WO2003028687A2

WO2003028687A2 - Dyeing composition comprising a diaminopyrazole oxidation base and an enzymatic type oxidizing agent

Info

Publication number: WO2003028687A2
Application number: PCT/FR2002/003316
Authority: WO
Inventors: Sylvain Kravtchenko; Alain Lagrange
Original assignee: L'oreal-D.I.P.I.
Priority date: 2001-09-28
Filing date: 2002-09-27
Publication date: 2003-04-10
Also published as: WO2003028687A3; EP1432392A2; FR2830193A1; FR2830193B1

Abstract

The invention concerns a dyeing composition comprising a diaminopyrazole oxidation base and an oxidoreductase type enzymatic oxidizing agent. The invention also concerns the use of said composition for dyeing keratinous fibres and the dyeing method using said composition.

Description

Enter the PATENT TEXT below

TINCTORIAL COMPOSITION COMPRISING AN OXIDATION BASE OF THE DIAMINOPYRAZOLE TYPE AND AN OXIDIZING AGENT OF AN ENZYMATIC NATURE

The subject of the invention is a dye composition comprising an oxidation base of the diaminopyrazole type and an oxidizing agent of enzymatic nature of the oxidoreductase type. Another subject of the invention is the use of this composition for dyeing keratin fibers as well as the dyeing process using this composition.

It is known to dye keratin fibers and in particular human hair with dye compositions containing oxidation dye precursors, generally called oxidation bases, such as ortho or paraphenylenediamines, ortho or paraaminophenols and heterocyclic compounds. These oxidation bases are colorless or weakly colored compounds which, associated with oxidizing products, can give rise, through an oxidative condensation process, to colored compounds.

We also know that we can vary the nuances obtained with these oxidation bases by associating them with couplers or color modifiers, the latter being chosen in particular from aromatic metadiamines, metaaminophenols, metadiphenols and certain heterocyclic compounds such as as indole compounds.

The variety of molecules involved in the oxidation bases and couplers, allows obtaining a rich palette of colors.

The so-called "permanent" coloration obtained thanks to these oxidation dyes must moreover satisfy a certain number of requirements. Thus, it must be without drawbacks from the toxicological point of view, it must make it possible to obtain nuances in the desired intensity and have good resistance to external agents such as light, bad weather, washing, permanent undulations, sweating and rubbing.

The dyes must also make it possible to cover white hair, and finally be the least selective possible, that is to say allow to obtain the smallest possible color differences throughout the same keratin fiber, which is in general differently sensitized (ie damaged) between its tip and its root. Dye compositions are already known comprising, as the oxidation base, diaminopyrazole derivatives. For example, patent application DE 3843892 describes dye compositions for dyeing keratinous fibers comprising 4,5-diaminopyrazole derivatives which can be substituted in position 2 by alkyl or hydroxyalkyl radicals. Patent application EP 692245 describes dye compositions comprising 4,5-diaminopyrazole derivatives associated with particular metaphenylenediamines. Patent application DE 19643059 describes dye compositions combining 4,5-diaminopyrazole derivatives with metaaminophenol and metaphenylenediamine couplers. Patent application DE 19646609 describes dye compositions combining 4,5-diaminopyrazole derivatives with benzoxazine couplers.

The oxidation dyeing of keratin fibers is generally carried out in an alkaline medium, in the presence of an oxidizing agent, in general hydrogen peroxide. However, the use of alkaline media in the presence of hydrogen peroxide leads to a significant degradation of the fibers as well as a significant discoloration of the keratin fibers which is not always desirable.

It is known to replace hydrogen peroxide with enzymatic systems. Thus, it has already been proposed to dye keratin fibers, in particular in patent application EP-A-0310675, with compositions comprising an oxidation base and optionally a coupler, in combination with enzymes of the oxidoreductase type to 2 electrons, such as pyranose oxidase, glucose oxidase or uricase, in the presence of a donor for said enzymes.

It has also already been proposed, in particular in patent applications FR-A-2112549, FR-A-2694018, EP-A-0504005, WO 95/07988, WO95 / 33836, WO95 / 33837, WO96 / 00290, WO97 / 19998, WO97 / 19999 and US Pat. No. 3,251,742, dyeing keratin fibers with compositions comprising in particular an oxidation dye precursor and an enzyme of the laccase type (4-electron oxidoreductase).

These dyeing processes, although being carried out under conditions which do not cause degradation of the keratin fibers comparable to that caused by the dyes produced in the presence of hydrogen peroxide, lead to coloring not entirely satisfactory, in particular from the point of view of their intensity.

