MXPA99010758A - Keratin fibre oxidation dyeing composition and dyeing method using same - Google Patents

Abstract

The invention concerns a ready-for-use keratin fibre oxidation dyeing composition, in particular for human keratin fibres such as hair, comprising, in a medium suitable for dyeing, at least a heterocyclic oxidation dye, at least an oxydoreductase enzyme with 2 electrons in the presence of at least a donor for said enzyme, and the dyeing method using said composition.

Description

COMPOSITION OF DYEING BY OXIDATION OF KERATINIC FIBERS AND DYEING PROCEDURE USED THIS COMPOSITION.

The subject of the invention is a composition for the oxidation dyeing of keratin fibers, and in particular of human keratin fibers such as hair comprising, in a medium suitable for dyeing, at least one heterocyclic oxidation dye, at least a 2-electron oxide-reductase-type enzyme in the presence of at least one donor for the indicated enzyme, as well as the dyeing process using this composition. It is known to dye keratin fibers and in particular human hair with dyeing compositions containing dye precursors by oxidation, in particular ortho or paraphenylenediamines, ortho or para-aminophenols, heterocyclic bases, generally called oxidation bases. Oxidation dye precursors, or oxidation bases, are colorless or weakly colored compounds which, associated with oxidizing products, can give rise to colored compounds and dyes by a process of oxidative condensation. It is also known that the EF: 32067 shades obtained with these oxidation bases associating them with copulators or color modifiers, the latter being chosen in particular between aromatic meta-diamines, meta-aminophenols, meta-diphenols and some heterocyclic compounds. The variety of molecules used at the level of oxidation bases and copulators allows obtaining a rich range of colors. The coloration called "permanent" obtained thanks to these oxidation dyes, must on the other hand meet a certain number of requirements. Thus, it should have no drawbacks on the toxicological level, it should allow obtaining tonalities in the desired intensity and present a good behavior with respect to external agents (light, bad weather, washing, perm, perspiration, friction). The dyes must likewise make it possible to cover the white hairs, and finally to be as less selective as possible, that is to say, to obtain a difference in coloration as low as possible throughout the same keratin fiber, which may be in differently sensitized effect (i.e. , spoiled) between its tip and its root. The oxidation coloring of the keratin fibers is generally carried out in an alkaline medium in the presence of hydrogen peroxide, however, the use of alkaline media in the presence of hydrogen peroxide has the drawback of producing a non-negligible degradation of the fibers, as well as a discoloration of the keratin fibers which is not always desirable.The oxidation coloring of the keratin fibers can also be carried out with the aid of oxidizing systems other than hydrogen peroxide such as enzymatic systems.Thus it has already been proposed to dye the fibers keratin preparations, particularly in the patent application EP-A-0310,675, with compositions comprising a benzene-type oxidation dye precursor, in association with enzymes such as pyranose oxidase, glucose oxidase or uricase, in the presence of of a donor for the indicated enzymes.These dyeing procedures, although they are carried out under conditions which do not produce a degradation of the keratin fibers comparable to that produced by the dyeings carried out in the presence of hydrogen peroxide, they lead to less strong deposits. However, the applicant now finishes discovering that it is possible to obtain new dyes, able to lead to strong colorations without producing significant degradation, or discoloration of the keratin fibers, which are not very selective and which resist the various aggressions that the hair may experience. , associating at least one oxidation base, at least one copulant, and at least one 2-electron oxide-reductase type enzyme in the presence of at least one donor for the indicated enzyme, the oxidation base (s) and / or the coupling (s) used being chosen from appropriately selected heterocyclic compounds. This discovery forms the basis of the present invention. The invention therefore has as its first object a ready-to-use composition for the oxidation dyeing of keratin fibers and in particular of human keratin fibers such as hair, which comprises the combination of at least one oxidation base and the less a copulator, characterized in that it comprises, in a medium suitable for dyeing, at least one 2-electron oxide-reductase-type enzyme in the presence of at least one donor for said enzyme, and because said base of oxidation and / or the indicated copulant is chosen from the heterocyclic compounds to the exclusion of the monocyclic pyridine compounds. The ready-to-use dye composition according to the invention leads to more potent colorations than those obtained with dye compositions containing only benzene dyes in the presence of a 2-electron oxido-reductase-type enzyme, and of a donor for the indicated enzyme, which is not the case with a 'classic oxidant system such as peroxide I hydrogen The colorations obtained with the ready-to-use dye composition composition according to the invention have, on the other hand, low selectivity and excellent properties of resistances at the same time with respect to atmospheric agents such as light and weathering and with respect to perspiration and different treatments. that can experience the hair (washes, deformations 1 permanent). The subject of the invention is also a process for dyeing by oxidation keratin fibers using this ready-to-use dye composition. The 2-electron oxido-reductases used in the ready-to-use dye composition according to the invention can be chosen in particular from pyranose oxidases, glucose oxidases, glycerol oxidases, lactate oxidases, pyruvate oxidases, and uricasas According to the invention, the 2-electron oxido-reductase is preferably chosen from uricases of animal, microbiological or biotechnological origin.

