MXPA99004998A - Oxidation dyeing composition for keratin fibres and dyeing method using said composition - Google Patents

Abstract

The invention concerns a ready-to-use oxidation dyeing composition for keratin fibres, and in particular for human keratin fibres such as hair comprising, in a medium appropriate for dyeing at least an oxidation base, at least a direct cationic dye, 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 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 oxidation base, at least a direct cationic dye, and at least one 2-electron oxide-reductase-type enzyme in the presence of at least one donor for said enzyme, as well as the dyeing process employing this composition.

It is known to dye 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. The oxidation dye precursors, or oxidation bases, are colorless or easily colored compounds which, associated with oxidizing products, can give rise, by an oxidative condensation process, to colored compounds and REF .: 30197 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.

It is also known that, in order to vary the shades obtained and to give them reflections, direct dyes, that is to say colored substances which give a coloration in the absence of an oxidizing agent, can be used in association with the oxidation dye precursors and the couplers.

These direct dyes belong mostly to the family of nitro compounds of the benzene series and have the drawback, when they are incorporated in dyeing compositions, of leading to discolourations which have insufficient tenacity, in particular - compared to shampooing .

The so-called "permanent" coloration obtained by these oxidation dyes must otherwise meet a certain number of requirements. Therefore, it should not have drawbacks on the toxicological level, 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, lastly, to be as non-selective as possible, that is to say allow the smallest possible deviations of coloration to be obtained throughout the same keratin fiber, which may be in effect sensitized in a different way. (ie, 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 oxidation coloring of the keratin fibers can also be carried out with the aid of oxidant systems other than hydrogen peroxide such as enzyme systems. Thus, it has already been proposed to dye keratin fibers, mainly in the patent application EP-A-0 310 675, with compositions comprising an oxidation base and optionally a copulator, in association with enzymes such as pyranose oxidase, glucose oxidase or 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 direct cationic dye, 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 direct cationic dye, - 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 bovine liver extract uricase, the uricase of Arthrobacter globiformis, and 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, one can cite 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 Ci-Cj, monohydroxyalkyl of C? -C4, polyhydroxyalkyl of C2-C4, akoxy (C? -C4) alkyl (Ci- C4), alkyl of C1 -C4 substituted by a nitrogenous group, phenyl or '-amino-phenyl; - R ^ represents a hydrogen atom, an alkyl radical of C-Cj, monohydroxyalkyl of C: -Ci polyhydroxyalkyl of C; -C, alkoxy (C? -C4) alkyl (C? -Ci) or alkyl of C? ~ C4 substituted 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? -C, hydroxyalkoxy of C1-C4, C 1 -C 4 acetylaminoalkoxy, C 1 -C 4 mesylaminoalkoxy or C 1 -C 4 carbamoylaminoalkoxy, R 4 represents a hydrogen atom, 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 (C? -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-hydroxyetiU-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-isopropyl paraphenylenediamine, N- (β-hydroxypropyl) paraphenylenediamine, 2-hydroxymethyl paraphenylenediamine, N, N-dimethyl 3-methyl paraphenylenediamine, N, N - (ethyl, β-hydroxyethyl) paraphenylenediamine, N- (β, β-dihydroxypropyl) paraphenylenediamine, N- (4'-aminophenyl) paraphenylenediamine, N-phenyl afenylenediamine, 2-β-hydroxyethyl-oxy-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 paraphenylenediamine, 2-β-acetylaminoethyloxy paraphenylenediamine, and its addition salts 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: - Zi and Z :, identical or different, represent a hydroxyl radical or -NH2 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 radicals or Ci-Cβ alkoxy; - R 5 and R 6 represent a hydrogen or halogen atom, a C 1 -C 4 alkyl radical, C 1 -C 4 monohydroxyalkyl, C 2 -C 4 polyhydroxyalkyl, C 1 -C 4 aminoalkyl or a Y linking arm; - R7, Re, R9,, or R11 and Ri2 *, which are identical or different, represent a hydrogen atom, a linking arm Y or an alkyl radical of C? -C4; it being understood that the compounds of formula (II) only comprise one linking arm Y per molecule.

