MXPA99004993A - Oxidation dyeing composition for keratin fibres - Google Patents

Abstract

The invention concerns a ready-to-use oxidation dyeing composition for keratin fibres, and in particular human keratin fibres such as hair comprising, in an appropriate medium for dyeing, at least an oxidation base, at least a C2 glycol C4-C8 ether and/or a C3-C9 glycol C1-C8 ether and at least an oxidoreductase type 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 DYE BY OXIDATION OF THE KERATINIC FIBERS AND DYE PROCEDURE USING THIS COMPOSITION The subject of the invention is a composition for oxidation dyeing of keratin fibers, and in particular human keratin fibers such as hair, comprising, in a medium suitable for dyeing, at least one oxidation base, at least an ether of 1 to 8 carbon atoms of glycol of 2 carbon atoms, and at least one 2-electron oxide-reductase type enzyme in the presence of at least one donor for said enema, as well as the dyeing process employed by this composition.

It is known to dye the keratin fibers and in particular human hair with dyeing compositions containing oxidation dye precursors, in particular ortho or para-phenylenediamines, ortho or para-aminophenols, heterocyclic bases, generally called oxidation bases. Oxidation dye precursors, or oxidation bases, are colorless or faintly colored stains that, when oxidized, can give rise to REF .: 30199 process of. oxidative condensation to colored compounds and dyes.

It is also known that the shades obtained with these oxidation bases can be varied by associating them with copulators or color modifiers, the latter being chosen mainly among the aromatic meta-diamines, the meta-aminophenols, the meta-diphenols and certain heterocyclic compounds.

The variety of molecules put into play at the level of oxidation bases and copulators allows obtaining a rich range of colors.

The so-called "permanent" coloration obtained by these oxidation dyes must otherwise meet a certain number of requirements. Therefore, it should not have toxicological drawbacks, it should allow obtaining tonalities at the desired intensity, and present a good resistance against external agents (light, bad weather, washing, permanent wave, perspiration, friction).

The dyes must also make it possible to cover the white hair, and finally to be as non-selective as possible, that is to say allow to obtain the smallest deviations of coloration possible throughout the same keratin fiber, which may be in effect sensitized in a different way. (that is, spoiled) between its tip and its root.

The coloration by oxidation of the keratin fibers is generally carried out in an alkaline medium, in the presence of hydrogen peroxide. However, the use of the alkaline media in the presence of hydrogen peroxide has the disadvantage of involving a non-negligible degradation of the fibers, as well as a significant discoloration of the keratin fibers which is not always desirable.

The coloration by oxidation of the keratin fibers can also be carried out with the aid of oxidant systems other than hydrogen peroxide such as enzymatic systems. Thus, it has already been proposed to dye keratin fibers, mainly in patent application EP-A-0 310 675, with compositions comprising an oxidation base and optionally a copulator, in association with enzymes such as pyranose-ox-dasa, the glucose oxidase or the uricase, in the presence of a donor for said enzymes. These dyeing processes, although used under conditions which do not involve a degradation of the keratin fibers comparable to that generated by the dyes carried out in the presence of hydrogen peroxide, lead to colorations which do not give complete satisfaction mainly from the point of view of their power, its chromaticity and its resistance to the various aggressions that the hair can suffer.

Now, the Applicant Firm has just discovered that it is possible to obtain new dyes, capable of leading to strong and chromatic colorations, without generating significant degradation of the keratin fibers, which are not very selective and which resist the various aggressions that the fibers can suffer. associating at least one oxidation base with at least one ether of 4 to 8 carbon atoms of glycol of 2 carbon atoms and / or at least one ether of 1 to 8 carbon atoms of glycol of 3 to 9 carbon atoms, and at least one 2-electron oxido-reductase type enzyme in the presence of at least one donor for said enzyme.

This discovery forms the basis of the present invention.

The invention therefore has, as a first object, a composition prepared for the use, for oxidative dyeing of keratin fibers and in particular of human keratin fibers such as hair, characterized in that it comprises, in a Appropriate medium for the dye: - at least one oxidation base, at least one ether of 4 to 8 carbon atoms, of a glycol of 2 carbon atoms and / or at least one ether of 1 to 8 carbon atoms of glycol of 3 to 9 carbon atoms carbon, - at least one 2-electron oxide-reductase type enzyme, and at least one donor for said enzyme.

The dye composition prepared for use according to the invention leads to powerful, chromatic colorations, which have a low selectivity and excellent properties of resistance at the same time against atmospheric agents, such as light and weathering and against perspiration and at different treatments that can suffer the hair (washes, permanent deformations).

Another subject of the invention is a dyeing process by oxidation of the keratin fibers using this dye composition prepared for use.

The 2-electron oxide-reductases used in the dye composition prepared for the use according to the invention can be chosen mainly from pyranose oxidases, glucose oxidases, glycerol oxidases, lactates oxidases, pyruvate oxidases, and uricases.

According to the invention, the 2-electron oxide reductases are preferably chosen from uricas of animal, microbiological or biotechnological origin.

By way of example, mention may be made, in particular, of the uricase of wild boar liver extract, the uricase of Arthrobacter globiformis, as well as the uricase of Asperillus flavus.

The 2-electron oxide-reductases can be used in pure crystalline form or in a dilute form in an inert diluent for said 2-electron oxide 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 dye composition prepared for use, and even more preferably from 0.1 to 5% by weight approximately of this weight .

According to the invention, the term "donor" means the different substrates involved in the operation of said or said 2-electron oxide reductases.

