FR2920090A1 - Composition for coloring keratin fibers, preferably human hair, comprises amino pyrazolopyridine oxidation bases, couplers, and surfactants comprising alkyl ether carboxylic acid and alkyl polyglucosides - 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 surfactants comprising alkyl(8-30C)ether carboxylic acid and its salts and alkyl(12-30C)polyglucosides, 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 surfactants comprising alkyl(8-30C)ether carboxylic acid and its salts and alkyl(12-30C)polyglucosides, 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 particular aminopyrazolopyridine base, at least one coupler and at least one particular surfactant. DESCRIPTION OF THE PREFERRED EMBODIMENTS 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.

  It is however desirable to further improve the power of the color obtained, its selectivity, as well as its resistance to external agents. This object is achieved with the present invention which relates to a dye composition comprising, in a dyeing medium suitable for dyeing keratinous fibers, one or more aminopyrazolopyridine oxidation bases of formula (I), R 2 NH 2 R 1 ( 1) R5 in which: - R ,, R2, R3, R4 and R5, 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 -PO4H2i or a group: R "'QY in which 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 surfactants chosen from (C 8 -C 30) alkylcarboxylic acids and their salts and (C 12 -C 30) alkyl polyglycosides.

  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 0-carbon chain, linear or branched, having 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, sulphonyl, -CO2H, -SO3H, -PO3H2, -PO4H2, -NHSO3H, sulphonamide, (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, -CO 2 H, -SO 3 H, -PO 3 H 2, -PO 4 H 2, 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 groups Y Y, there may be mentioned acetamide, dimethylurea, O-methylcarbamate, methylcarbonate, N-dimethylcarbamate and the esters.

  Among the compounds of formula (I) above, 3-amino pyrazolo [1,5-a] pyridines corresponding to the following sub-formula, and their addition salts with an acid or with a base, are preferred. in which: R 1, R 2, R 3, which may be identical or different, represent a hydrogen or halogen atom; 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 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 as defined above; a sulfonamide radical, a carbonyl radical, a (C 1 -C 4) alkoxycarbonyl radical, 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 or NH (C 1 -C 4) alkyl group, and Y represents a hydroxyl, amino, C 1 -C 4 alkyl, (C 1 -C 4) alkoxy or (C 1 -C 4) alkylamino radical; 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-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%. The composition according to the invention further comprises one or more surfactants chosen from (C 8 -C 30) alkyl carboxylic ether acids and their salts, (C 12 -C 30) alkyl polyglycosides. More particularly, the alkyl ether carboxylic acid (s) and their salts are chosen from the compounds of formula (II) below: ## STR2 ## in which: R 8 represents a linear or branched C 8 -C 22 alkyl or alkylene radical, an alkyl radical (C8-C9) aryl such as a (C8-C9) alkyl phenyl radical; A represents an oxygen atom or a group -CO-, -NH- or -CO-O-; B is constituted by a random sequence or blocks of -C3H6O units and -C2H4O- units; n 'is an integer from 1 to 30; p 'is an integer from 0 to 15; q 'is an integer equal to 0 or 1; X 'denotes a hydrogen atom or else Na, K, Li, V2 Mg or a monoethanolamine, ammonium or triethanolamine residue.

  According to a particular embodiment of the invention, the alkyl ether carboxylic acids and their salts are chosen from those of formula (II) in which R8 denotes a C8-C22 alkyl radical, preferably C10-C18, A represents a oxygen atom, X 'denotes a hydrogen or sodium atom, p' = 0, n 'ranges from 1 to 20, and preferably 1 to 10, and q' is equal to 0 or 1.