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

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), N, N'-bis- (β-hydroxyethyl) N, N '-bis- (4'-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: - R13 represents a hydrogen or halogen atom, an alkyl radical of C? -C4, monohydroxyalkyl of C? -C4, alkoxy (C? -C4) alkyl (C1-C4), aminoalkyl of C1-C4 or hydroxyalkyl (C? -C4) aminoalkyl of C1-C4, - R; 4 represents a hydrogen or halogen atom, a C1-C4 alkyl radical, a C1-C4 monohydroxyalkyl, a C2-C4 polyhydroxyalkyl, a C1-C4 aminoalkyl, a C1-C4 cyanoalkyl or a (C1-C4) alkoxy ) (C1-C4) alkyl, it being understood that at least one of the radicals R13 or RH 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- (4'-chlorobenzyl) pyrazole, 4,5-diamino-1,3-dimethyl pyrazole, 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- (-hydroxy-ethyl) 3-methyl pyrazole, 4,5-diamino-1-ethyl-3-methyl-pyrazole, 4,5-diamino-1-ethyl-3- (4'-methoxyphenyl) pyrazole, 4,5-diamino-1-ethyl-3-hydroxymethyl pyrazole, 4,5-diamino-3-hydroxymethyl-1-methyl pyrazole, 4,5-diamino-3-hydroxymethyl-1-isopropyl pyrazole, 4,5-diamino-3-methyl-1-isopropylpyrazole, 4-amino-5 (2'-aminoethyl) amino 1,3-d imetyl pyrazole, 3, 4, 5-triamine pyrazole, 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 its 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: - R15 Riß / Ri7, and Riß identical or different, designate a hydrogen atom, a C1-C4 alkyl radical, an aryl radical, a hydroxyalkyl radical of C? -C4, a polyhydroxyalkyl radical of C2-C4 , a (C 1 -C 4) alkoxy radical of C 1 -C 4, an aminoalkyl radical of C 1 -C 4 (the amine may be protected by an acetyl, ureido or sulfonyl radical), a radical (C 1 -C 4) alkylamino C1 alkyl -C4, a di- [(C1-C4) alkyl] amino-C1-C4 alkyl radical, the dialkyl radicals being able to form a carbon-cyclic ring or a 5- or 6-membered heterocycle), a hydroxy (C1-C4) alkyl radical or di [hydroxy (C 1 -C 4) alkyl] amino C 1 -C 4 alkyl; - the radicals X designate, identical or different, a hydrogen atom, an alkyl radical of C? -C4, an aryl radical, a hydroxyalkyl radical of C1-C4, a polyhydroxyalkyl radical of C2-C4, an amino radical of C-alkyl ~ C4, a radical (C1-C4) alkyl amino C: -C4 alkyl, a di- [(C1-C4) alkyl] amino radical of C1-C4 alkyl (the dialkyls can form a carbon cycle or a heterocycle with 5 or 6 links), a hydroxy (Ci- C4) alkyl radical or di- [hydroxy (C1-C4) alkyl] aminoCi C4 alkyl, 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 0, 1, 2 or 3; - p is o or 1; - q is 0 or 1; - n is 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 NR? 5R? 6 and occupy the 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 NR1R18) 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. Scholten, 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. Matthews, 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-Marquina, C. Al era, J. Elguero, J. Heterocyclic Chem., 11 (3), 423, 1974. - K. Saito, I. Hori, M. Higarashi, H. Midorikawa, Bull. Chem. Soc. Japan, 47 (2), 76, 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 cationic direct dye (s) which may be used in the dye composition prepared for use according to the invention are preferably chosen from cationic amino-anthraquinones, cationic mono- or di-azoates, cationic naphthoquinones.

By way of example, mention may be made in particular of [8- [(p-aminophenyl) azol] -7-hydroxy-2-naphthyl] trimethylamine chloride (also called Basic Brown 16 or Arianor Mahogany 306002 in the Color Index), 3- [(4-amino-6-bromo-5,8-dihydro-l-hydroxy-8-imino-5-oxo-2-naphthalenyl) -amino] -N,, -trimethyl-benzenaminium chloride (also called Basic Blue 99 or Arianor Steel Blue 306004 in the Color Index), the 7-hydroxy-8- [(2-methoxyphenyl) azo] -N, N, N-trimethyl-2-naphthalenemine chloride (also called the Basic Red 76 or Arianor Madder Red in the Color Index), the chloride of [8- [4-amino-2-nitrophenyl] azo] -7-hydroxy-2-naphthyl] trimethylammonium (also called Basic Brown 17 or Arianor Sienna Brown 306001 in the Color Index) and 3- [4,5-dihydro-3-methyl-5-oxo-l-phenyl-lH-pyrazol-4-yl) azo] -N, N, N-trimethyl-benzenaminium chloride ( also called Basic Yellow 57 or Arianor Straw Yellow 306005 in the Color Index).