The nature of the donor (or substrate) for said enzyme varies depending on the nature of the 2-electron oxide-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, mention may be made of D-glucose, as a donor for glycerol oxidases, mention may be made of 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) (or substrates) used according to the invention preferably represent from 0.01 to 20% by weight approximately of the total weight of the dye composition prepared for the use according to the invention and even more preferably from 0.1 to 5% in approximately this weight.

The nature of the oxidation base (s) used in the ready-to-use dye composition is not critical, it can be chosen mainly from para-phenylenediamines, double bases, para-aminophenols, ortho-aminophenols and heterocyclic oxidation bases.

Among the para-phenylenediamines which can be used as the oxidation base in the dyeing compositions according to the invention, mention may be made in particular of the compounds of the formula (I) (supra) and their addition salts with an acid: wherein: - Ri represents a hydrogen atom, an alkyl radical of C? -C4, monohydroxyalkyl of C1-C4, polyhydroxyalkyl of C; -C4, akoxy (C1-C4) alkyl (Ci- C), alkyl of C1 -C4 substituted by a nitrogenous group, phenyl or '-amino-phenyl; - R: represents a hydrogen atom, an alkyl radical of C; -C, monohydroxyalkyl of C? -C4 polyhydroxyalkyl of C.-C4, alkoxy (C1-C4) alkyl (C1-C4) or substituted C1-C4 alkyl by a nitrogenous group; Rj represents a hydrogen atom, a halogen atom such as a chlorine, bromine, iodine or fluorine atom, an alkyl radical of C, -C4, monohydroxyalkyl of C, -C4, hydroxyalkoxy of C1-C4, acetylaminoalkoxy of C; -C4, C 1 -C 4 mesylaminoalkoxy or C 1 -C 4 carbamoylaminoalkoxy; - R 4 represents a hydrogen, a halogen atom or a C 1 -C 4 alkyl radical.

Among the nitrogen groups of the formula (I) above, mention may be made, in particular, of the amino, mono (C1-C4) amino, dialkyl (C1-C4) amino, trialkyl (C1-C4) amino, monohydroxyalkyl (C1-C4) radicals amino, imidazolinium and ammonium.

Among the para-phenylenediamines of formula (I) above, mention may be made more particularly of para-phenylenediamine, para-tolylene-diamine, 2-chloro-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine and 2,6-diethyl-para-phenylenediamine. 2,5-dimethyl paraphenylenediamine, N, N-dimethyl paraphenylenediamine, N, N-diethyl paraphenylenediamine, N, N-dipropyl paraphenylenediaxaine, 4-amino N, N-diethyl 3-methyl aniline, N, N -bis- (β-hydroxyethylD-para-phenylenediamine, 4-N, N-bis- (β-hydroxyethyl) amino 2-methyl aniline, 4 ~ N, N-bis- (β-hydroxyethyl) amino 2-chloroaniline, -β-hydroxyethyl paraphenylenediamine, 2-fluorophenylenediamine, 2-iopropyl paraphenylenediamine, N- (β-hydroxypropyl) paraphenylenediamine, 2-hydroxymethyl paraphenylenediamine, N, -dimethyl 3-methyl paraphenylenediamine, N, N- ( ethyl, ß-hydroxyethyl) paraphenylenediamine, N- (ß,? - dihydroxypropyl) paraphenylenediamine, N- (4'-aminophenyl) paraphenylenediamine, N-phenyl para-phenylenediamine, 2-β-hydroxyethyloxy paraphenylenediamine, 2-β-acetylaminoethyloxy paraphenylenediamine, N- (β-methoxyethyl) paraphenylenediamine, and their addition salts with an acid.

Among the para-phenylenediamines of formula (I) above, para-phenylenediamine, para-tolylenediamine, 2-isopropyl para-phenylenediamine, 2-β-hydroxyethyl paraphenylenediamine, 2-β-hydroxyethyloxy paraphenylenediamine, 2,6-dimethyl paraphenylenediamine, are particularly preferred. 2,6-diethyl paraphenylenediamine, 2,3-dimethyl paraphenylenediamine, N, N-bis- (β-hydroxyethyl) paraphenylenediamine, 2-chloro-para-phenylenediamine, 2-β-acetylaminoethyloxy paraphenylenediamine, and more particularly, its salts of addition with an acid.

According to the invention, double bases are understood to be compounds comprising at least two aromatic nuclei on which amino and / or hydroxyl groups are carried.

Among the double bases which can be used as oxidation bases in the dyeing compositions according to the invention, mention may be made in particular of the compounds corresponding to the following formula (II), and their addition salts with an acid: wherein: - Z; and Z :, identical or different, represent a hydroxyl radical or -NH; which can be substituted by a C 1 -C 4 alkyl radical or by a linking arm Y; - the linking arm Y represents an alkylene chain comprising from 1 to 14 carbon atoms, linear or branched, which can be interrupted or terminated by one or more nitrogen groups and / or by one or more heteroatoms, such as oxygen atoms, of sulfur or nitrogen, and optionally substituted by one or more hydroxyl or C6-C6 alkoxy radicals; - R5 and Re represent a hydrogen or halogen atom, an alkyl radical of C? -C4, monohydroxyalkyl of C? ~ C4, polyhydroxyalkyl of C2-C4, aminoalkyl of C1-C4 or a linking arm Y; - R7, Re, R9, Rio, Rn and R? 2, identical or different, represent a hydrogen atom, a linking arm Y or a C1-C4 alkyl radical; it being understood that the compounds of formula (II) only comprise one linking arm Y per molecule.