The aim of the present invention is to provide new dye compositions for dyeing keratin fibers which do not degrade keratin fibers, while being capable of generating intense colorings in varied shades, not very selective and particularly resistant.

This object is achieved with the present invention which relates to a dye composition comprising, in an appropriate dyeing medium, • at least one 4,5-diaminopyrazole oxidation base of formula (I) or the corresponding addition salts:

in which R ₁ is an alkyl radical in

substituted by one or more OR radicals, R being a C ₆ -C ₆ alkyl radical, and

• an enzymatic oxidizing agent chosen from (a) an enzymatic system comprising an oxidoreductase with 2 electrons and a donor for this oxidoreductase or (b) an oxidoreductase with 4 electrons.

The invention also relates to a dyeing process using this composition.

Another subject of the invention is the use of the composition of the present invention for dyeing keratin fibers, in particular human keratin fibers such as the hair.

The composition of the present invention makes it possible in particular to obtain a coloration of chromatic keratin fibers, very powerful, not very selective and tenacious while avoiding the degradation of these fibers. In the context of the present invention, the term “alkyl” means linear or branched radicals, for example methyl, ethyl, n-propyl, iso-propyl, butyl, etc.

According to a particular embodiment, the 4,5-diaminopyrazole oxidation base of formula (I) is such that R1 represents an alkyl radical in CC ,, preferably C2-C4 substituted by an OR radical, R being a C _r C ₄ alkyl radical, preferably C1-C2.

Preferably, the oxidation base of formula (I) is 4,5-diamino-1- (2'-methoxyethyl) -pyrazole. In the composition of the present invention, the 2-electron oxidoreductase is chosen from pyranose oxidases, glucose oxidases, glycerol oxidases, lactate oxidases, pyruvate oxidases, uricases, choline oxidases, sarcosine oxidases, bilirubin oxidases and amino acid oxidases. The 2-electron oxidoreductase is preferably chosen from uricases of animal, microbiological or biotechnological origin. By way of example, mention may in particular be made of uricase extracted from boar liver, the uricase of Arthrobacter globiformis, as well as the uricase of Aspergillus flavus.

The 2-electron oxidoreductase (s) can be used in pure crystalline form or in a diluted form in an inert diluent for said 2-electron oxidoreductase.

According to the invention, the term “donor” is understood to mean the various substrates necessary for the functioning of the 2-electron redoxases.

The nature of the donor for said enzyme varies depending on the nature of the 2-electron redoxase which is used. For example, as a donor for 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 the glycerol oxidases, mention may be made of glycerol and dihydroxyacetone; as lactate oxidase donors, there may be mentioned lactic acid and its salts; as the donor for pyruvate oxidases, mention may be made of pyruvic acid and its salts; as uricase donors, mention may be made of uric acid and its salts; as a donor for the choline oxidases, mention may be made of choline and its addition salts with an acid such as choline hydrochloride, and betaine aldehyde; as a donor for sarcosine oxidases, mention may be made of sarcosine, N-methyl-L-leucine, N-methyl-DL-alanine, and N-methyl-DL-valine; and finally, as a donor for bilirubin oxidases, mention may be made of bilirubin. The 2-electron oxidoreductase generally represents from 0.01 to 20%, preferably from 0.1 to 5% by weight of the total weight of the dye composition and the donor generally represents from 0.01 to 20%, preferably 0.1 to 5% by weight of the total weight of the dye composition. We can also define the amount of enzyme according to its activity.

The enzymatic activity of the 2-electron oxidoreductases useful in the present invention can be defined from the oxidation of the donor under aerobic conditions.

One unit U corresponds to the quantity of enzyme leading to the generation of one μmole of H ₂ O ₂ per minute at a pH of 8.5 and at a temperature of 25 ° C. Preferably, the amount of 2-electron oxidoreductase according to the invention is between 10 and 10 ^ units U approximately per 100 g of dye composition.

The 4-electron oxidoreductase (s) useful in the dye composition of the invention can in particular be chosen from laccases, tyrosinases, catechol oxidases and polyphenol oxidases.

According to a particular and preferred embodiment, the oxidoreductase (s) with 4 electrons are chosen from laccases.

These laccases can in particular be chosen from laccases of plant origin, of animal origin, of fungal origin (yeasts, molds, fungi) or of bacterial origin, the organisms of origin being able to be mono- or multicellular. Laccases can also be obtained by biotechnology.