By way of example, one can particularly mention the uricase extracted from boar liver, the uricase from Arthrobacter globiformis, as well as the uricase from Aspergillus flavus. The 2-electron oxido-reductases can be used in pure crystalline form or in a dilute form in an inert diluent for the indicated 2-electron oxido-reductase. The 2-electron oxide-reductases according to the invention preferably represent from 0.01 to 20% by weight approximately of the total weight of the ready-to-use dye composition, and even more preferably from 0.1 to 5% by weight approximately of this weight. According to the invention, "donor" is understood to mean the different substrates equally necessary for the operation of the indicated one or of said 2-electron oxido-reductases. The nature of the donor (or substrate) for the indicated enzyme varies depending on the nature of the 2-electron oxido-reductase that is used. For example, as a donor for the pyranose oxidases, mention may be made of D-glucose, L-sorbose and D-xylose; as a donor for glucose oxidases, D-glucoses can be mentioned, as a donor for glycerol oxidases, there may be mentioned glycerol and dihydroxyacetone; as a donor for lactate oxidases, mention may be made of lactic acid and its salts; as a donor for pyruvate oxidases, mention may be made of pyruvic acid and its salts; and finally as a donor for uricasas, we can mention uric acid and its salts. The donor (s) (s) used according to the invention preferably represent 0.01 to 20% by weight approximately of the total weight of the dye composition ready for use according to the invention and even more preferably from 0.1 to 5% approximately this weight. Among the heterocyclic oxidation bases which can be used in the ready-to-use dye composition according to the invention, mention may be made, in particular, of the pyrimidine derivatives, the pyrazole derivatives and their addition salts with an acid. Among the pyrimidine derivatives, mention may be made more particularly of the compounds described, for example, in German Patents 2,359,399 or Japanese Patents JP 88-169,571 and JP 91-106-059, such as 2,4,5,6-tetraaminopyridine, 4-hydroxy-2, 5,6-triaminopyrimidine, and its addition salts with an acid, as well as the pyrazolopyrimidine derivatives such as pyrazolo- [1,5-a] -pyrimidine-3,7-diamine, 2- methyl pyrazolo- [1, 5-a] -pyrimidine-3,7-diamine, 2-5-dimethylpyrazolo- [1, 5-a] -pyrimidine-3,7-diamine, pyrazolo- [1, 5 -a] pyrimidine-3, 5-diamine, 2,7-dimethylpyrazolo- [1, 5-a] pyrimidine-3-5-diamine, 3-amino pyrazolo- [1, 5-a] -pyrimidine- 7-ol, 3-amino 5-methyl 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, 3-amino-7-β-hydroxyethylamine-5-methyl-pyrazolo- [1, 5-a] -pyrimidine, 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-dimethylpyrazolo- [1,5-a] -pyrimidine-3,7-diamine, 2,6-dimethylpyrazolo- [1,5-a] -pyrimidine-3, 7-diamine, 2,5, N-7-tetramethyl pyrazolo- [1,5-a] -pyrimidine-3,7-diamine, and their addition salts and their tautomeric forms, when there is a tautomeric equilibrium. Among the pyrazole derivatives, the compounds described in the patents or patent applications DE 3,843,892, DE 4,133,957, DE 4,234,886, DE 4,234,887, FR 2,733,749, FR 2,735,685, can be cited more particularly. WO 94/08969 and WO 94/08970, such as 4,5-diamino pyrazole, 4,5-diamino-1-methyl pyrazole, 1-benzyl 4,5-diamino pyrazole, 3,4-diamino pyrazole, 1-benzyl 4,5-diamino-3-methyl pyrazole, 4-amino-1,3-dimethyl-5-hydrazinopyrazole, 4,5-diamino-3-methyl-1-phenyl-pyrazole, 4,5-diamino-3-methyl 1-tert-butyl pyrazole, 4,5-diamino-1-methyl-3-tert-butyl pyrazole, 4,5-diamino-1-ethyl-3-methyl-pyrazole, 4,5-dia-tert-1-ethyl 3- (4 * -methoxyphenyl) pyrazole, 4,5-diamino-1-ethyl-3-hydroxymethyl pyrazole, 4,5-diamino-3-hydroxymethyl-1-methyl-pyrazole, 4,5-diamino-3-hydroxymethyl-1-isopropyl pyrazole, 4,5-diamino-3-methyl-1-isopropyl pyrazole, and its addition salts with an acid. When present, the heterocyclic oxidation base or bases according to the invention preferably represent from 0.0005 to 12% by weight approximately of the total weight of the ready-to-use dye composition, and even more preferably from 0.005 to 6% by weight approximately of this weight. Among the heterocyclic couplers which can be used in the ready-to-use dye composition according to the invention, mention may be made in particular of the indole derivatives, the indoline derivatives, the benzimidazole derivatives, the benzomorpholine derivatives, the sesamol derivatives, the pyrazole-azolic derivatives, pyrrolozole derivatives, imidazole-azole derivatives, pyrazolo-pyrimidine derivatives, pyrazolin-3, 5-diones derivatives, pyrrolo- [3, 2-d] -oxazole derivatives, pyrazole derivatives [3, 4-d] -thiazoles, the thiozole-azolic S-oxide derivatives, the S, S-dioxide-thiazole-azolic derivatives, and their addition salts with an acid. Among the indole derivatives which can be used as heterocyclic couplers in the dyeing composition according to the invention, mention may be made more particularly of the compounds of the following formula (I) and their addition salts with an acid: wherein Rx represents a hydrogen atom, an alkyl radical of C? ~ C4, a mono- or polyhydroxyalkyl radical of C2-C or aminoalkyl of Cj.-C4 whose amine is mono- or disubstituted by an alkyl group of C? _C4; R 2 represents a hydrogen atom or a C 1 -C 4 alkyl radical; R3 represents a hydrogen atom, an alkyl radical of C-C4 O hydroxyl; X represents a hydroxyl radical or NHR4 in which R4 represents a hydrogen atom, an alkyl radical of C? -C4 or hydroxyalkyl of C? ~ C4.