The cationic direct dye (s) can also be chosen from: a) the compounds of formula (V) below: in which: D represents a nitrogen atom or the group -CH, R1 and R2n identical or different, represent a hydrogen atom; a C1-C4 alkyl radical which can be substituted by a radical -CN, -OH or -NH2 or form with a carbon atom of the benzene ring a possibly oxygenated or nitrogenated heterocycle, which can be substituted by one or more alkyl radicals of C1-C4; a 4'-aromatic radical, R :: and R ': i / identical or different, represent a hydrogen or halogen atom chosen from chlorine, bromine, iodine and fluorine, a cyano radical, C1-C4 alkoxy or acetyloxy, X represents an anion selected preferably from chloride, methyl sulfate and acetate, A represents a group chosen by the following structures Al to A19: A 4 A5 «A, A A, A, A, A12 A «A ,, A "14 5 ^ 16 A17 1ß wherein R 22 represents a C 1 -C 4 alkyl radical which may be substituted by a hydroxyl radical and R 23 represents a radial C 1 -C 4 alkoxy; b) the compounds of formula (VI) below: in which: R_4 represents a hydrogen atom or an alkyl radical of C; -C, R25 represents a hydrogen atom, an alkyl radical which can be substituted by a radical -CH or by an amino group, a 4'-aminophenyl radical or a R24 form with an optionally oxygenated and / or nitrogenated heterocycle which can be substituted by a radical C1-C alkyl, R. ,, and R_-, identical or different, represent a hydrogen atom, a halogen atom such as bromine, chlorine, iodine or fluorine, a C1-C4 alkyl radical or C1-C14 alkoxy, a radical -CN, X represents an anion preferably chosen from chloride, methyl sulfate and acetate, B represents a group chosen by the following structures Bl to B6: B4 B5 B6 in which R2s represents an alkyl radical of C1-C4, R29 and R30, identical or different, represent a hydrogen atom or an alkyl radical of C? -C4; c) the following compounds of formulas (VII) and (VII '): in which: R3? represents a hydrogen atom, a C-C4 alkoxy radical, a halogen atom such as bromine, chlorine, iodine or fluorine or an amino radical, R3: represents a hydrogen atom, a C1-C4 alkyl radical or a carbon atom of the benzene ring, a heterocycle optionally oxygenated and / or substituted by one or more C1-C4 alkyl groups, R33 represents a hydrogen atom or halogen such as bromine, chlorine, iodine or fluorine, 3 and R35 identical or different, represent a hydrogen atom or a C1-C4 alkyl radical, Di and D2, identical or different, represent a nitrogen atom or the -CH group, m = 0 or 1, it being understood that when R31 represents an unsubstituted amino group, then Dx and D2 simultaneously represent a group -CH and m = 0, X represents an anion preferably chosen from chloride, methyl sulfate and acetate, E represents a group chosen by the following El a E8 structures: E1 wherein R36 represents an alkyl radical of C? -C; when m = 0 and when Di represents a nitrogen atom, then E can also designate a group of structure E9 as follows: wherein R 36 represents a C 1 -C 4 alkyl radical.

The cationic direct dyes of formulas (V), (VI), (VII) and (VII ') which can be used in the dye composition prepared for use according to the invention are known compounds and are described, for example, in WO patent applications. 95/01772, WO 95/15144 and EF-A-0 714 954.