Among the laccases of vegetable origin, mention may be made of laccases produced by plants carrying out chlorophyll synthesis, such as those indicated in patent application FR-A-2694018. Mention may in particular be made of the laccases present in the extracts of Anacardiaceae such as for example the extracts of Magnifera indica, of Schinus molle or of Pleiogynium timoriense; in extracts from Podocarpaceae; of Rosmarinus off. ; Solanum tuberosum; Iris sp. ; from Coffea sp. ; Daucus carrota; of Vinca minor; Persea americana; Catharenthus roseus; from Musa sp. ; Malus pumila; Gingko biloba; Monotropa hypopithys (sucepin), Aesculus sp. ; Acer pseudoplatanus; of Prunus persica and Pistacia palaestina.

Among the laccases of fungal origin, possibly obtained by biotechnology, mention may be made of the laccase (s) derived from Polyporus versicolor, from Rhizoctonia practitionola and Rhus vernicifera as described for example in patent applications FR-A-2 112 549 and EP-A-504005; the laccases described in patent applications WO95 / 07988, WO95 / 33836, WO95 / 33837, WO96 / 00290, WO97 / 19998 and WO97 / 19999, such as for example the laccase (s) from Scytalidium, Polyporus pinsitus, Myceliophtora thermophila , Rhizoctonia solani, Pyricularia orizae, and their variants. Mention may also be made of the laccase (s) originating from Trametes versicolor, Fomes fomentarius, Chaetomium thermophile, Neurospora crassa, Colorius versicol, Botrytis cinerea, Rigidoporus lignosus, Phellinus noxius, Pleurotus ostreatus, Aspergillus nidulans, Podospora anserina, Agaricus bisporus, Ganoderma lucidum, Glomerella cingulata, Lactarius piperatus, Russula delica, Heterobasidion annosum, Thelephora terrestris, Cladosporium cladosporioides, Cerrena unicolor, Coholus hirsutus Coprinus cinereus, Panaeolus papilionaceus, Panaeolus sphinctrinus, Schizophyllum commune, Dichomitius squalens, and their variants.

More preferably, laccases of fungal origin, possibly obtained by biotechnology, will be chosen.

The enzymatic activity of laccases can be defined from the oxidation of syringaldazine under aerobic conditions. The Lacu unit corresponds to the quantity of enzyme catalyzing the conversion of 1 mmol of syringaldazine per minute at a pH of 5.5 and at a temperature of 30 ° C. The unit U corresponds to the quantity of enzyme producing an absorbance delta of 0.001 per minute, at a wavelength of 530 nm, using syringaldazine as substrate, at 30 ° C. and at a pH of 6, 5. The enzymatic activity of the laccases used according to the invention can also be defined from the oxidation of paraphenylenediamine. The ulac unit corresponds to the quantity of enzyme producing an absorbance delta of 0.001 per minute, at a wavelength of 496.5 nm, using paraphenylenediamine as substrate (64 mM), at 30 ° C and at a pH of 5.

In general, the oxidoreductase (s) with 4 electrons represent from 0.01 to 20% by weight approximately of the total weight of the dye composition, and preferably from 0.1 to 5% by weight approximately of this weight. In particular, and when one or more laccases are used, the amount of laccase (s) present in the dye composition according to the invention varies according to the nature of the laccase (s) used. Preferably, the amount of laccase (s) is between 0.5 and 2000 Lacu approximately (either between 10000 and 40.10 ⁶ units U approximately or between 20 and 20.10 ⁶ units ulac) per 100 g of dye composition.

The composition of the present invention may also comprise one or more additional oxidation bases conventionally used in oxidation dyeing other than those described above. By way of example, these additional oxidation bases are chosen from paraphenylenediamines, bisphenylalkylenediamines, para-aminophenols, ortho-aminophenols, heterocyclic bases other than those described above and their addition salts.