Among the nitrogen groups of the formula (II) above, mention may be made, in particular, of the amino, mono (C1-C4) amino, dialkyl (C1-C4) amino, trialkyl (C1-C4) amino, monohydroxyalkyl (C1-C4) radicals amino, imidazolium and ammonium radicals.

Among the double bases of formulas (II) above, N, N'-bis- (β-hydroxyethyl) N, N '-bis- (4'-aminophenyl) -1,3-diamino propanol, N, N'-bis- (β-hydroxyethyl) N, N '-bis- (4'-aminophenyl) ethylenediamine, N, N'-bis- (4-aminophenyl) tetramethylenediamine, N, N'-bis- (ß-hydroxyethyl) N, N'-bis- (4-aminophenyl) tetramethylenediamine, N, N'-bis- (4-methyl aminophenyl) tetramethylenediamine, N, N'-bis- (ethyl) N, N ' -bis- (4'-amino, 3'-methylphenyl) ethylenediamine, 1,8-bis- (2,5-diaminophenoxy) -3,5-dioxaoctane, and their addition salts with an acid.

Among these double bases of formula (II), the N, N'-bis- (β-hydroxyethyl) N, N 1 -bis- (4α-aminophenyl) 1,3-diamino propanol, 1,8-bis- (2,5-diaminophenoxy) -3,5- dioxaoctane or one of its addition salts with an acid are particularly preferred.

Among the para-aminophenols which can be used as oxidation bases in the dyeing compositions according to the invention, mention may be made in particular of the compounds corresponding to the following formula (III), and their addition salts with an acid: wherein: - R 13 represents a hydrogen or halogen atom, a C 1 -C 4 alkyl radical, C 1 -C 4 monohydroxyalkyl, (C 1 -C 4) alkoxy (C 1 -C 4) alkyl, C 1 -C 4 aminoalkyl or hydroxyalkyl ( C1-C4) C 1 -C 4 aminoalkyl, - Ri4 represents a hydrogen or halogen atom, a C1-C4 alkyl radical, a C1-C4 monohydroxyalkyl, a C-C4 polyhydroxyalkyl, a C1-C4 aminoalkyl, a C1-C cyanoalkyl or a (C1-C4) alkoxy alkyl (C1-C4), it being understood that at least one of the radicals Ri 3 or R 1 represents a hydrogen atom.

Among the paraminophenols of formula (III) above, mention may be made more particularly of para-aminophenol, 4-amino-3-methyl phenol, 4-amino-3-fluoro-phenol, 4-amino-3-hydroxymethyl-phenol, 4-amino-2 -methyl phenol, 4-amino-2-hydroxymethyl phenol, 4-amino-2-methoxymethyl phenol, 4-amino-2-aminomethyl phenol, 4-amino 2- (β-hydroxyethyl aminomethyl) phenol, 4-amino 2 -fluoro phenol, and its addition salts with an acid.

Among the ortho-aminophenols which can be used as oxidation bases in the dyeing compositions according to the invention, mention may be made more particularly of 2-amino-phenol, 2-amino-5-methyl-phenol, 2-amino-6-methyl-phenol, -acetamido 2-amino phenol, and its addition salts with an acid.

Among the heterocyclic bases which can be used as oxidation bases in the dyeing compositions according to the invention, mention may be made more particularly of the pyridine derivatives, the pyrimidine derivatives, the pyrazole derivatives, the pyrazolo-pyrimidine derivatives and their addition salts with a acid.

Among the pyridine derivatives, mention may be made more particularly of the compounds described, for example, in 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- (β-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 more particularly of the compounds described, for example, in German patents DE 2 359 399 or Japanese patents JP 88-169 571 and JP 91-10659 or patent applications WO 96/15765, such as 2, 4, 5,6-tetra-aminopyrimidine, 4-hydroxy 2,5-, 6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine, 2, 5, 6 -triaminopyrimidine, and its addition salts with an acid.

Among the pyrazole derivatives, mention may be made more particularly of the compounds described in DE 3 843 892, DE 4 133 957 and patent applications WO 94/08969, W094 / 08970, FR-A-2 733 749 and DE 195 43 988 such as 4,5-diamino-1-methyl pyrazole, 3,4-diamino pyrazole , 4,5-diamino 1- ('-chlorobenzyl) pyrazole, 4,5-diamino-1,3-dimethylpyrazole, 4,5-diamino-3-methyl-1-phenyl-pyrazole, 4,5-diamino-1 -methyl 3-phenyl pyrazole, 4-amino-1,3-dimethyl-5-hydrazine pyrazole, 1-benzyl-4,5-diamino-3-methyl-pyrazole, 4,5-diamino-3-tert-butyl-1-methyl-pyrazole , 4,5-diamino-1-tert-butyl 3-methyl pyrazole, 4,5-diamino 1- (β-hydroxyethyl) 3-methyl pyrazole, 4,5-diamino-1-ethyl-3-methyl pyrazole, 4,5 diamino 1-ethyl 3- (4'-methoxypheniDpyrazole, 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-isopropylpyrazole, 4-amino-5- (2'-aminoethyl) amino-1,3-dimethylpyrazole, 3, 4, 5-triaminopyrazole, 1-methyl-3, 4,5-triamino pyrazole, 3,5-diamino-1-methyl-4-methylamino pyrazole, 3,5-diamino-4- (β-hydroxyethyl) amino-1-methyl pyrazole, and their addition salts with an acid.