Among the cationic direct dyes of formula (V) which can be used in the dyeing compositions prepared for use according to the invention, mention may be made more particularly of the compounds which respond to the following structures (VI) to (V52): Cl '(V30) Cl "(V45) Cl (V50) Among the compounds of structures (VI) to (V52) described above, compounds which respond to structures (VI), (V2), (V4), (V14) and (V31) are particularly preferred. Among the direct cationic dyes of formula (VI) which can be used in the dyeing compositions prepared for use according to the invention, mention may be made more particularly of the compounds which respond to the following structures (VII) to (VI12): CH3SO4"(VI11) CHjSO," (VI12) Among the cationic direct dyes of formula (VII) which can be used in the dyeing compositions prepared for use in accordance with the invention, mention may be made more particularly of the compounds which respond to the following structures (HIV) to (VII18): - CHjCOO "(V1I16) Among the particular compounds of structures (HIV) to (VII18) described above, compounds which respond to structures (VII4), (VII5) and (VII13) are particularly preferred.

Among the direct cationic dyes of formula (VII ') which can be used in the dyeing compositions prepared for use according to the invention, mention may be made more particularly of the compounds which correspond to the following structures (VII' I) to (VII '3) : The cationic direct dye (s) used according to the invention 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 0.05 to 5% by weight approximately of this weight.

The dye composition according to the invention can also contain one or more non-cationic direct couplers and / or dyes mainly for modifying the shades or enriching them with reflections.

Among the couplers that may be present in the dye composition as prepared for use according to the invention, mention may be made in particular of meta-phenylenediamines, meta-aminophenols, meta-diphenols, heterocyclic couplers, and their addition salts with an acid. .

When present, these additional couplers preferably represent from 0.0001 to 10% by weight approximately of the total weight of the dye composition prepared for use 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 context of the dyeing compositions of the invention (oxidation bases and couplers) are chosen mainly from hydrochlorides, hydrobromides, sulfates and tartrates, lactates and acetates.

The appropriate medium for the dye (or support) of the dye composition prepared for the use according to the invention is generally constituted by water or by a mixture of water and at least one organic solvent to solubilize the compounds that would not be sufficiently soluble in water. Water. As the organic solvent, there may be mentioned, for example, d-C4 alkanols, such as ethanol and isopropanol; glycerol; glycols and ethers of glycols such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, monoethyl ether and diethylene glycol monomethyl ether, as well as aromatic alcohols such as benzyl alcohol or phenoxyethanol, analogous products and mixtures thereof.

The solvents can be present in proportions preferably comprised between 1 and 40% by weight approximately with respect to the total weight of the dye composition, and even more preferably between 5 and 30% by weight approximately.

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 (VIII) below: ^ 37 ^ 3 N-W-N (VIII) R3 * 0 wherein W is a propylene moiety optionally substituted by a hydroxyl group or an alkyl radical of C? -C4; R37, R3ß / R39 and Rio 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 thickeners, 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-forming 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 in storing separately, on the one hand, a composition (A) comprising, in a medium suitable for dyeing, at least one oxidation base , at least one direct cationic dye and, on the other hand, a composition (B) 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 proceed to its mixing at the time of use before applying this mixture on the keratin fibers.

Another object of the invention is a device with several compartments or "kit" of dye or another conditioning system with several compartments, whose first compartment contains the composition (A) as defined above and a second compartment contains the composition (B) 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 EXAMPLES 1 to 3 OF DYE The dyeing compositions prepared for the following use (contained in grams) were prepared: (*) Common dye support: - Ethanol 20.0 g - Hydroxyethylcellulose sold under the name NATROSOL 250 HR® by the company AQUALON 1.0 g -Alkyl (C8-C: o) polyglucoside in aqueous solution at 60% of active material (M.A.) buffered by ammonium citrate (0.5%), sold under the name ORAMIX CGllO® by the company SEPPIC 8.0 g - Monoethanolamine c.s. pH = 9.5 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 the shades shown in the following table: EXAMPLE Tonality Obtained Intense red Light blond coppery red Blonde purple red 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 (35)