Among the paraphenylenediamines, there may be mentioned by way of example, paraphenylenediamine, paratoluylenediamine, 2-chloro paraphenylenediamine, 2,3-dimethyl paraphenylenediamine, 2,6-dimethyl paraphenylenediamine, 2,6-diethyl paraphenylenediamine, 2,5-dimethyl paraphenylenediamine, N, N-dimethyl paraphenylenediamine, N, N-diethyl paraphenylenediamine, N, N-dipropyl paraphenylenediamine, 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-chloro aniline, 2-β-hydroxyethyl paraphenylenediamine, 2-fluoro paraphenylenediamine, 2-isopropyl paraphenylenediamine, N- (β-hydroxypropyl) paraphenylenediamine,

2-hydroxymethyl paraphenylenediamine, N, N-dimethyl 3-methyl paraphenylenediamine, N, N- (ethyl, β-hydroxyethyl) paraphenylenediamine, N- (β, γ- dihydroxypropyl) paraphenylenediamine, N- (4'-aminophenyl ) paraphenylenediamine, N-phenyl paraphenylenediamine, 2-β-hydroxyethyloxy paraphenylenediamine, 2- β-acetylaminoethyloxy paraphenylenediamine, N- (β-methoxyethyl) paraphenylenediamine, 4-aminophenylpyrrolidine, 2-thenyl, par-2-thenyl hydroxyethylamino 5-amino toluene, 3-hydroxy 1- (4'-aminophenyl) pyrrolidine and their addition salts with an acid.

Among the paraphenylenediamines mentioned above, paraphenylenediamine, paratoluylenediamine, 2-isopropyl paraphenylenediamine, 2-β-hydroxyethyl paraphenylenediamine, 2-β-hydroxyethyloxy paraphenylenediamine, 2,6-dimethyl paraphenylenediamine, 2,6-diethyl paraphenylenediamine, 2,3-dimethyl paraphenylenediamine, NN-bis- (β-hydroxyethyl) paraphenylenediamine, 2-chloro paraphenylenediamine, 2-β-acetylaminoethyloxy paraphenylenediamine, and their addition salts with an acid are particularly preferred.

Among the bis-phenylalkylenediamines, there may be mentioned by way of example, 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-diamino phenoxy) -3,6-dioxaoctane, and their addition salts with an acid.

Among the para-aminophenols, there may be mentioned by way of example, 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 their addition salts with an acid. Among the ortho-aminophenols, there may be mentioned by way of example, 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.