Among the pyrazolo-pyrimidine derivatives, mention may be made more particularly of the pyrazolo- [1, 5-a] -pyrimidines of the following formula (IV), their addition salts with an acid or a base and their tautomeric forms, when there is a Tautomeric balance: wherein: - Ris Rie R17, and Ria, identical or different, designate a hydrogen atom, a C1-C4 alkyl radical, an aryl radical, a hydroxyalkyl radical of C1-C4, a polyhydroxyalkyl radical of C2-C4, a (C 1 -C 4) alkoxy C 1 -C 4 alkyl radical, a C 1 -C 4 aminoalkyl radical (the amine may be protected by an acetyl, ureido or sulfonyl radical), a C 1 -C 4 alkylamino alkyl radical C4, a di- [(C1-C4) alkyl] amino-C1-C4 alkyl radical, wherein the dialkyl radicals can form a carbon cycle or a heterocycle with 5 or 6 links), a hydroxy radical (C1-C4) alkyl- or di [hydroxy (C1-C4) alkyl] amino C1-C alkyl; - the radicals X designate, identical or different, a hydrogen atom, a C 1 -C 4 alkyl radical, an aryl radical, a hydroxyalkyl radical of C 1 -C 4, a polyhydroxyalkyl radical of C 2 -C 4, an amino alkyl radical of a radical (C1-C4) alkyl amino C1-C4 alkyl, a di- [(C1-C4) alkyl] amino radical of C1-C4 alkyl (the dialkyls may form a carbon cycle or a heterocycle with 5 or 6 links), a hydroxy (dC) alkyl or di- [hydroxy (CI-CJ) alkyl] amino alkyl radical of dC, an amino radical, a (C1-C4) alkyl- or di- [(C? -C) alkyl] -amino radical; a halogen atom, a carboxylic acid group, a sulfonic acid group; - i is equal to 0, 1, 2 or 3; - p is equal to o or 1; - q equals 0 or 1; - n is equal to 0 or 1; provided that: - the sum p + q is different from 0; - when p + q is equal to 2, then n is 0 and the groups NR15R? 6 and NR17RIT occupy positions (2,3); (5,6); (6,7); (3.5) or (3.7); - when p + q is equal to 1, then n is 1 and the group NR15R16 (or NRnRiß) and the group OH occupy the positions (2,3); (5,6); (6,7); (3.5) or (3.7); When the pyrazolo- [1, -5-a] -pyrimidines of formula (IV) above are such that they comprise a hydroxyl group on one of positions 2, 5 or 7 on a of a nitrogen atom, there is a tautomeric equilibrium represented ,. for example, by the following scheme: Among the pyrazolo- [1, 5-a] -pyrimidines of formula (IV) above, mention may be made principally of: - 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 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-hydroxy-ethyl) -amino] -ethanol 2- [(7-Amino-pyrazolo [1,5-a] pyrimidin-3-yl) - (2-hydroxy-ethyl) -amino] -ethanol-5,6-dimethyl-pyrazolo- [1,5-a] -pyrimidin-3,7-diamine; - 2,6-dimethylpyrazolo- [1,5-a] -pyrimidine-3,7-diamine; 2, 5, N 7, N 7 -tetramethyl pyrazolo- [1,5-a] -pyrimidine-3,7-diamine; and its addition salts and tautomeric forms, when there is a tautomeric equilibrium.

The pyrazolo- [1, 5-a] -pyrimidines of formula (IV) above can be prepared by cyclization from an aminopyrazole according to the syntheses described in the following references: - EP 628559 BEIERSDORF-LILLY - R. Vishdu, H. Navedul, Indian J. Chem., 34b (6), 514, 1995. - N.S. Ibrahim, .K.U. Sadek, F.A. Abdel-Al, Arch. Pharm., 320, 240, 1987. - R.H. Springer, M.B. Scholt.en, D.E. O'Brien, T. Novinson, J.P. Miller, R.K. Robins, J. Med. Chem., 25, 235, 1982. - T. Novinson, R.K. Robins, T.R. Matthe s, J. Med. Chem., 20, 296, 1977. - US 3907799 ICN PHARMACEUTICALS The pyrazolo- [1, 5-a] -pyrimidines of formula (IV) above can also be prepared by cyclization from hydrazine according to the syntheses described in the following references: - A. McKillop and R.J. Kobilecki, Heterocycles, 6 (9), 1355, 1977 - E. Alcade, J. De Mendoza, J.M. Marcia-Marquma, C. Almera, J. Elguero, J. Heterocyclic Chem., 11 (3), 423, 1974. - K. Saito, I. Hori, M. Higarashi, H. Midopkawa, Bull. Chem. Soc. Japan, 47 (2), 476, 1974.

The oxidation base or bases preferably represent from 0.0005 to 12% by weight approximately of the total weight of the dye composition according to the invention, and even more particularly from 0.005 to 6% by weight approximately of this weight.

The ready-to-use dye composition according to the invention could also contain one or more couplers. These couplers can be chosen in particular for meta-phenylenediams, meta-aminophenols, meta-diphenols, heterocyclic couplers such as, for example, indole derivatives, indoline derivatives, benzimidazole derivatives, benzomorfolm derivatives, sesamol derivatives and pyridine, pyrimidine and pyrazole derivatives, and the addition salts thereof with an acid.