1. Composition prepared for use, for the 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 cationic direct dye - 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 para-phenylenediamines, double bases, para-aminophenols, ortho-aminophenols 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: - R; represents a hydrogen atom, an alkyl radical of C: -C4, monohydroxyalkyl of C1-C4, polyhydroxyalkyl of C2-C4, akoxy (C1-C4) alkyl (Ci- C4), C1-C4 alkyl substituted by a nitrogenous group , phenyl or 4'-amino-phenyl; - R 2 represents a hydrogen atom, a C 1 -C 4 alkyl radical, a C 1 -C 4 monohydroxyalkyl polyhydroxyalkyl radical, -C 4 alkoxy (C 1 -C 4) alkyl (C 1 -C 4) or a C 1 -C 4 alkyl substituted by a group nitrogenous; - R5 represents a hydrogen atom, a halogen atom such as a chlorine, bromine, iodine or fluorine atom, an alkyl radical of C, -C4, monohydroxyalkyl of C1-C4, hydroxyalkoxy of C1-C4, acetylaminoalkoxy of C1-C4, C 1 -C 4 mesylaminoalkoxy or C-C, 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, 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) amino 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 paraphenylenediamine, N , N- (ethyl, ß-hydroxyethyl) paraphenylenediamine, N- (ß,? - dihydroxypropyl) paraphenylenediamine, N- (4'-aminophenyl) paraphenylenediamine, N-phenyl paraphenylenediamine, 2-b-hydroxyethyloxy paraphenylenediamine, 2-β-acetylaminoethyloxy paraphenylenediamine, N- (β-methoxyethyl) paraphenylenediamine, and its 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: Z: and Z2, identical or different, represent a hydroxyl radical or -NH2 which can be substituted by a C1-C4 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, sulfur or nitrogen, and optionally substituted by one or more hydroxyl radicals or C? -C6 alkoxy; - 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; - R7, R8, R9,, Rio, Rn and R12, identical or different, represent a hydrogen atom, a linking arm Y or an alkyl radical of C: -C4; 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- (' -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 its addition salts with a 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: Ri, represents a hydrogen or halogen atom, a C1-C4 alkyl radical, a C1-C4 monohydroxyalkyl, a (C1-C4) alkoxy (C1-C4) alkyl, a C1-C4 aminoalkyl or a hydroxyalkyl (C1-C4) C1-C4 aminoalkyl, - R 1 represents a hydrogen or halogen atom, a C 1 -C 4 alkyl radical, a C 1 -C 4 monohydroxyalkyl, a C 2 -C 4 polyhydroxyalkyl, a C 1 -C 4 aminoalkyl, a C 1 -C 4 cyanoalkyl or a (C 1 -C 4) alkoxy alkyl (C1-C4), it being understood that at least one of the radicals Ri3 or R14 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 orthoaminophenols are chosen from 2-amino phenol, 2-amino-5-methyl phenol, 2-amino-6-methyl phenol, 5-acetamido-2-amino phenol, and their. 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 the cationic direct dye (s) are chosen from cationic amino-anthraquinones, cationic mono- or di-azoates, cationic naphthoquinones.

21. Composition according to claim 20, characterized in that the cationic direct dye (s) are chosen from [8- [8- (p-aminophenyl) azol] -7-hydroxy-2-naphthyl] trimethylammonium chloride, the chloride of 3- [(4-amino-6-bromo-5,8-dihydro-l-hydroxy-8-imino-5-oxo-2-naphthalenyl) amino] -N, N, N-trimethyl-benzenamine, chloride of 7-hydroxy-8 - [(2-methoxy-phenyl) azo] -N, N, N-trimethyl-2-naphthalene ammonium, [8- [(4-amino-2-nitrophenyl) azo] -7 chloride -hydroxy-2-naphthyl] trimethylammonium chloride and 3- [(4,5-dihydro-3-methyl-5-oxo-l-phenyl-lH-pyrazol-4-yl) azo] -N, N, N chloride -trimetil-bencenaminio.