Among the indole compounds of formula (I) indicated above, one may more particularly cite 4-hydroxy indole, 6-hydroxy indole, 7-amino indole, 6-a.mip.o indole, 7-hydroxy indole, 7-ethyl 6- (ß-hydroxyethyl) amino indole, 4-amino indole, 6-hydroxy-1-methyl indole, 5,6-dihydroxy indole, 4-hydroxy 1-N-methyl indole, 4-hydroxy 2-methyl indole, 4-hydroxy 5-methyl indole, 4-hydroxy 1-N- (ß-hydroxyethyl) indole, 4-hydroxy 1-N- (ß-hydroxypropyl) indole, lN- (ß,? - dihydroxypropyl) 4-hydroxy indole, 4-hydroxy-lN- (ß-hydroxyethyl) -5-methyl indole, 1-N- (? - dimethylaminopropyl) 4-hydroxy indole, and its addition salts with an acid. Among the indoline derivatives usable as heterocyclic couplers in the. dye composition according to the invention, mention may be made in particular of 4-hydroxy indoline, 6-hydroxy indoline, 6-amino indoline, 5,6-dihydroxy indoline, and their addition salts with an acid. Among the benzimidazole derivatives which can be used as heterocyclic couplers in the dye composition according to the invention, the following compounds of formula (II) and their addition salts with an acid can be mentioned more particularly: wherein Rs represents a hydrogen atom or an alkyl radical of C? ~ C, R6. represents a hydrogen atom, an alkyl radical of C? -C4 or phenyl, R7 represents a hydroxyl, amino or methoxy radical, Re represents a hydrogen atom, a hydroxyl radical, methoxy or C? -C4 alkyl; with the proviso that - when R7 designates an amino radical, then it occupies position 4, - when R? occupies position 4. then Rs occupies position 7, - when R7 occupies position 5. then R8 occupies position 6. Among the benzimidazole derivatives of formula (II) indicated above, can more particularly be mentioned 4-hydroxybenzimidazole, 4-amino benzimidazole, 4-hydroxy-7-methylbenzimidazole, 4-hydroxy-2-methylbenzimidazole, 1-butyl-4-hydroxybenzimidazole, 4-amino-2-methyl-benzimidazole, 5,6-dihydroxy-benzimidazole, 5-hydroxy-6-methoxy-benzimidazole, 4,7-dihydroxy-benzimidazole, 4,7-dihydroxy-1-methyl-benzimidazole, 4,7 -dimethoxy benzimidazole, 5,6-dihydroxy-1-methyl benzimidazole, 5,6-dihydroxy-2-methyl-benzimidazole, 5,6-dimethoxy-benzimidazole, and their addition salts with an acid. Among the benzomorpholine derivatives which can be used as heterocyclic couplers in the ready-to-use dye composition according to the invention, mention may be made more particularly of the compounds of formula (III) below, and their addition salts with an acid. wherein: R9 and R10, identical or different, represent a hydrogen atom or an alkyl radical of C? ~ C, Z represents a hydroxyl or amino radical. Among the benzomorpholine derivatives of formula (III) indicated above, can be more particularly cited 6-hydroxy 1,4-benzomorpholine, N-methyl 6-hydroxy-1-4-benzomorpholine, 6-amino 1,4-benzomorpholine, and its addition salts with an acid Among the sesamol derivatives which can be used as a heterocyclic coupler in the ready-to-use dye composition according to the invention, the following compounds of formula (IV) and their addition salts with an acid can be mentioned in particular: wherein: Ru designates a hydroxyl radical, amino (C? -C4) amino, monohydroxyalkyl (C? ~ C) amino ~ or polyhydroxyalkyl (C2-C) amino, Rx2 designates a hydrogen or halogen atom or a C? -C alkoxy radical. __ -Among the sesamol derivatives of formula (IV) indicated above, mention may be made more particularly of 2-bromo-4,5-methylenedioxy phenol, 2-methoxy-4,5-methylenedioxy aniline, 2- (β-hydroxyethyl) amino 4,5-methylenedioxy benzene, and its addition salts with an acid. - Among the pyrazolo-azolic derivatives which can be used as a heterocyclic coupler in the ready-to-use dye composition according to the invention, the compounds described in the following patent and patent applications can be cited more particularly: FR 2,075,583, EP- A-119,860, EP-A-285,274, EP-A-244,160, EP-A-578,248, GB 1,458,377, US 3,227,554, US 3,419,391, US 3,061,432, US 4,500,630, US 3,725. .067, US 3,926,631, US 5,457,210, JP 84/99437, JP 83/42045, JP 84/162548, JP 84/171956, JP 85/33552, JP 85/43659, JP 85/172982, JP 85 / 190779_ as well as in the following publications: Chem. Ber. 32, 797 (1899), Chem. Ber. 89, 2550, (1956), J. Chem, Soc. Perkin trans I, 2047, (1977), J. Prakt. Chem., 320, 533, (1978); whose teachings form an integral part of the present application. As the pyrazolozole derivatives, mention may be made in particular of: 2-methyl pyrazolo [1, 5-b] -1,2,4-triazole, 2-ethyl pyrazolo [1,5-b] -1, 2, 4-triazole, - 2-isopropyl pyrazolo [1, 5-bl -1,2, 4-triazole, - 2-phenyl-pyrazolo [1, 5-b] -1, 2, -triazole , - 2,6-dimethylpyrazolo [1,5-b] -1,2,4-triazole, - 7-chloro-2,6-dimethylpyrazolo [1,5-b] -1,2-triazole , - 3,6-dimethyl-pyrazolo [3,2-c] -1,2,4-triazole - 6-phenyl-3-methylthio-pyrazolo [3, 2-c] -1, 2, 4- triazole, - 6-amino-pyrazolo [1,5-a] benzimidazole, and its addition salts with an acid. Among the pyrrolozole derivatives which can be used as a heterocyclic coupler in the ready-to-use dye composition according to the invention, the compounds described in the following patent and patent applications can be cited more particularly: US 5,256,526, EP-A -557,851, EP-A-578,248, EP-A-518,238, EP-A-456,226, EP-A-488-909, EP-A-488-248, and in the following publications: - DR Liljegren Ber. 1964, 3436; - E.J. Bro ne, J.C.S., 1962, 5149; - P. Magnus, J.A.C.S., 1990, 112, 2465; - P. Magnus, J.A.C.S., 1987, 109, 2711; - Angew. Chem. 1960, 72, 9'56; - and Rec. Trav. Chim. 1961, 80, 1075; whose teachings form an integral part of the present application. As pyrrolozole derivatives, the following may be particularly mentioned: - 5-cyano-4-ethoxycarbonyl-8-methyl pyrrolo [1,2-b '] -1,2,4-triazole, - cyano-8-methyl-4-phenyl pyrrolo [1,2-b] -1,2,4-triazole, 7-amido-6-ethoxycarbonyl pyrrolo [1,2-a] -benzimidazole and its addition salts with an acid. Among the imidazolezole derivatives which can be used as a heterocyclic coupler in the ready-to-use dye composition according to the invention, the compounds described in the following patent and patent applications can be cited more particularly: US Pat. No. 5,441,863; JP 62-279-337; JP 06-236 011 and JP 07-092 632, whose teachings form an integral part of the present application. As imidazole-azole derivatives, the following may particularly be mentioned: 7,8-dicyano-imidazole [3, 2-a] -imidazole, 7,8-dicyano-4-rnethyl-imidazole [3] , 2-a] -imidazole, and its addition salts with an acid. Among the pyrazolo-pyrimidine derivatives which can be used as the heterocyclic copolymer in the ready-to-use dye composition according to the invention. more particularly, the compounds described in the following patent application can be cited: EP-A-304,001 the teachings of which form an integral part of the present application. As pyrazolo-pyrimidine derivatives, the following may be particularly mentioned: - pyrazolo [1,5-a] pyrimidin-7-one, - 2,5-dimethylpyrazolo [1,5-a] pyrimidin-7-one , 2-methyl-6-ethoxycarbonyl pyrazolo [1,5-a] pyrimidin-7-one, - 2-methyl-5-methoxymethyl pyrazolo [1,5-a] pyrimidin-7-one, - 2- tert-butyl-5-trifluoromethylpyrazolo [1, 5-a] pyrimidin-7-one, - 2,7-dimethylpyrazolo [1,5-a] pyrimidin-5-one, and its addition salts with an acid. Among the 3, 5-pyrazoline derivatives which can be used as a heterocyclic coupler in the ready-to-use dye composition according to the invention, the compounds described in the following patent and patent applications can be mentioned more particularly: JP 07- 036159, JP 07-84348 and US 4,128,425, and in the following publications: - L. WYZGOWSKA, Acta. Pol. Pharm. 