These couplers can be chosen more particularly from 2-methyl-5-aminophenol, 5-N- (β-hydroxyethyl) amino-2-methylphenol, 3-aminophenol, 1,3-dihydroxybenzene, 1,3-dihydroxy-2- methylbenzene, 4-chloro-1,3-dihydroxybenzene, 2,4-diamino-1- (β-hydroxyethyloxy) -benzene, 2-amino-4- (β-hydroxyethylamino) -1-methoxybenzene, 1,3-diaminobenzene, 1, 3-bis (2,4-diaminophenoxy) propane, sesamol, α-naphthol, 6-hydroxyindole, 4-hydroxyindole, 4-hydroxy-N-methylindole, 6-hydroxyindole, 2,6-dihydroxy-4-methylpyridine, lH-3-methylpyrazol-5-one and l-phenyl-3-phenyl-pyrazol-5-one, and the addition of the salts thereof with an acid.

When the coupler (s) is present, they preferably represent from 0.001 to 10% by weight approximately of the total weight of the dye composition prepared for use and even more preferably from? .005 to 5? in weight approximately of this weight.

In a general manner, the addition salts with an acid which can be used in the context of the dyeing compositions of the invention (oxidation bases and couplers) are chosen primarily from hydrochlorides, brohydrates, sulfates and tartrates, lactates and the acetates.

The ether (s) of 4 to 8 carbon atoms of a glycol of 2 carbon atoms used in the ready-to-use dye composition according to the invention, is (are) preferably selected from alkyl ethers of 4 to 8 carbon atoms of a glycol of 2 carbon atoms, such as ethylene glycol monobutyl ether, and aryl ethers of 6 to 8 carbon atoms of a glycol of 2 carbon atoms, such as ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether .

The ether (s) - of C 1 - glycol of C. - C. used in the ready-to-use dye composition according to the invention is (are) preferably selected from alkyl of 1 to 8 carbon atoms, alkyl ethers 1 to 8 carbon atoms of a glycol of 3 to 9 carbon atoms, such as propylene glycol monomethyl ether, propylene glycol onoethylether, i = opropylene glycol diethyl ether, diethylene glycol monomethyl ether and monoethyl ether, dipropylene glycol monomethyl ether and tripropylene glycol monomethyl ether, and aryl ethers of 6 to 8 carbon atoms a glycol of 3 to 9 carbon atoms, such as propylene glycol monophenyl ether, propylene glycol monobenzyl ether, diethylene glycol monophenyl ether and diethylene glycol monobenzyl ether.

The ether (s) of 4 to 8 carbon atoms of a glycol of 2 carbon atoms and / or the ether (s) of 1 to 8 carbon atoms of a glycol of 3 to 9 carbon atoms carbon represents (s) from 1 to 40% by weight approximately relative to the total weight of the dye composition, and even more preferably from 5 to 30% by weight approximately.

The ready-to-use dye composition according to the invention may also contain one or more direct dyes, in particular in order to modify the forms or enrich them with intensity.

The pH of the composition prepared for the use according to the invention is chosen so that the enzymatic activity of the 2-electron oxide reductase is sufficient. It is generally comprised between about 5 and 11, and preferably between about 6.5 and about 10. It can be adjusted to the desired value by means of acidifying or alkalizing agents commonly used in dyeing 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 triethanolamines, 2-methyl-2-aminopropanol and its derivatives, sodium hydroxides. or of potassium and the compounds of formula (v) below: R 37 ^ 3 \ N-W-N (V) < -3R R40 in which W is a propylene residue optionally substituted by a hydroxyl group or an alkyl radical of C? -C4; R37, 38 R39 and R40 identical or different, represent a hydrogen atom, a C1-C4 alkyl radical or hydroxyalkyl The dye composition prepared for use in accordance with the invention can also contain various adjuvants conventionally used in hair dyeing compositions, such as anionic, cationic, non-ionic, amphoteric, zwitterionic surfactants or mixtures thereof, polymers anionic, cationic, non-ionic, amphoteric, zwitterionic or their mixtures, mineral or organic thickening agents, antioxidant agents, enzymes other than the 2-electron oxide 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, volatile or non-volatile silicones, modified or unmodified, smoke-killing agents, ceramides, preserving agents, opacifying agents.

Of course, the technician will endeavor to choose this or these possible complementary compounds in such a way that the advantageous properties intrinsically bound to the dye composition prepared for use according to the invention are not substantially altered by the addition (s) considered.

The dye composition prepared for use according to the invention can be present in various forms, such as in the form of liquids, creams, gels, optionally pressurized, or in any other form suitable for dyeing the keratin fibers, and mainly of the human hair. In this case, the oxidation dye (s) and the 2-electron oxide (s) reductases are present in the same composition prepared for use, and therefore said composition must be free of gaseous oxygen, in order to avoid any premature oxidation of the oxidation dye (s).

The subject of the invention is also a dyeing process for keratin fibers and in particular for human keratin fibers such as hair using the dye composition prepared for use as defined above.

According to this method, at least one dye composition prepared for use as defined above is applied to the fibers for a sufficient time to develop the desired coloration, after which it is rinsed, optionally washed with shampoo, rinsed again and it dries.

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 method comprises a preliminary stage consisting of storing separately, on the one hand, a composition (Al) comprising, in a medium suitable for dyeing, at least one oxidation base and at least one ether of 4 to 8 carbon atoms, of a glycol of 2 carbon atoms and / or at least one ether of 1 to 8 carbon atoms of glycol of 3 to 9 carbon atoms, and, on the other hand , a composition (Bl) containing, 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, then proceeding to its mixing at the time of employment before applying this mixture on the keratin fibers.