  The commercial products may consist of a mixture of the alkyl ether carboxylic acids or their salts, and in this case it is the average of the values of n 'or of p' which are indicated. Among the commercial products, the products sold by CHEM Y under the names AKYPO NP 70 (R 8 = nonylphenyl, A = O, n '= 7, p' = 0, q '= 1, X '= H); AKYPO NP 40 (R 8 = nonylphenyl, A = O, n '= 4, p' = 0, q '= 1, X' = H); AKYPO OP 40 (R 8 = octylphenyl, A = O, n '= 4, p' = 0, q '= 1, X' = H); AKYPO OP 80 (R 8 = octylphenyl, A = O, n '= 8, p' = 0, q '= 1, X' = H); AKYPO OP 190 (R 8 = octylphenyl, A = O, n '= 19, p' = 0, q '= 1, X' = H); AKYPO RLM 38 (R8 = C12-C14 alkyl, A = O, n = 3.8, p '= 0, q' = 1, X '= H); AKYPO RLM 38 NV (R8 = C12-C14 alkyl, A = O, n '= 4, p' = 0, q '= 1, X' = Na); AKYPO RLM 45 (R8 = (C12-C14) alkyl, A = O, n = 4.5, p '= 0, q' = 1, X '= H); 0, q '= 1, AKYPO RLM 45 NV (R8 = C12-C14 alkyl, A = O, average = 4.5, p' = X '= Na); AKYPO RLM 100 (R8 = C12-C14 alkyl, A = O, n '= 10, p' = 0, q '= 1, X' = H); AKYPO RLM 100 NV (R8 = C12-C14 alkyl, A = O, n '= 10, p' = 0, q '= 1, X' = Na); AKYPO RLM 130 (R8 = C12-C14 alkyl, A = O, n '= 13, p' = 0, q '= 1, X' = H); AKYPO RLM 160 NV (R8 = C12-C14 alkyl, A = O, n '= 16, p' = 0, q '= 1, X' = Na); AKYPO RS 60 (R8 = alkyl (C17), A = -CO-O-, n '= 6, p' = 0, q '= 1, X' = H); AKYPO SCR 60 (R8 = cetyl, A = O / R8 = alkyl (C17), A = -CO-O-; n '= 6, p' = 0, q '= 1, X' = H); AKYPO RS 100 (R8-A = stearyl, n '= 10, p' = 0, q '= 1, X' = H); - AKYPO RO 50 (R8-A = oleyl, n '= 5, p' = 0, q '= 1, X' = H); AKYPO SOFT 70 NV; AKYPO SOFT 45 NV; AKYPO SOFT 100 NV; AKYPO RLM 45 CA; AKYPO RLM 70; AKYPO TFC; AKYPO FOM (R8 = lauryl, A = NH); AKYPO SURFINE WLL; or by SANDOZ under the names: SANDOPAN ACA-48 (R8 = cetyl, A = O / alkyl (C17), A = -CO-O-; n '= 24, p' = 0, q '= 1, X '= H); SANDOPAN DTC-Acid (R8 = alkyl (C13), A = O, n '= 6, p' = 0, q '= 1, X' = H); SANDOPAN DTC (R8 = alkyl (C13), A = O, n '= 6, p' = 0, q '= 1, X' = Na); SANDOPAN LS 24 (R8 = C12-C14 alkyl, A = O, n '= 12, p' = 0, q '= 1, X' = Na); SANDOPAN JA 36 (R8 = alkyl (C13), A = O, n '= 18, p' = 0, q '= 1, X' = H). The alkyl polyglycoside (s) are well known and may be more particularly represented by the following general formula: R 9 O- (R 10 O) y- (G) - (III) in which R 9 represents a linear or branched alkyl and / or alkylene radical having about from 12 to 30 carbon atoms, an alkylphenyl radical in which the linear or branched alkyl radical contains from 12 to 30 carbon atoms, Rio represents one or more alkylene radicals comprising approximately 2 to 4 carbon atoms, G represents a sugar unit comprising from 5 to 6 carbon atoms, t 'denotes a value ranging from 0 to 10, preferably 0 to 4, and v denotes a value ranging from 1 to 15. Preferred alkyl polyglycosides according to the present invention are compounds of formula ( III) in which R 9 more particularly denotes a saturated or unsaturated, linear or branched alkyl radical containing from 12 to 30 carbon atoms, t 'denotes a value ranging from 0 to 3 and more particularly still even 0, G may denote glucose, fructose or galactose, preferably glucose. The degree of polymerization, ie the value of v in formula (III), can range from 1 to 15, preferably from 1 to 4. The average degree of polymerization is more particularly between 1 and 2 and even more preferably from 1 to , 1 to 1.5. The glycosidic linkages between the sugar units are of the 1-6 or 1-4 type and preferably 1-4.

