino, C1-C4 alkyl, (C1-C4) alkoxy, (C1-C4) alkylamino radical; or di (C 1 -C 4) alkylamino. 3. A composition according to claim 1 or 2 wherein the 3-amino pyrazolo [1,5-a] pyridines of formula (I) are selected from: 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] pyridine-5-ol - 3-amino-pyrazolo [1,5-a] pyridine-4-ol - 3-amino-pyrazolo [1,5-a] a] pyridine-6-ol; 3-amino-pyrazolo [1,5-a] pyridine-7-ol - 2-methoxy-6,7-dimethylpyrazolo [1,5-a] pyridin-3-amine; 2 - [(3-aminopyrazolo [1,5-a] pyridin-2-yl) oxy] ethanol; - the   4-ethyl-2-methoxy-7-methylpyrazolo [1,5-a] pyridin-3-amine hydrochloride; 1- (3-aminopyrazolo [1,5-a] pyridin-2-yl) pyrrolidin-3-ol; 2,2 '- [(3-aminopyrazolo [1,5-a] pyridin-2-yl) imino] diethanol; 2 - [(3-aminopyrazolo [1,5-a] pyridin-2-yl) amino] ethanol; N2- (2-pyridin-3-ylethyl) pyrazolo [1,5-a] pyridine-2,3-diamine; and their addition with an acid or with a base. 4. Composition according to any one of the preceding claims, characterized in that the content of compounds of formula (I) is between 0.001 to 10% by weight approximately of the total weight of the dye composition.   5. Composition according to any one of the preceding claims, characterized in that the coupler or couplers are chosen from meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalenic couplers, heterocyclic couplers and their addition salts.   6. Composition according to claim 5, characterized in that the amount of each of the couplers is between 0.001 and 10% by weight approximately of the total weight of the dye composition.   7. Composition according to any one of the preceding claims, characterized in that it comprises one or more additional oxidation bases selected from para-phenylenediamines, bis-phenylalkylenediamines, para-aminophenols, ortho-aminophenols, heterocyclic bases. other than the oxidation bases of formula (I) and their addition salts.   8. Composition according to the preceding claim wherein the amount of each of the additional oxidation bases is between 0.001 to 10% by weight of the total weight of the dye composition.   9. Composition according to any one of the preceding claims wherein the polyol or polyols are C4-C15.   10. The composition of claim 9 wherein the one or more polyols are selected from hexylene glycol; neopentyl glycol; isoprene.   11. Composition according to any one of the preceding claims wherein the polyol or polyols are present in proportions of between 0.1 and 40% by weight of the total weight of the dye composition.   12. Composition according to any one of the preceding claims, comprising one or more oxidizing agents.   13. Composition according to claim 12, characterized in that the oxidizing agent is chosen from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts, peracids and oxidase enzymes.   14. Process for the oxidation dyeing of keratinous fibers, characterized in that a dye composition as defined in any one of Claims 1 to 11 is applied to the fibers in the presence of an oxidizing agent for a time sufficient to develop the desired color.   15. The method of claim 14, characterized in that the oxidizing agent is selected from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts, peracids and oxidase enzymes.   16. Multi-compartment device in which a first compartment contains a dye composition as defined in any one of claims 1 to 11 and a second compartment contains an oxidizing agent.   17. Use for the oxidation dyeing of keratinous fibers of a composition as defined in any one of claims 1 to 13.