According to a second specific embodiment of the invention, the process includes a first step which consists in separately storing, in a manner, a composition (A2) comprising, in a medium which is suitable for the dye, at least one oxidation base and, on the other hand, a composition (B2) comprising, in a suitable medium which is suitable for the intendant, at least one ether of 4 to 8 carbon atoms, of a glycol of 2 carbon atoms and / or at least one ether of 1 to 8 carbon atoms of glycol of 3 to 9 carbon atoms, and at least one enzyme of oxidoreductase type of 2 electrons in the presence of at least one donor for said enzyme, followed by the mixed thereof together at the time of use, after which, this mixture is applied to the keratin fibers.

Another object of the invention is a device with several compartments or dye "kit" or another conditioning system with several compartments, whose first compartment contains the composition (Al) or (A2) as defined above and a second compartment contains the composition (Bl) or (B2) as defined above. These devices may be equipped with a means for dispensing the desired mixture on the hair, such as the devices described in patent FR-2 586 913 in the name of the Applicant Firm.

The following examples are intended to illustrate the invention without, however, limiting the scope.

EXAMPLES DYE EXAMPLE 1 The dye compositions prepared for the following use (contents in grams) were prepared: -for-phenylenediamine 0.324 g -1, 3-dihydroxybenzene 0.33 g -monomethyl ether of 20.0 g propylene glycol -Urricasa of Arthrobacter 1.5 g globiformis to 20 International Units (I.U) / mg, sold by the Sigma Company.

- Uric acid 1.5 g - Hydroxyethylcellulose sold under the name NATROSOL 1.0 g 250 HR® by the company AQUALON -Alkyl (Ce-Cio) polyglycoside 8.0 g in aqueous solution at 60 of active material (M.A.) buffered by ammonium citrate (0.5%), sold under the name ORAMIX CG110® by the company SEPPIC -monoethanolamine c.s pH = 9.5 -demineralized water that 100.0 g Each of the dye compositions prepared for the use described above was applied to wicks of natural gray hair with 90% blanks for 30 minutes. The hair was then rinsed, washed with a standard shampoo, then dried.

The hair was dyed in shades of a dark blond tone It is noted that in relation to this date, the best method known to the applicant, to put into practice the aforementioned invention is that which is clear from the manufacture of the objects to which it refers.

Having described the invention as above, the content of the following is claimed as property.

Claims (38)

1. Composition prepared for use, for oxidation dyeing of keratin fibers and in particular of human keratin fibers such as hair, characterized in that it comprises, in an appropriate medium for dyeing: - at least one oxidation base, - at least one ether of 4 to 8 carbon atoms, of a glycol of 2 carbon atoms and / or at least one ether of 1 to 8 carbon atoms of glycol of 3 to 9 atoms of carbon, - at least one 2-electron oxide-reductase type enzyme, - and at least one donor for said enzyme.

2. Composition according to claim 1, characterized in that the 2-electron oxide reductases are chosen from the pyranose oxidases, the glucose oxidases, the glycerol oxidases, the lactate oxidases, the pyruvate oxidases, and the uricases.

3. composition according to any one of claims 1 or 2, characterized in that the 2-electron oxide reductases are chosen from uricas of animal, microbiological or biotechnological origin.

4. Composition according to any one of the preceding claims, characterized in that the 2-electron oxide-reductases represent from 0.01 to 20% by weight of the total weight of the dye composition prepared for use.

5. Composition according to claim 4, characterized in that the 2-electron oxide-reductases represent from 0.1 to 5% by weight of the total weight of the dye composition prepared for use.

6. composition according to claim 3, characterized in that the donor (or substrate) for said 2-electron oxide reductase is chosen from uric acid and its salts.

7. 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 prepared for use.

8. composition according to claim 7, characterized in that the donor (s) represent from 0.1 to 5% by weight of the total weight of the dye composition prepared for use.

9. composition according to any one of the preceding claims, characterized in that the oxidation base (s) are chosen from paraphenylenediamines, double bases, para-aminophenols, ortho-ammophenols and heterocyclic oxidation bases.

10. Composition according to claim 9, characterized in that the para-phenylenediamines are chosen from the following compounds of formula (1) and their addition salts with an acid: wherein: - Ri represents a hydrogen atom, an alkyl radical of C: -C4, monohydroxyalkyl of C1-C4, polyhydroxyalkyl of C; -C4, akoxy (C1-C4) alkyl (Ci- C4), alkyl of C1 -C4 substituted by a nitrogenous group, phenyl or 4'-amino-phenyl; - R; represents a hydrogen atom, an alkyl radical of C: -Ci, monohydroxyalkyl of C-C4 polyhydroxyalkyl of C.-C4, alkoxy (C1-C4) alkyl (C; -C4) or C1-C4 alkyl substituted by a nitrogen group; R5 represents a hydrogen atom, a halogen atom such as a chlorine, bromine, iodine or fluorine atom, an alkyl radical of C, -C, monohydroxyalkyl of C1-C4, hydroxyalkoxy of C? -C4, acetylaminoalkoxy of C1-C4, C 1 -C 4 mesylaminoalkoxy or C 1 -C 4 carbamoylaminoalkoxy, - R represents a hydrogen atom, a halogen atom or a C 1 -C 4 alkyl radical.