1982, 39 (1-3), 83. - E HANNIG, Phar azie, 1980, 35 (4), 231 - M. H. ELNAGDI, Bull. Chem. Soc. Jap., 46 (6), 1830, 1973 - G. CARDILLO, Gazz, Chim, Itai. 1966, 96, (8-9), 973. whose teachings form an integral part of the present application. As the 3, 5-pyrazoline dione derivatives, mention may be made particularly of: 1,2-diphenyl 3,5-pyrazoline dione, 1,2-diethyl 3,5-pyrazoline dione and its salts addition with an acid. Among the pyrrolo- [3, 2-d] -oxazole derivatives which can be used as a heterocyclic coupler in the ready-to-use dye composition according to the invention, the compounds described in the patent application JP 07 325 can be cited more particularly. 375 whose teachings form an integral part of the present application. Among the pyrazolo- [3,4-d] -thiazole derivatives which can be used as the heterocyclic coupler in the ready-to-use dye composition according to the invention, the compounds described in the patent applications JP 07 244 361 can be cited more particularly. and in J. Heterocycl. Chem. 16, 13, (1979). Among the S-oxide-thiazolo-azole and S, S-dioxide-thiazole-azole derivatives which can be used as a heterocyclic coupler in the ready-to-use dye composition according to the invention, the compounds described in US Pat. following documents: - JP 07 098489; - Khim. Geterotsilk, Soedin, 1967, page 93; - J. Prakt. Chem., 318, 1976, page 12; - Indian J. Heterocycl. Chem. 1995, 5 (2), page 135; - Act. Pol. Pharm. 1995, 52 (5), 415; - Heterocycl. Commun. 1995, 1 (4), 297; Arch. Pharm. (Weinheim, Ger.), 1994, 327 (12), 825. When present, this or these heterocyclic copulators preferably represent from 0.0001 to 10% by weight approximately of the total weight of the ready-to-use dye composition and even more preferably from 0.005 to 5% by weight approximately of this weight. The ready-to-use dye composition according to the invention can also contain, in addition to the dyes defined above, other oxidation bases and / or other couplers and / or other dyes, such as for example direct dyes, in particular for modifying the tones or enriching them with reflexes. Among the oxidation bases which may be present additionally in the ready-to-use dye composition according to the invention, mention may be made in particular of the paraffinylenes inas, the bis-phenylalkylenediamines, the orthophenylenediamines, the para-aminophenols, the ortho-aminophenols, and their addition salts with an acid. When used, these additional oxidation bases preferably represent from 0.0005 to 12% by weight approximately of the total weight of the dyeing composition, and even more preferably from 0.005 to 6% by weight approximately of this weight. Among the copulators which may additionally be present in the ready-to-use dye composition according to the invention, mention may be made in particular of meta-phenylenediarrines, meta-aminophenols, meta-diphenols and their addition salts with an acid. When these additional couplers are present they preferably represent from 0.0001 to 10% by weight approximately of the total weight of the ready-to-use dye composition and even more preferably from 0.005 to 5% by weight approximately of this weight. In a general manner, the addition salts with an acid which can be used in the framework of the dyeing compositions of the invention (oxidation bases and couplers) are particularly chosen from hydrochlorides, hydrobromides, sulfates and tartrates, lactates and acetates. The suitable medium for the dye (or support) of the ready-to-use dye composition according to the invention is generally constituted by water or by a mixture of water and by at least one organic solvent to solubilize the compounds that were not sufficiently soluble in the composition. Water. As the organic solvent, mention may be made, for example, of C?-C 4 alkanols, such as ethanol and isopropanol; glycerol; glycols and ethers of glycols such as 2-butoxyethanol, propylene glycol, monomethylether of propylene glycol, monoethylether and monomethylether of diethylene glycol, as well as aromatic alcohols such as benzyl alcohol or phenoxyethanol, analogous products and mixtures thereof. The solvents can be present in proportions, preferably between 1 and 40% by weight, based on the total weight of the dyeing composition, and even more preferably between 5 and 30% by weight. The pH of the ready-to-use composition according to the invention is chosen in such a way that the enzymatic activity of the 2-electron oxido-reductase is not altered. Generally it is comprised between 5 and 11 approximately, and preferably between 6.5 and 10 approximately. It can be adjusted to the desired value by means of acidifying or alkalizing agents usually used in the dyeing of keratin fibers. Among the acidulating 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, acid lactic, sulfonic acids. Among alkalizing agents, mention may be made, by way of example, of ammonia, alkali metal carbonates, alkanolamines such as mono-, di- and triethanolanes, 2-methyl-2-aminopropanol as well as their derivatives, hydroxides of sodium or potassium and the compounds of formula (V) below: wherein W is a propylene moiety optionally substituted by a hydroxyl group or an alkyl radical of C? -C4; R? 3, RI4? R and Ri 6f identical or different represent a hydrogen atom, a C 1 -C 4 alkyl radical or a C 1 -C 4 hydroxyalkyl radical. The ready-to-use dye composition according to the invention can also include various adjuvants conventionally used in dyeing compositions for hair, such as anionic, cationic, non-ionic, amphoteric, zwitterionic surfactants or mixtures thereof, polymers anionic, canonic, non-ionic, amphoteric, zwitterionic or their mixtures, mineral or organic thickeners, agents 'Antioxidants, enzymes different from the 2-electron oxido-reductases used according to the invention such as for example peroxidases, penetrating agents, sequestering agents, perfumes buffers, dispersing agents, conditioning agents such as for example silicones, smoke-killing agents, Preservative agents, opacifying agents It is understood that the person skilled in the art will try to choose this or these possible complementary compounds in such a way that the advantageous properties intrinsically related to the ready-to-use dye composition according to the invention are not, or substantially, altered by the additive (s) under consideration The ready-to-use dye composition according to the invention can be presented in various forms, such as in the form of liquids, creams, gels, optionally pressurized, or in any other suitable form "for a dyeing of the keratin fibers, and particular mind the human hair. In this case, the oxidation dye (s) and the 2-electron oxido-reductases are present within the same composition ready for use, and therefore said composition must be free of gaseous oxygen, in order to avoid all premature oxidation of the colorant (s) by oxidation. The subject of the invention is also a process for dyeing keratin fibers and in particular human keratin fibers such as hair using the ready-to-use dye composition as defined above. According to this process, at least one ready-to-use dye composition is applied on the fibers as defined above, for a sufficient time to develop the desired coloration, after which it is rinsed, washed optionally with shampoo, The time necessary for the development of the coloration on the keratin fibers is generally between 3 and 60 minutes and even more precisely between 5 and 40 minutes According to a particular embodiment of the invention, the The method comprises a "preliminary step" consisting in separately storing, on the one hand, a composition (A) comprising, in a medium suitable for dyeing, at least one base of heterocyclic oxidation as defined above and / or at least one heterocyclic coupler as defined above and, on the other hand, a composition (B) including, in a medium suitable for dye, at least one 2-electron oxido-reductase-type enzyme in the presence of at least one donor for the indicated enzyme, then it would be mixed at the time of use before applying this mixture on the keratin fibers.