Among the heterocyclic bases that may be mentioned, for example, pyridine derivatives, pyrimidine derivatives and pyrazole derivatives. Among the pyridine derivatives, mention may be made of the compounds described for example in patents GB 1,026,978 and GB 1,153,196, such as 2,5-diamino pyridine, 2- (4-methoxyphenyl) amino 3-amino pyridine, 2,3-diamino 6-methoxy pyridine, 2- (β-methoxyethyl) amino 3-amino 6-methoxy pyridine, 3,4-diamino pyridine, and their addition salts with an acid. Other pyridine oxidation bases useful in the present invention are the 3-amino pyrazolo- [1,5-a] -pyridine oxidation bases or their addition salts described for example in patent application FR 2801308. For example, we may include pyrazolo [1,5-a] pyridin-3-ylamine; 2-acetylamino pyrazolo- [1,5-a] pyridin-3-ylamine; 2-morpholin-4-yl-pyrazolo [1,5-a] pyridin-3-ylamine; 3-amino-pyrazolo [1,5-a] pyridin-2-carboxylic acid; 2-methoxy-pyrazolo [1,5-a] pyridine-3-ylamino; (3-amino-pyrazolo [1,5-a] pyridine-7-yl) -methanol; 2- (3-amino-pyrazolo [1,5-a] pyridine-5-yl) -ethanol; 2- (3-amino-pyrazolo [1,5-a] pyridine-7-yl) - ethanol; (3-amino-pyrazolo [1,5-a] pyridine-2-yl) -methanol; 3,6-diamino-pyrazolo [1,5-a] pyridine; 3,4-diamino-pyrazolo [1,5-a] pyridine; pyrazolo [1,5-a] pyridine-3,7-diamine; 7-morpholin-4-yl-pyrazolo [1,5-a] pyridin-3-ylamine; pyrazolo [1,5-a] pyridine-3,5-diamine; . 5-morpholin-4-yl-pyrazolo [1,5-a] pyhdin-3-ylamine; 2 - [(3-amino-pyrazolo [1,5-a] pyridin-5-yl) - (2-hydroxyethyl) -amino] -ethanol; 2 - [(3-amino-pyrazolo [1,5-a] pyridin-7-yl) - (2-hydroxyethyl) -amino] -ethanol; 3-amino-pyrazolo [1,5-a] pyridine-5-ol; 3-amino-pyrazolo [1,5-a] pyridine-4-ol; 3-amino-pyrazolo [1,5-a] pyridine-6-ol; 3-amino-pyrazolo [1,5-a] pyridine-7-ol; as well as their addition with an acid or with a base. Among the pyrimidine derivatives, mention may be made of the compounds described, for example, in patents DE 2359399; JP 88-169571; JP 05-63124; EP 0770375 or patent application 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 pyrazolo-pyrimidine derivatives such as those mentioned in patent application FR-A-2750048 and among which mention may be made of pyrazolo- [1, 5-a] -pyrimidine-3,7-diamine; 2,5-dimethyl pyrazolo- [1,5-a] - pyrimidine-3,7-diamine; pyrazolo- [1,5-a] -pyrimidine-3,5-diamine; 2,7-dimethyl pyrazolo- [1,5-a] -pyrimidine-3,5-diamine; 3-amino pyrazolo- [1,5-a] -pyrimidin-7-ol; 3-amino pyrazolo- [1,5-a] -pyrimidin-5-ol; 2- (3-amino pyrazolo- [1,5-a] -pyrimidin-7-ylamino) -ethanol, 2- (7-amino pyrazolo- [1,5-a] -pyrimidin-3-ylamino) - ethanol, 2 - [(3-amino-pyrazolo [1, 5-a] pyrimidin-7-yl) - (2-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] -pyrimidine-3,7-diamine, 2,6-dimethyl pyrazolo- [1,5-a] -pyrimidine-3,7-diamine, 2,5,5 N 7, N 7-tetramethyl pyrazolo- [1,5-a] -pyrimidine-3, 7-diamine, 3-amino-5-methyl-7-imidazolylpropylamino pyrazolo- [1,5-a] -pyrimidine and their addition salts with an acid and their tautomeric forms, when there is a tautomeric equilibrium. Among the pyrazole derivatives, mention may be made of the compounds described in patents DE 3843892, DE 4133957 and patent applications WO 94/08969, WO 94/08970, FR-A-2 733 749 and DE 195 43 988 such as 4.5 -diamino 1 -methyl pyrazole, 4,5-diamino l- (β-hydroxyethyl) pyrazole, 3,4-diamino pyrazole, 4,5-diamino 1- (4'-chlorobenzyl) pyrazole, 4,5 -diamino 1, 3-dimethyl pyrazole, 4,5-diamino 3-methyl 1-phenyl pyrazole, 4,5-diamino 1 -methyl 3-phenyl pyrazole, 4-amino 1, 3-dimethyl 5-hydrazino pyrazole , 1-benzyl 4,5-diamino 3-methyl pyrazole, 4,5-diamino 3-tert-butyl 1 -methyl pyrazole, 4,5-diamino 1-tert-butyl 3-methyl pyrazole, 4, 5-diamino l- (β-hydroxyethyl) 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-diamin o 3-methyl 1-isopropyl pyrazole, 4-amino 5- (2'-aminoethyl) amino 1, 3-dimethyl pyrazole, 3,4,5-triamino pyrazole, 1-methyl 3,4,5-triamino pyrazole, 3,5-diamino 1-methyl 4-methylamino pyrazole, 3,5-diamino 4- (β-hydroxyethyl) amino 1 -methyl pyrazole, and their addition salts with an acid.

The oxidation base or bases present in the composition of the invention are generally each present in an amount of between 0.001 to 10% by weight approximately of the total weight of the dye composition, preferably between 0.005 and 6%. The composition according to the invention may contain one or more couplers conventionally used for dyeing keratin fibers. Among these couplers, mention may especially be made of metaphenylenediamines, meta-aminophenols, metadiphenols, naphthalene couplers, heterocyclic couplers and their addition salts. By way of example, mention may be made of 2-methyl 5-aminophenol, 5-N- (β-hydroxyethyl) amino 2-methyl phenol, 6-chloro-2-methyl-5-aminophenol, 3-amino phenol, 1,3-dihydroxy benzene, 1,3-dihydroxy 2-methyl benzene, 4-chloro 1,3-dihydroxy benzene, 2,4-diamino l- (β-hydroxyethyloxy) benzene, 2- amino 4- (β- hydroxyethylamino) 1-methoxybenzene, 1, 3-diamino benzene, 1, 3-bis- (2,4-diaminophenoxy) propane, 3-ureido aniline, 3-ureido 1-dimethylamino benzene , sesamol, 1-β-hydroxyethylamino-3,4-methylenedioxybenzene, α-naphthol, 2 methyl-1-naphtol, 6-hydroxy indole, 4-hydroxy indole, 4-hydroxy N-methyl indole, 2-amino-3-hydroxy pyridine, 6-hydroxy benzomorpholine 3,5-diamino-2,6-dimethoxypyridine, 1-N- (β-hydroxyethyl) amino-3,4-methylene dioxybenzene, 2,6-bis- (β-hydroxyethylamino) toluene and their addition salts with an acid.