11. Composition according to claim 10, characterized in that the para-phenylenediamines of formula (I) are chosen from para-phenylenediamine, para-tolylene-diamine, 2-chloro-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-diethyl paraphenylenediamine, 2,5-dimethyl paraphenylenediamine, N, -dimethyl paraphenylenediamine, N, N-diethyl paraphenylenediamine, N, N-dipropyl paraphenylenediaxaine, 4-amino N, N-diethyl 3-methyl aniline, N, N-bis- (β-hydroxyethyl) paraphenylenediamine, 4-N, N-bis- (β-hydroxyethyl) mino 2-methyl aniline, 4 ~ N, N-bis- (β-hydroxyethyl) amino 2-chloroaniline, 2-β-hydroxyethyl paraphenylenediamine, 2-fluorophenylenediamine, 2-isopropyl paraphenylenediamine, N- (β-hydroxypropyl) paraphenylenediamine, 2-hydroxymethyl paraphenylenediamine, N, N-dimethyl 3-methyl para-phenylenediamine, N-, N- (ethyl, β-hydroxyethyl) paraphenylenediamine, N- (β, β-dihydroxypropyl) paraphenylenediamine, N- ('-aminophenyl) paraphenylenediamine, N-phenyl paraphenylenediamine, 2-β-hydroxyethyl-oxy para-phenylenediamine, 2-β-acetylaminoethyloxy paraphenylenediamine, N- (β-methoxyethyl) paraphenylenediamine, and their addition salts with an acid.

12. Composition according to claim 9, characterized in that the double bases are chosen from the compounds of formula (II), and their addition salts with an acid: wherein: - 2i and Z :, identical or different, represent a hydroxyl radical or -NH; which can be substituted by a C 1 -C 4 alkyl radical or by a linking arm Y; - the linking arm Y represents an alkylene chain comprising from 1 to 14 carbon atoms, linear or branched, which can be interrupted or terminated by one or more nitrogen groups and / or by one or more heteroatoms, such as oxygen atoms, of sulfur or nitrogen, and optionally substituted by one or more hydroxyl or Ci-Ce alkoxy radicals; - R5 and R6 represent a hydrogen or halogen atom, a C1-C4 alkyl radical, a C1-C4 monohydroxyalkyl, a C2-C4 polyhydroxyalkyl, a C1-C4 aminoalkyl or a Y-linking arm; - R-, R8, Rg, Re R11 and Rio, identical or different, represent a hydrogen atom, a linking arm Y or an alkyl radical of C; -Ci; it being understood that the compounds of formula (II) only comprise one linking arm Y per molecule.

13. Composition according to claim 12, characterized in that the double bases of formula (II) are chosen from N, N'-bis- (β-hydroxyethyl) N, N '-bis- (4'-aminophenyl) 1 , 3-diamino propanol, N, N'-bis- (β-hydroxyethyl) N, N'-bis- (4'-aminophenyl) ethylenediamine, N, N'-bis- (4-aminophenyl) tetramethylenediamine, N, N'-bis- (β-hydroxyethyl) N, N'-bis- (4-aminophenyl) tetramethylenediamine, N, N'-bis- (4-methyl aminophenyl) tetramethylenediamine, N, N'-bis- (ethyl) N, N'-bis- (4'-amino, 3'-methylphenyl) ethylenediamine, 1,8-bis- (2,5-diaminophenoxy) -3,5-dioxaoctane, and their addition salts with an acid

14. Composition according to claim 9, characterized in that the para-aminophenols are chosen from the compounds of formula (III), and their addition salts with an acid: wherein: - R 13 represents a hydrogen or halogen atom, a C 1 -C 4 alkyl radical, C 1 -C 4 monohydroxyalkyl, C 1 -C 4 alkoxy (C 1 -C 4) alkyl, C 1 -C 4 aminoalkyl or hydroxy (C1-C4) aminoalkyl of C1-C4, - R: ^ represents a hydrogen or halogen atom, a C: -C alkyl radical, a C1-C4 monohydroxyalkyl, a C2-C4 polyhydroxyalkyl, a C1-C4 aminoalkyl, a C? -C cyanoalkyl or an alkoxy ( C: -C?) (C1-C4) alkyl, it being understood that at least one of the radicals R13 or Ri4 represents a hydrogen atom.

15. Composition according to claim 14, characterized in that the para-aminophenols of formula (III) are chosen from para-aminophenol, 4-amino-3-methyl phenol, 4-amino-3-fluoro-phenol, 4-amino-3-amino hydroxymethyl phenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol, 4-amino-2- (p-hydroxyethyl-aminomethyl) ) phenol, the 4-amino-2-fluoro phenol, and its addition salts with an acid.

16. Composition according to claim 9, characterized in that the ortho-aminophenols are chosen from 2-amino phenol, 2-amino-5-methyl phenol, 2-amino-6-methyl phenol, 5-acetamido-2-amino phenol, and its addition salts with an acid.

17. composition according to claim 9, characterized in that the heterocyclic oxidation bases are chosen from the pyridine derivatives, the pyrimidine derivatives, the pyrazole derivatives, the pyrazolopyrimidine derivatives, and their addition salts with an acid.

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

19. Composition according to claim 18, characterized in that the oxidation base (s) represent from 0.005 to 6% by weight of the total weight of the dye composition.

20. Composition according to any one of the preceding claims, characterized in that it contains one or more couplers can be chosen from for meta-phenylenediamines, meta-aminophenols, meta-diphenols, heterocyclic couplers such as, for example, indole derivatives, indoline derivatives, benzimidazole derivatives , benzomorpholine derivatives, sesamol derivatives and pyridine, pyrimidine and pyrazole derivatives, and the addition salts thereof with an acid.