The "compositions A and B according to the invention can be conditioned in a multi-compartment device or dyeing kit or any other multi-compartment conditioning system of which a first compartment includes the composition (A) such as the one defined above and a second compartment includes the composition (B) as defined above. These devices can be equipped with a means for supplying the desired mixture to the hair, such as the devices described in patent FR-2,586,913 in the name of the applicant. The following examples are intended to illustrate the invention without thereby limiting the scope.

EXAMPLES COMPARATIVE EXAMPLES 1 AND 2 The following ready-to-use dye compositions were prepared (contained in grams) (*) Example that does not form part of the invention (**): Common dyeing support: -. Ethanol "- 10.0 g - Hydroxypropylated guar gum sold under the designation JAGUAR HP 60 by the Company MAYHA, LL 0.8 g - Alkyl (Cß-Cio) polyglucoside in 60% aqueous solution of active material (M.A.) buffered by ammonium citrate (0.5%), sold under the name ORAMIX CG110. by the Society SC 8.0 g - Monoethanolamine c.s pH = 9.5 It is important to appreciate that each of the ready-to-use dye compositions described above contain the same molar amount of each of the oxidation bases, namely 3.10-3 moles. Each of the ready-to-use dye compositions described above was applied to natural gray hair strands at 90% white for 30 minutes. The hair was then rinsed, washed with a standard shampoo, then dried. The color of the wicks was then evaluated before and after coloring in the MUNSELL system by means of a CM 2002 MINOLTA colorimeter in order to determine the strength of the placements obtained with each of the compositions described above. The difference between the color of the wick before dyeing and the color of the wick after dyeing was calculated by applying the NICKERSON formula:? E = 0.4 Co? H + 6? V + 3? C such as that described by example in "Couleur, Industrie et Techmque"; pages 14-17; vol. No. 5; 1978. In this formula? E represents the color difference between two wicks,? H,? Vy? C represent the variation in absolute value of the parameters H, V and C and Co represents the purity of the wick in relation to which you want to evaluate the color difference. The strength of coloration (? E) is all the more important the higher the figure indicated.

The results are given in Table I given below: Table I (*): Example that is not part of the invention. These results show that in the presence of the Uricase / Uric Acid oxidizing system, the "ready-to-use dye composition for example 1 which does not form part of the invention as it contains no heterocyclic oxidation dye leads to a clearly less potent coloration than the dye composition. ready for the use of Example 2 according to the invention and containing at least one heterocyclic compound, namely a heterocyclic oxidation base which is 2, 4, 5, 6-tetra-aminopyrimidine.