In the composition of the present invention, the coupler or couplers are each generally present in an amount of between 0.001 and 10% by weight approximately of the total weight of the dye composition, preferably between 0.005 and 6%.

In general, the addition salts of the oxidation bases and of the couplers which can be used in the context of the invention are in particular chosen from addition salts with an acid such as hydrochlorides, hydrobromides, sulfates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates and addition salts with a base such as soda, potash, ammonia, amines or alkanolamines.

The dye composition in accordance with the invention may also contain one or more direct dyes which can in particular be chosen from nitro dyes from the benzenic series, azo direct dyes and methine direct dyes. These direct dyes can be of nonionic, anionic or cationic nature.

The medium suitable for dyeing, also called dye support, generally consists of water or of a mixture of water and at least one organic solvent to dissolve the compounds which are not sufficiently soluble in water. As organic solvent, mention may, for example, be made of lower C _r C ₄ alkanols, such as ethanol and isopropanol; polyols and polyol ethers 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, and mixtures thereof.

The solvents are preferably present in proportions preferably of between 1 and 40% by weight approximately relative to the total weight of the dye composition, and even more preferably between 5 and 30% by weight approximately. The dye composition in accordance with the invention may also contain various adjuvants conventionally used in compositions for dyeing the hair, such as anionic, cationic, nonionic surfactants, amphoteric, zwitteric or mixtures thereof, anionic, cationic, nonionic polymers, amphoteric, zwitterionic or mixtures thereof, inorganic or organic thickeners, and in particular associative thickeners, anionic, cationic, nonionic and amphoteric polymers antioxidants, penetrating agents, sequestering agents, perfumes, buffers, dispersing agents, conditioning agents such as, for example, volatile or non-volatile silicones, modified or unmodified, film-forming agents, ceramides, agents preservatives, clouding agents.

The above adjuvants are generally present in an amount for each of them of between 0.01 and 20% by weight relative to the weight of the composition. Of course, those skilled in the art will take care to choose this or these optional additional compounds in such a way that the advantageous properties intrinsically attached to the oxidation dye composition according to the invention are not, or not substantially, altered. by the addition (s) envisaged. The pH of the dye composition according to the invention is generally between 3 and 12 approximately, and preferably between 5 and 11 approximately. It can be adjusted to the desired value by means of acidifying or basifying agents usually used in dyeing keratin fibers or even using conventional buffer systems. Among the acidifying agents, there may be mentioned, by way of example, mineral or organic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid, lactic acid, sulfonic acids.

Among the basifying agents, there may be mentioned, by way of example, ammonia, alkali carbonates, alkanolamines such as mono-, di- and triethanolamines as well as their derivatives, sodium or potassium hydroxides and compounds of formula (II) below:

RF ^cd (ll) in which W is a propylene residue optionally substituted by a hydroxyl group or a C _r C ₄ alkyl radical; R _a , R _b , R _c and R _d , identical or different, represent a hydrogen atom, an alkyl radical in C, ^ or hydroxyalkyl in 0, -0 ₄ .

The dye composition according to the invention can be in various forms, such as in the form of liquids, creams, gels, or in any other form suitable for dyeing keratin fibers, and in particular human hair.

In the dye composition according to the invention, the oxidation bases and the oxidoreductase (s) with 2 electrons or with 4 electrons are present within the same composition, and therefore the composition if it is stored before use must be free of gaseous oxygen, so as to avoid premature oxidation of the oxidation dye (s).

The invention also relates to a process for dyeing keratin fibers and in particular human keratin fibers such as the hair, using the dye composition as defined above. According to this process, the dye composition as defined above is applied to the fibers, for a time sufficient to develop the desired coloration. Preferably, the fibers are then rinsed, optionally washed with shampoo, then dried.

The application temperature is preferably between room temperature and 60 ° C and even more preferably between 35 ° C and 50 ° C.

The time sufficient to develop the coloration on the keratin fibers is generally between 1 and 60 minutes and preferably between 5 and 30 minutes. Another object of the invention is a device with several compartments in which a first compartment contains a dye composition comprising an oxidation base of formula (I) and a second compartment contains an enzymatic oxidizing agent as defined above. These devices can be equipped with a means enabling the desired mixture to be delivered to the hair, such as the devices described in patent FR-2,586,913 in the name of the applicant.