21. Composition according to claim 20, characterized in that the coupler (s) are selected from 2-methyl-5-aminophenol, 5-N- (β-hydroxyethyl) amino-2-methylphenol, 3-aminophenol, 1,3-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene, 4-chloro-l, 3-dihydroxybenzene, 2,4-diamino-l- (β-hydroxyethyl-oxy) -benzene, 2-amino-4- (β -hydroxyethylamino) -1-methoxybenzene, 1,3-diaminobenzene, 1,3-bis (2,4-diaminophenoxy) propane, sesamol, α-naphthol, 6-hydroxyindole, 4-hydroxyindole, 4-hydroxy-N-methylindole, 6-hydroxyindole, 2,6-dihydroxy-4-methylpyridine, lH-3-methylpyrazol-5-one and l-phenyl-3-phenyl-pyrazol-5-one, and the addition of the salts thereof with an acid .

22. Composition according to any of claims 20 to 21, characterized in that the coupler (s) preferably represent from 0.0001 to 10 * by weight approximately of the total weight of the dye composition. -

23. Composition according to claim 22, characterized in that the coupler (s) represent (s) from 0.005 to 5% by weight relative to the total weight of the ready-to-use dye composition.

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

25. Composition according to any one of the preceding claims, characterized in that the ether of 4 to 8 carbon atoms, of a glycol of 2 carbon atoms is (are) chosen from an alkyl ether of 4 to 8 carbon atoms of a glycol of 2 carbon atoms and the aryl ethers of 6 to 8 carbon atoms of glycol of 2 carbon atoms.

26. Composition according to claim 25, characterized in that the ether (s) of a glycol of 2 carbon atoms is (are) selected from the monobutyl ether of ethylene glycol, monophenylether of ethylene glycol, and monobenzylether of ethylene glycol.

27. Composition according to any one of claims 1 to 24, characterized in that Composition according to any one of the preceding claims, characterized in that the ether (s) of 1 to 8 carbon atoms, of a glycol of 3 to 9 carbon atoms is (are) chosen from an alkyl ether of 1 to 8 carbon atoms of a glycol of 3 to 9 carbon atoms and the aryl ethers of 6 to 8 carbon atoms of glycol of 3 to 9 carbon atoms.

28. Composition according to claim 27, characterized in that the ether (s) of a glycol of 1 to 8 carbon atoms of a glycol of 3-9 carbon atoms are selected from propylene glycol monomethyl ether, propylene glycol monoethyl ether, ether isopropylene glycol diethyl, monomethyl ether and diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether and tripropylene glycol monomethyl ether, propylene glycol monophenyl ether, propylene glycol monobenzyl ether, diethylene glycol monophenyl ether and diethylene glycol monobenzyl ether.

29. Compositions according to any one of the claims, characterized in that the ether (s) of 4 to 8 carbon atoms of a glycol of 2 carbon atoms and / or the ether (es) of 1 to 8 carbon atoms of a glycol of 3 to 9 carbon atoms represent from 1 to 40% by weight approximately relative to the total weight of the dye composition.

30. Compositions according to claim 1, characterized in that the ether (s) of 4 to 8 carbon atoms of a glycol of 2 carbon atoms and / or the ether (s) of 1 to 8 carbon atoms of a glycol of 3 to 9 carbon atoms represents (s) from 5 to 30% by weight approximately relative to the total weight of the dye composition.

31. Composition according to any one of the preceding claims, characterized in that the medium which is suitable for dyeing, consists of water or a mixture of water and at least one organic solvent.

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

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

34. Dyeing process of keratin fibers and in particular of human keratin fibers such as hair, characterized in that at least one dye composition prepared for use as defined in any one of the claims is applied to said fibers. precedents, for a sufficient time to develop the desired coloration.

35. Process according to claim 33, characterized in that a preliminary stage consists in storing separately, on the one hand, a composition (Al) comprising, in an appropriate medium for dyeing, at least one oxidation base and at least one ether of 4 to 8 carbon atoms, of a glycol of 2 carbon atoms and / or at least one ether of 1 to 8 carbon atoms of glycol of 3 to 9 carbon atoms, and, on the other hand, a composition (Bl) containing, in an appropriate medium for the dye, at least one 2-electron oxide-reductase-type enzyme in the presence of at least one donor for said enzyme, then in mixing it at the time of use before applying this mixture on the keratin fibers.

36. Process according to claim 33, characterized in that it includes a first step which consists in separately storing, in a manner, a composition (A2) comprising, in a medium which is suitable for dyeing, at least one oxidation base and, on the other hand, a composition (B2) comprising, in a suitable medium which is suitable for the inten, at least one ether of 4 to 8 carbon atoms, of a glycol of 2 carbon atoms and / or less an ether of 1 to 8 carbon atoms of glycol of 3 to 9 carbon atoms, and at least one enzyme of oxidoreductase type of 2 electrons in the presence of at least one donor for said enzyme, followed by the mixing of the same together at the time of use, after which, this mixture is applied to the keratin fibers.

37. A multi-compartment dyeing device or "kit" characterized in that it includes a first compartment comprising a composition (Al) as defined in claim 35 and a second compartment comprising a second compartment comprising a composition (Bl) as defined in claim 35.

38. A multi-compartment dyeing device or "kit" characterized in that it includes a first compartment comprising a composition (A2) as defined in claim 36 and a second compartment comprising a second compartment comprising a composition (B2) as defined in claim 36.