COMPARATIVE EXAMPLES 3 AND 4 The following ready-to-use dye compositions were prepared (contained in grams): (*) Example that does not form part of the invention (***): Common dyeing support: - Ethanol - - 20.0 g - Hydroxypropylated guar gum sold under the name JAGUAR HP 60 by the MAYRALL company - 1.6 g - Alkyl (Cs-Cio) polyglucoside in 60% aqueous solution of active material (M.A.) buffered by ammonium citrate (0.5%), sold under the name ORAMIX CG110 by the company S 8.0 g - Monoethanolamine c.s. pH 9.5 It is important to appreciate that each of the ready-to-use dye compositions described above contains the same amount of each of the oxidation bases, namely 6.10-3 moles. At the time of use, each of the ready-to-use dye compositions described above was mixed with an equal amount by weight of a 20 volume hydrogen peroxide solution. (6% by weight). Each of the resulting mixtures was applied on wicks of natural gray hair to 90% of whites for 30 minutes. The hair strands were then rinsed, washed with an ordinary shampoo, rinsed again and then dried. As described above for the examples 1 and 2 indicated above, the coloration was evaluated by the MUNSELL system, before and after the dyeing, by means of a CM2002 MINOLTA colorimeter. The strength of the coloring was calculated applying the NICKERSON formula. The results are indicated in Table II given below: Table II (*): Example that is not part of the invention. Contrary to what has been demonstrated above for comparative examples 1 and 2, these results show that using a classical oxidant system that does not form part of the invention, "as for example here hydrogen peroxide, the substitution of a benzene dye by a heterocyclic dye (here the paraphenylenediamine was substituted by 2, 4, 5, 6-tetra-aminopirimidina), does not allow to increase the strength of the obtained placements.

EXAMPLES 5 AND 6 COMPARATIVE The following ready-to-use dye compositions were prepared (contained in grams) (*) Example that does not form part of the invention (**): Common dyeing support: It is identical to that used for examples 1 and 2 indicated above. It is important to appreciate that each of the ready-to-use dye compositions described above contains the same molar amount of each of the oxidation bases, namely 3.10"3 moles Each of the ready-to-use dye compositions described above is applied on natural gray hair to 90% whites for 30 minutes The hair was then rinsed, washed with a normal shampoo, then dried, as described above for examples 1 and 2 indicated above, coloring It was evaluated by the MUNSELL system, before and after the dye, by means of a CM2002 MINOLTA colorimeter The strength of the coloration was calculated applying the NICKERSON formula The results are indicated in the following table III.

(*): Example that is not part of the invention. These results show that in the presence of the Uricase / Uric Acid oxidizing system, the ready-to-use dye composition for example 5, which does not form part of the invention, since it contains 2,5-diaminopyridine, which is a base of monocyclic pyridine oxidation, excluded from the invention leads to a clearly less strong coloration than the ready-to-use dye composition for the use of example 6 according to the invention and containing at least one heterocyclic compound according to the invention, namely a base of heterocyclic oxidation which is 2.4 , 5,6-tetraaminopyrimidine. EXAMPLES 7 TO 13 OF DYING The ready-to-use dye compositions according to the invention were prepared as follows (contents in grams): t o o > Os ** Support e tten com n It is identical to the one used for the examples 1 and 2 indicated above. Each of the ready-to-use dye compositions described above was applied on gray hair strands to 90% white, natural or permed, for 30 minutes. The hair was then rinsed, washed with an ordinary shampoo, and then dried. The hair strands were stained in the shades listed in Table IV given below.

Table IV It is noted that in relation to this date, the best method known by the applicant, to implement the aforementioned invention, is that which is clear from the manufacture of the objects to which it refers.

Having described the invention as above it is claimed as "property contained in the following.

Claims (37)

1. Ready-to-use composition for the oxidation dyeing of keratin fibers and in particular of human keratin fibers such as hair, which "comprises the combination of at least one oxidation base and at least one copulator, characterized by the The fact that it comprises, in a medium suitable for dyeing, at least one 2-electron oxide-reductase-type enzyme in the presence of at least one donor for said enzyme, and because said oxidation base and / or said copulator is chosen from the heterocyclic compounds excluding the monocyclic pyridine compounds 2.

Composition according to claim 1, characterized in that the oxidoreductase with 2 electrons is chosen among uricases of animal, microbiological or biotechnological origin.

Claim 1 or 2, characterized in that the 2-electron oxido-reductases represent from 0.01 to 20% in pe of the total weight of the dye composition ready for use.

Composition according to claim 3, characterized in that the 2-electron oxide or reductases represent from 0.1 to 5% by weight of the total weight of the ready-to-use dye composition.

5. Composition according to claim 2, characterized in that the donor (or substrate) for the indicated 2-electron oxido-reductase is chosen from uric acid and its salts.

Composition according to any one of the preceding claims, characterized in that the donor (s) represent from 0.01 to 20% by weight of the total weight of the dye composition ready for use.

Composition according to Claim 6, characterized in that the donor (s) represent from 0.1 to 5% by weight of the total weight of the dye composition ready for use.

8. Composition according to any one of the preceding claims, characterized in that the heterocyclic oxidation base (s) are chosen from the pyrimidine derivatives, the pyrazole derivatives and their addition salts with an acid.

9. The composition according to claim 8, characterized in that the pyrimidine derivatives are selected from 2, 4, 5, 6-tetra-aminopyrimidine, 4-hydroxy-2, 5, 6-triaminopyrimidine, pyrazole pyrimidine derivatives, and its addition salts with an acid.

Composition according to Claim 9, characterized in that the pyrazole pyrimidine derivatives are chosen from pyrazolo [1,5-a] -pyrimidine-3,7-diamine, 2-methyl pyrazolo- [1,5-a] ] -pyrimidine-3,7-diamine, 2,5-dimethylpyrazolo- [1,5-a] -pyrimidine-3,7-diamine, pyrazolo [1,5-a] -pyrimidine-3, 5- diamine, 2,7-dimethylpyrazolo [1,5-a] -pyrimidine-3,5-diamine, 3-amino pyrazolo- [1,5-a] pyrimidin-7-ol, 3-amino-5- methyl pyrazolo- [1, 5-a] -pyrimidin-7-ol, 3-amino pyrazolo- [1, 5-a] -? irimidin-5-ol, 2 (3-amino pyrazolo- [1, 5] -a] -pyrimidin-7-ylamino) -ethanol, 3-amino-7-β-hydroxyethylamino-5-methyl-pyrazolo- [1,5-a] -pyrimidine, 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-dimethylpyrazolo- [1,5 -a] -p? rimidma-3, 7-diamine, the 2,6-dime Useful pyrazolo- [1, 5-a] -pyrimidine-3,7-diamine, 2,5, N-7-tetramethyl pyrazolo- [1, 5-a] -pyrimidine-3,7-diamine, and its salts of addition and its tautomeric forms, when there is a tautomeric equilibrium.