22. Composition according to any one of claims 1 to 19, characterized in that the cationic direct dye (s) are chosen from: a) the compounds of formula (V) below: (V) in which: D represents a nitrogen atom or the group -CH, R19 and R2o identical or different, represent a hydrogen atom; a C1-C4 alkyl radical which can be substituted by a radical -CN, -OH or -NH2 or form with a carbon atom of the benzene ring a possibly oxygenated or nitrogenated heterocycle, which can be substituted by one or more alkyl radicals of C1-C4; a 4'-aminophenyl radical, R2? and R 21, identical or different, represent a hydrogen or halogen atom chosen from chlorine, bromine, iodine and fluorine, a cyano radical, a C 1 -C 4 alkoxy or acetyloxy, X represents an anion preferably chosen from chloride, methyl sulfate and acetate, A represents a group chosen by the following structures Al a Al9: , A4 Ae A7 * «A ,, 12 n « 16 A17"18 wherein R 22 represents a C 1 -C 4 alkyl radical which may be substituted by a hydroxyl radical and R 23 represents a radial C 1 -C 4 alkoxy; b) the compounds of formula (VI) below: in which: R; 4 represents a hydrogen atom or an alkyl radical R25 represents a hydrogen atom, an alkyl radical which may be substituted by a radical -CH or by an amino group, a radical '-aminophenyl or form with R24 an optionally oxygenated and / or nitrogenated heterocycle which may be substituted by an alkyl radical of C1-C4, R: e and R: -, identical or different, represent a hydrogen atom, a halogen atom such as bromine, chlorine, iodine or fluorine, a C1-C4 alkyl radical or Ci-Cn alkoxy, a radical -CN, X represents an anion preferably chosen from chloride, methyl sulfate and acetate, B represents a group chosen by the following structures Bl to B6: B4 B5 B6 in which R28 represents a C 1 -C 4 alkyl radical, R 29 and R 30, identical or different, represent a hydrogen atom or an alkyl radical of C 1 -C 4; c) the following compounds of formulas (VII) and (VII '): in which: R31 represents a hydrogen atom, a C1-C4 alkoxy radical, a halogen atom such as bromine, chlorine, iodine or fluorine or an amino radical, R: represents a hydrogen atom, a C 1 -C 4 alkyl radical or, with a carbon atom of the benzene ring, a heterocycle optionally oxygenated and / or substituted by one or more C 1 -C 4 alkyl groups, R 33 represents a hydrogen atom or halogen such as bromine, chlorine, iodine or fluorine, R34 and R35, which are identical or different, represent a hydrogen atom or a C1-C4 alkyl radical, Di and D2, identical or different, represent a nitrogen atom or the -CH group, = O or 1, it being understood that when R31 represents an unsubstituted amino group, then Di and D2 simultaneously represent a group -CH and m = 0, X represents an anion preferably chosen from chloride, methyl sulfate and acetate, E represents a group chosen by the following El a E8 structures: wherein R6 represents an alkyl radical of C? -C4; when m = 0 and when Di represents a nitrogen atom, then E can also designate a group of structure E9 as follows: wherein R 36 represents a C 1 -C 4 alkyl radical.

23. Composition according to claim 22, characterized in that the cationic direct dyes of formula (V) are chosen from the compounds that respond to the following structures (VI) to (V52): Cl "(V45) •

24. Composition according to claim 22, characterized in that the cationic direct dyes of formula (VI) are chosen from the compounds that respond to the following structures (VII) to (VI12):

25. Composition according to claim 22, characterized in that the cationic dyes of formula (VII) are chosen from the compounds that respond to the following structures (HIV) to (VII18): H3C- -N 1 ++ XN CH3SO4 * (V || 7) Cl (Vil 14) OO (VII15) CH3COO- (VII16)

26. Composition according to claim 22, characterized in that the cationic direct dyes of formula (VII ') are chosen from the compounds that respond to the following structures (VII' 1) to (VII'3):

27. Composition according to any one of the preceding claims, characterized in that the cationic direct dye (s) represent from 0.001 to 10% by weight of the total weight of the dye composition prepared for use.

.28. Composition according to claim 27, characterized in that the cationic dye (s) represent from 0.05 to 5% by weight of the total weight of the dye composition prepared for use.

29. 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.

30. Composition according to any one of the preceding claims, characterized in that the appropriate medium for the dye is constituted by water or by a mixture of water and at least one organic solvent.

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

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

33. 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.

34. Procedure according to the claim 33, characterized in that a preliminary step consists in storing separately, on the one hand, a composition (A) comprising, in a medium suitable for dyeing, at least one oxidation base, at least one dye cationic direct and, on the other hand, a composition (B) 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 proceeding to its mixture at the time of use before applying this mixture on the keratin fibers.

35. Device with several compartments or "kit" of dye characterized in that it comprises a first compartment containing the composition (A) as defined in claim 34 and a second compartment contains the composition (B) as defined compartment in claim 34.