From this device, it is possible to dye the keratin fibers using a process which comprises mixing a dye composition comprising at least one oxidation base of formula (I) with an enzymatic oxidizing agent such as as defined above, and the application of the mixture obtained on the keratin fibers for a time sufficient to develop the desired coloration.

The compounds useful in the composition of the present invention are known compounds which can be obtained from general preparation methods known to those skilled in the art. For example, the synthetic approach shown below is described in the literature up to intermediary (2) (JHP Juffermanns, C. L; Habraken; J. Org. Chem., 1986, 51, 4656; Klebe and al.; Synthesis, 1973, 294; R. Hϋttel, F. Bϋchele; Chem. Ber.; 1955, 88, 1586.). In the present case, the passage from compound 3 to compound 2 is carried out by means of a NI-yEtOH mixture.

The alkylation and amination to arrive at the compounds of formula (I) according to the invention are mentioned in document DE 42 34 885.

The examples which follow serve to illustrate the invention without, however, being limiting in nature. EXAMPLES

Example 1. Synthesis of 4,5-Diamino-1- (2'-methoxyethyl) -pyrazole dihydrochloride

A mixture of 5-benzylamino-3-bromo-1- (2'-methoxyethyl) -4-nitropyrazole

(4 g, 2.8 mmol) in ethanol (500 ml) containing a 10% Pd / C catalyst (Johnson-Mattey Type 487, dry weight 0.5 g) and 36% hydrochloric acid (0.57 g , 5.6 mmol) is hydrogenated in a Parr Autoclave (1 I) at 1 MPa for 1 h. The catalyst is then removed by filtration, washed with ethanol and the filtrate evaporated under reduced pressure. A crude orange solid (2.8 g) is thus obtained which has been triturated in AcOEt (20 ml) for 1 h. The solid is then filtered and washed with cold AcOEt (20 ml) then dried under vacuum to give 4,5-Diamino-1- (2'-methoxyethyl) - pyrazole in the form of a beige solid (0, 7 g, 27%). HPLC (purity): 99.5% m.p .: 168.1-173.0 ° C

NMR: ¹ H (400 MHz, d ⁶ -DMSO): 7.34 (1 H, s, NH _arom ), 5.18 (1 H, s _broad , NH), 4.09 (2 H, t, J = 5.5 Hz, CH ₂ N), 3.61 (2 H, t, J = 5.5 Hz, CH ₂ O), 3.23 (3 H, s, OCH ₃ ).

Example 2. Dye composition containing 4,5-Diamino-1- (2-methoxyethyl) -pyrazole dihydrochloride

The following dye composition was prepared:

means Active Matter

U: unit (amount of uricase which oxidizes one μmol of uric acid per minute at 25 ° C and at pH 8.5 in a borate buffer) The mixture is applied to gray hair containing 90% white hairs, whether permanent or not, at a rate of 10 g per 1 g of hair. After 30 min. the hair is then rinsed, washed with a standard shampoo, rinsed again and dried.

Hair color is assessed visually. The reflection on the wick is an intense coppery red.

Claims

1. Dye composition comprising, in an appropriate dyeing medium,

• at least one 4,5-diaminopyrazole oxidation base of formula (I) or the corresponding addition salts:

in which R 1 is a C 1 -C 4 alkyl radical substituted by one or more radicals

OR, R being a C ^ Ce alkyl radical, and

2. Composition according to claim 1 in which the oxidation base of formula (I) is such that R represents a C _r C ₄ alkyl radical substituted by an OR radical, R being a C _r C ₄ alkyl radical.

3. Composition according to claim 2 in which the oxidation base of formula (I) is 4,5-diamino-1- (2'-methoxyethyl) -pyrazole.

4. Composition according to any one of claims 1 to 3 in which the oxidoreductase with 2 electrons is chosen from pyranose oxidases, glucose oxidases, glycerol oxidases, lactate oxidases, pyruvate oxidases, uricases, choline oxidases, sarcosine oxidases, bilirubin oxidases and amino acid oxidases.

5. Composition according to claim 1 or 4 in which the enzymatic system comprising a 2-electron oxidoreductase and a donor for this 2 electron oxidoreductase is chosen from the following oxidoreductase / donor systems:

- pyranose oxidases / D-glucose, L-sorbose and D-xylose;

- glucose oxidases / D-glucose;

- glycerol oxidases / glycerol and dihydroxyacetone; - lactate oxidases / lactic acid and its salts;

- pyruvate oxidases / pyruvic acid and its salts;

- uricases / uric acid and its salts;

- choline oxidases / choline and its salts; - sarcosine oxidases / sarcosine, N-methyl-L-leucine, N-methyl-DL-alanine, and N-methyl-DL-valine;

- bilirubin oxidases / bilirubin.