  Compounds of formula (III) are in particular represented by the products sold by the company COGNIS under the names PLANTAREN (600 CS / U, 1200 and 1300) or PLANTACARE (818 and 1200), lauryl ether carboxylic acids, alkyl (012 / 014/016 68/26/6) polyglycosides. The above surfactant (s) are each present in the composition according to the invention in an amount of between 0.01% and 30% by weight, preferably between 0.1% and 15% by weight relative to the total weight of the composition. dye 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 and heterocyclic bases other than oxidation bases. 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-O 3, - dihydroxypropyl) paraphenylenediamine, N- (4'-aminophenyl) para-phenylenediamine, N-phenyl-para-phenylenediamine, 2-hydroxy-3-hydroxyethyloxy para-phenylenediamine, 2-13-acetylaminoethyloxy para-phenylenediamine, N- (R) 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 paraphenylenediamine, 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 para-aminophenols, para-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluoro phenol, 4-amino-3-hydroxymethylphenol, 4-amino-2 are exemplified. methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol, 4-amino-2- (13-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, 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 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- (R-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-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-methyl-3-methyl pyrazole, 4,5-diamino-1-ethyl-3-methyl pyrazole, 4,5-diamino-1-ethyl-3- (4'-methoxyphenyl) pyrazole, 4,5 1-ethyl-3-hydroxymethyl pyrazole, 4,5-diamino-3-hydroxymethyl-1-methyl pyrazole, 4,5-diamino-3-hydroxymethyl-1-isopropyl pyrazole, 4,5-diamino-3-methyl 1-isopropyl pyrazole, 4-amino 5- (2'-aminoethyl) amino 1,3-dimethyl pyrazole, 3,4,5-triamino pyrazole, 1-methyl 3,4,5-triamino pyrazole, 3 5-diamino-1-methyl-4-methylamino pyrazole, 3,5-diamino-4-yl-hydroxyethyl) amino-1-methyl pyrazole, and their addition salts 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 a dyeing medium, generally comprises water or a mixture of water and at least one organic solvent to solubilize the compounds that would not be present. not sufficiently soluble in water. As organic solvent, there may be mentioned for example lower alkanols C1-C4i 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 and 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 dye 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 other than those of the invention, anionic, cationic polymers, nonionic, amphoteric, zwitterionic 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 following formula: Ra \ R bi NW-NR ~ Rd wherein W is a propylene residue optionally substituted by 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 surfactants 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 0.006 moles per 100 g 1-Methyl-2-hydroxy-4- aminobenzene 0.006 mol per 100 g introduced into the following medium: lauryl ether carboxylic acid 4.5 EO 7.0 g (Akypo RLM 45 sold by CHEM Y) Lauryl alcohol 2 EO (Dehydol LS-2-DEO-N sold by COGNIS 4.0 g Alcohol decyl ether 5 EO 8.0 g (Empilan KA-5/90-FL sold by ALBRIGHT & WILSON) Oleyl alcohol 3.0 g Monoethanolamide of akyl acid (C13 / 015) carboxylic ether with 25 g moles of ethylene oxide Cationic associative polymer (Quatrisoft LM 2008 sold by 1.0 g AMERCHOL) Monoethanolamine 20.0 g Polyquaternium 6 (Merquat 8 100 sold by CALGON) 1.5 g Ethanol 11.0 g Propylene glycol 5.0 g Dipropylene glycol 5.0 g Reducing agents, antioxidants qs Sequestering qs Fragrance qs

  Ammonia (20.5% NH3) 1.6 g Demineralized water Q.S.P 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 a rate of 30 g for 3 g of hair for 30 minutes at room temperature (22 C 3). The hair is then rinsed, washed with standard shampoo and dried.

  Results Capillary staining is evaluated visually. Height of tone Reflection Composition 1 Dark Blonde Red slightly purplish This coloration is stubborn and uniform.