The composition according to claim 8, characterized in that the pyrazole derivatives are chosen from 4,5-diamino pyrazole, 4,5-diamino-1-methyl pyrazole, 1-benzyl 4,5-diamino pyrazole, 3,4-diamino pyrazole, 1-benzyl 4,5-diamino-3-methyl pyrazole, 4-amino-1,3-dimethyl-5-hydrazinopyrazole, 4,5-diamino-3-methyl-1-phenyl-pyrazole, 4,5-diamino-3-methyl-1-tert-butyl pyrazole, 4,5-diamino-1-methyl-3-tert-butyl pyrazole, 4,5-diamino-1-ethyl-3-methyl-pyrazole, 4, 5-diamino-ethyl-3- (4'-methoxyphenyl) pyrazole, 4,5-diamino-1-ethyl-3-hydroxymethyl pyrazole, 4,5-diamino-3-hydroxymethyl-1-methyl-pyrazole, 4,5- diamino 3-hydroxymethyl-1-isopropyl pyrazole, 4,5-diamino-3-methyl-1-isopropyl pyrazole, and their addition salts with an acid.

Composition according to any one of the preceding claims, characterized in that the heterocyclic oxidation base (s) represent from 0.0005 to 12% by weight of the total weight of the ready-to-use dye composition.

13. Composition according to claim 12, characterized in that the heterocyclic oxidation base (s) represent from 0.005 to 6% by weight of the total weight of the ready-to-use dye composition.

Composition according to any one of the preceding claims, characterized in that he or the heterocyclic couplers are chosen from the indole derivatives, the indoline derivatives, the benzimidazole derivatives, the benzomorpholine derivatives, the sesamol derivatives, the pyrazole-azole derivatives, pyrrolo-azole derivatives, imidazole-azole derivatives, pyrazolo-pyrimidine derivatives, pyrazolin-3, 5-diones derivatives, pyrrolo- [3, 2-d] -oxazole derivatives, derivatives pyrazolo- [3, -d] -thiazoles, the thiozole-azole S-oxide derivatives, the S, S-dioxide-thiazole-azole derivatives, and their addition salts with an acid.

15. Composition according to claim 14, characterized in that the indole derivatives are chosen from the following compounds of formula (I), and their addition salts with an acid: wherein: R1 represents a hydrogen atom, an alkyl radical of Ct.-C4, a mono- or polyhydroxyalkyl radical of C2-C4 or ammoalkyl of C? -C4 whose amine is mono or disubstituted by an alkyl group of C? -C4; R2 represents a hydrogen atom or an alkyl radical of C? _C; R3 represents a hydrogen atom, a C1-C4 alkyl radical or hydroxyl; X represents a hydroxyl radical or NHR4 in which R4 represents a hydrogen atom, an alkyl radical of Ci-C4 or hydroxyalkyl of C1-C4.

16. - The composition according to claim 15, characterized in that the indole derivatives are chosen from 4-hydroxy indole, 6-hydroxy indole, 7-amino indole, 6-amino indole, 7-hydroxy indole , 7-ethyl 6- (β-hydroxyethyl) amino indole, 4-amino indole, 6-hydroxy 1-methyl indole, 5,6-dihydroxy indole, 4-hydroxy 1-N-methyl indole, 4-hydroxy 2-methyl indole, 4-hydroxy 5-methyl indole, 4-hydroxy-lN- (β-hydroxyethyl) indole, 4-hydroxy 1-N- (β-hydroxypropyl) indole, 1-N- (β, α-dihydroxypropyl) 4-hydroxy indole, 4-hydroxy 1-N- (β-hydroxyethyl) 5-methyl indole, 1-N- (β-dimethylaminopropyl) 4-hydroxy indole, and their addition salts with an acid.

17. The composition according to claim 14, characterized in that the indoline derivatives are chosen from 4-hydroxy indoline, 6-hydroxy indoline, 6-amino indoline, 5,6-dihydroxy indoline, and their salts. addition with an acid.

18. Composition according to claim 14, characterized in that the benzimidazole derivatives are chosen from the following compounds of formula (II), and their addition salts with an acid wherein: R5 represents a hydrogen atom or an alkyl radical of C? -C4, Rg represents a hydrogen atom, a radical "C? -C4 alkyl or phenyl, R7 represents a hydroxyl, amino or methoxy radical, R8- represents a hydrogen atom, a hydroxy, methoxy or alkyl radical of C? -C4, with the proviso that: - when R7 designates an amino radical, then it occupies position 4, when R7 _ occupies position 4, then R8 occupies position 7, when R occupies position 5, then R8 occupies position. position 6

19. Composition according to claim 18, characterized in that the benzimidazole derivatives are chosen 4-hydroxybenzimidazole, 4-aminobenzimidazole, 4-hydroxy-7-methylbenzimidazole, 4-hydroxy-2-methylbenzimidazole, -butyl 4-hydroxybenzimidazole, 4-amino-2-methyl-benzimidazole, 5,6-dihydroxy-benzimidazole, 5-hydroxy-6-methoxy-benzimidazole, 4,7-dihydroxy-benzimidazole, 4,7-dihydroxy-1-methyl benzimidazole, 4,7-dimethoxy benzimidazole, 5,6-dihydroxy 1-methyl benzimidazole, 5,6-dihydroxy 2-methyl benzimidazole, 5,6-dimethoxy benzimidazole, and their addition salts with an acid.