6. Composition according to any one of claims 1 to 3 in which the 4-electron oxidoreductase is chosen from laccases, tyrosinases, catechol oxidases and polyphenol oxidases.

7. The composition as claimed in claim 6, in which the 4-electron oxidoreductase is a laccase chosen from laccases of vegetable, animal, fungal or bacterial origin and from laccases obtained by biotechnology. .

8. Composition according to claim 7 in which the laccase is of vegetable origin and chosen from the laccases present in the extracts of Anacardiaceae; Podocarpaceae; of Rosmarinus off. ; Solanum tuberosum; Iris sp. ; from Coffea sp. ; Daucus carrota; of Vinca minor; Persea americana; Catharenthus roseus; from Musa sp. ; Malus pumila; Gingko biloba; Monotropa hypopithys (sucepin), Aesculus sp. ; Acer pseudoplatanus; of Prunus persica and Pistacia palaestina.

9. Composition according to claim 7 in which the laccase is of fungal origin or obtained by biotechnology.

10. Composition according to claim 9, in which the laccase is chosen from laccases derived from Polyporus versicolor, from Rhizoctonia pratola, from

Rhus vernicifera, Scytalidium, Polyporus pinsitus, Myceliophtora thermophila, Rhizoctonia solani, Pyriculaha orizae, Trametes versicolor, Fomes fomentarius, Thermophilic Chaetomium, Neurospora crassa, Colorius versicol, Botrytis cinerea, Rigryidus cinerea Phellinus noxius, Pleurotus ostreatus, Aspergillus nidulans, Podospora anserina, Agaricus bisporus, Ganoderma lucidum, Glomerella cingulata, Lactarius piperatus, Russula delica, Heterobasidion annosum, Thelephora terrorris cladosporioides, Cerrena unicolor, Coriolus hirsutus, Ceriporiopsis subvermispora, Coprinus cinereus, Panaeolus papilionaceus, Panaeolus sphinctrinus, Schizophyllum commune, Dichomitius squalens, and their variants.

11. Composition according to any one of claims 1 to 5 in which the 2-electron oxidoreductase represents from 0.01 to 20% by weight of the total weight of the dye composition and the donor represents from 0.01 to 20 % by weight of the total weight of the dye composition.

12. Composition according to any one of claims 1, 6 to 10 in which the 4-electron oxidoreductase represents from 0.01 to 20% by weight of the total weight of the dye composition.

13. Composition according to any one of the preceding claims, comprising an additional oxidation base chosen from paraphenylenediamines, bis-phenylalkylenediamines, para-aminophenols, ortho-aminophenols, heterocyclic bases other than the oxidation bases of formula (I) and their addition salts.

14. Composition according to any one of the preceding claims, comprising a coupler chosen from metaphenylenediamines, meta-aminophenols, metadiphenols, naphthalene couplers, heterocyclic couplers and their addition salts.

15. Composition according to any one of the preceding claims, in which the amount of each of the oxidation bases is between 0.001 to 10% by weight approximately of the total weight of the dye composition.

16. Composition according to Claim 14, in which the amount of each of the couplers is between 0.001 and 10% by weight approximately of the total weight of the dye composition.

17. An oxidation dyeing process for keratin fibers, characterized in that a dye composition as defined in any one of claims 1 to 16 is applied to the fibers for a time sufficient to develop the desired coloration.

18. The method of claim 17 wherein the composition is applied at a temperature between room temperature and 60 ° C.

19. The method of claim 17 or 18 wherein the time sufficient to develop the coloring is between 1 and 60 minutes.

20. A process for dyeing keratin fibers which comprises: mixing a dye composition comprising at least one oxidation base as defined in claims 1 to 3 with an enzymatic oxidizing agent as defined in claims 1, 4 to 12, and applying the mixture obtained on the keratin fibers for a time sufficient to develop the desired coloration.

21. Multi-compartment device in which a first compartment contains a dye composition comprising an oxidation base as defined in any one of claims 1 to 3 and a second compartment contains an enzymatic oxidizing agent as defined in the claims

1, 4 to 12.

22. Use of the composition defined in claims 1 to 16 for the dyeing of keratin fibers.