Claims (19)

  A dye composition comprising, in a dyeing medium suitable for dyeing keratinous fibers, one or more aminopyrazolopyridine oxidation bases of the following formula (I): R 1 (1) R 5 in which: R 1, R 2, R 3, R4 and R5, which may be identical or different, represent a hydrogen or halogen atom; a radical -NHSO3H; a hydroxyl radical; a (C1-C4) alkyl radical; a (C1-C4) alkoxy radical; a (C1-C4) alkylthio radical; mono (C1-C4) alkylamino; a di (C1-C4) 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 atoms; ; a heterocycle; a nitro radical; a phenyl radical; a carbonyl radical; a (C1-C4) 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 -PO4H2i or a group: R "'\ Q / \ Y in which R"' represents an oxygen or nitrogen atom, Q represents an oxygen atom, a group NH or NH (C1-C4) alkyl, and Y represents a hydroxyl, amino, C 1 -C 4, (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 surfactants selected from C 8 -C 30 alkyl ether carboxylic acids and their salts and C 12 -C 30 alkyl polyglycosides.   2. Composition according to claim 1 characterized in that the compounds of formula (I), and their addition salts with an acid or with a base, correspond to the following sub-formula: in which: R 1, R 2, R 3 , identical or different, represent a hydrogen or halogen atom; 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 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 as defined above; a sulfonamide radical, a carbonyl radical, a (C 1 -C 4) alkoxycarbonyl radical, 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 or NH (C 1 -C 4) alkyl group, and Y represents a hydroxyl, amino, C 1 -C 4 alkyl, (C 1 -C 4) alkoxy or (C 1 -C 4) alkylamino radical; or di (C 1 -C 4) alkylamino.   3. Composition according to claim 1 or 2 wherein the 3-amino pyrazolo [1,5-a] pyridines of formula (I) are chosen 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-aminopyrazolo [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] pyridin-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 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, in which the alkyl ether carboxylic acid (s) and their salts are chosen from compounds of the following formula (II): ## STR2 ## in which: R 8 represents a linear or branched C8-C22 alkyl or alkylene radical, a (C8-C9) alkyl radical aryl such as a (C8-C9) alkyl phenyl radical; A represents an oxygen atom or a group -CO-, -NH- or -CO-O-; B is constituted of a random sequence or blocks of p 'units -C3H60- and n' units -C2H40-; n 'is an integer from 1 to 30; p 'is an integer from 0 to 15; q 'is an integer equal to 0 or 1; X 'denotes a hydrogen atom or else Na, K, Li, 1/2 Mg or a monoethanolamine, ammonium or triethanolamine residue.   10. Composition according to the preceding claim, characterized in that, in formula (II), R8 denotes a C8-C22 alkyl radical, preferably C10-C18, A represents an oxygen atom, X 'denotes an atom of hydrogen or sodium, p '= 0, n' ranges from 1 to 20, and preferably 1 to 10, and q 'is 0 or 1.   A composition according to any one of the preceding claims wherein the alkyl polyglycoside (s) are represented by the following general formula: R 90 - (R 100) y - (G) - (III) wherein R 9 represents an alkyl radical and / or linear or branched alkylene having from 12 to 30 carbon atoms, an alkylphenyl radical in which the linear or branched alkyl radical contains from 12 to 30 carbon atoms, Rio represents one or more alkylene radicals comprising approximately 2 to 4 R8-A atoms Carbone, G represents a sugar unit comprising from 5 to 6 carbon atoms, t 'denotes a value ranging from 0 to 10, preferably 0 to 4, and v denotes a value ranging from 1 to 15.   12. Composition according to any one of the preceding claims, characterized in that the surfactant or surfactants are selected from lauryl ether carboxylic acids, alkyl (C12 / C14 / C16 68/26/6) polyglycosides.   13. Composition according to any one of the preceding claims, characterized in that the surfactant or surfactants are each present in an amount of between 0.01% and 30% by weight of the total weight of the dyeing composition.   14. Composition according to any one of the preceding claims, comprising one or more oxidizing agents.   15. Composition according to claim 14, characterized in that the oxidizing agent is chosen from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts, peracids and oxidase enzymes.   16. Process for the oxidation dyeing of keratinous fibers, characterized in that a dye composition as defined in any one of Claims 1 to 13 is applied to the fibers in the presence of an oxidizing agent for a time sufficient to develop the desired color.   17. The method of claim 16, characterized in that the oxidizing agent is selected from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts, peracids and oxidase enzymes.   18. Multi-compartment device in which a first compartment contains a dye composition as defined in any one of claims 1 to 13 and a second compartment contains an oxidizing agent.   19. Use for the oxidation dyeing of keratin fibers of a composition as defined in any one of claims 1 to 15.