The composition according to claim 14, characterized in that the benzomorpholine derivatives are chosen from the following compounds of formula (III), and their addition salts with an acid: in which R_ and Rio, identical or different, represent a hydrogen atom or a C 1 -C 4 alkyl radical, Z represents a hydroxyl or amino radical.

21. The composition according to claim 20, characterized in that the benzomorpholine derivatives are chosen from 6-hydroxy-1,4-benzomorpholine, N-methyl-6-hydroxy-1,4-benzomorpholine, 6-amino-1 , 4-benzomorpholine, and its addition salts with an acid.

22. The composition according to claim 14, characterized in that the sesamol derivatives are chosen from the following compounds of formula (IV), and their addition salts with an acid: wherein: R n denotes a hydroxyl radical, amino alkyl '(C? -C4) amino, monohydroxyalkyl (C? ~ C4) amino or polyhydroxyalkyl (C2-C4) amino, R12 designates a hydrogen or halogen atom or a C? -C4 alkoxy radical

23. Composition according to claim 22, characterized in that the sesamol derivatives are chosen from 2-bromo 4, 5-methylenedioxy phenol, 2-methoxy 4,5-methylenedioxy aniline, 2- (β-hydroxyethyl) amino 4,5-methylenedioxy benzene, and their addition salts with an acid.

24. Composition according to claim 14, characterized in that the pyrazolo-azolic derivatives are chosen from: - 2-methyl pyrazolo [1,5-b] -1,2,4-triazole, - 2- ethyl pyrazolo [1,5-b] -1,2,4-triazole, - 2-isopropyl pyrazolo [1,5-b] -1,2,4-triazole, - 2-phenyl pyrazolo [1,5 -b] -1, 2, 4-triazole, - 2,6-dimethylpyrazolo [1,5-b] -1,2,4-triazole, - 7-chloro-2,6-dimethylpyrazolo [1, 5-b] -1, 2, 4-triazole, - 3,6-dimethyl-pyrazolo [3,2-c] -1,2,4-triazole - 6-phenyl-3-methylthio-pyrazolo [3, 2-c] -1, 2, 4- triazole, 6-Amino-pyrazolo [1, 5-a] benzimidazole, and its addition salts with an acid.

25. The composition according to claim 14, characterized in that the pyrrolozole derivatives are chosen from: - 5-cyano-4-ethoxycarbonyl-8-methyl pyrrolo [1,2-b] -1, 2, 4 -triazole, - 5-cyano-8-methyl-4-phenyl pyrrolo [1,2-b] -1, 2,4-triazole, 7-amido-6-ethoxycarbonyl pyrrolo [1,2-a] -benzimidazole and its addition salts with an acid. TO

26. Composition according to claim 14, characterized in that the imidazole-azolic derivatives are chosen from: - 7, 8-dicyano-imidazole- [3, 2-a] -imidazole, - 7, 8-dicyano-4 -methyl-imidazole- [3, 2-a] -imidazole, and its addition salts with an acid.

Composition according to claim 14, characterized in that the pyrazolopyrimidine derivatives are chosen from: - pyrazolo [1,5-pyrimidin-7-one, - 2,5-dimethylpyrazolo [1,5-a] ] pyrimidin-7-one, 2-methyl-6-ethoxycarbonyl pyrazolo [1,5-a] pyrimidin-7-one, - 2-methyl-5-methoxymethyl pyrazolo [1,5-a] pyrimidine-7 ona, - 2-tert-butyl-5-trifluoromethyl-pyrazolo [1, 5-a] pyrimidin-7-one, - 2,7-dimethyl pyrazolo [1, 5-a] pyrimidin-5-one, and its salts of addition with an acid.

Composition according to Claim 14, characterized in that the pyrazolin-3, 5-diones derivatives are chosen from: - 1,2-diphenylpyrazolin-3,5-dione, - 1,2-diethylpyrazolin-3, 5-dione, and its salts and addition with an acid.

29. Composition according to any one of the preceding claims, characterized in that the heterocyclic coupler (s) represent from 0.0001 to 10% by weight of the total weight of the ready-to-use dye composition.

30. Composition according to claim 29, characterized in that the heterocyclic coupler (s) represent from 0.005 to 5% by weight of the total weight of the dye composition ready for use.

31. Composition according to any one of the preceding claims, characterized in that it contains at least one additional oxidation base selected from paraphenylenediamines, bis-phenylalkylenediamines, orthophenylenediamines, "para-aminophenols, ortho-aminophenols, and their addition salts. with an acid and / or at least one additional coupler selected from eta-phenylenediamines, meta-aminophenols, meta-diphenols, and their addition salts with an acid

32. Composition according to any one of the preceding claims, characterized by The fact that the addition salts with an acid are chosen from hydrochlorides, hydrobromides, sulfates and tartrates, lactates and acetates.

33. Composition according to any one of the preceding claims, characterized in that the means suitable for dyeing is constituted by water or by a mixture of water and by at least one organic solvent.

Composition according to any one of the preceding claims, characterized in that it has a pH comprised between 5 and 11.

35. Composition according to any one of the preceding claims, characterized in that it contains at least one peroxidase. .

36. Method of dyeing keratin fibers _ and in particular human keratin fibers such as hair, characterized in that at least one ready-to-use dye composition as defined in any one of the above-mentioned fibers is applied to said fibers. previous claims, for a sufficient time to develop the desired coloration.

37. The method according to claim 36, characterized in that it comprises a preliminary step consisting of storing separately, on the one hand, a composition (A) comprising, in a medium suitable for dyeing, at least one base of heterocyclic oxidation as defined in any one of claims 1, 8 to 13 and 32 and / or at least one heterocyclic coupler as defined in any one of claims 1, 14 to 30 and 32, and, on the other hand, a composition (B) that includes, in a medium suitable for dyeing, at least one 2-electron oxido-reductase-type enzyme in the presence of at least one donor for the indicated enzyme, then in proceeding to its mixing at the time of use before applying this mixture on the keratin fibers.