WO2002074259A2

WO2002074259A2 - Dyeing compositions for keratin fibres containing paraphenylenediamine derivatives with pyrrolidinyl group

Info

Publication number: WO2002074259A2
Application number: PCT/FR2002/000858
Authority: WO
Inventors: Marie-Pascale Audousset
Original assignee: L'oreal
Priority date: 2001-03-21
Filing date: 2002-03-11
Publication date: 2002-09-26
Also published as: WO2002074259A3; AU2002253223A1; FR2822374A1; FR2822374B1

Abstract

The invention relates to novel compositions for the oxidation dyeing of keratin fibres comprising a first oxidation base of the paraphenylenediamine with pyrrolidinyl group type, a second paraphenylenediamine-type oxidation base and a 1,3-dihydroxybenzene coupling agent. The invention also relates to a dyeing method and a device using said composition.

Description

COMPOSITIONS FOR DYEING KERATINIC FIBERS CONTAINING PYRROLIDINYL GROUPED PARAPHENYLENEDIAMINE DERIVATIVES

The subject of the invention is new compositions for the oxidation dyeing of keratin fibers comprising a first oxidation base of the paraphenylenediamine type with pyrrolidinyl group, a second oxidation base of the paraphenylene diamine type and a coupler of the type 1, 3 -dihydroxybenzene, as well as a dyeing process and a device using these compositions.

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

It is also known that the shades obtained with these oxidation bases can be varied by combining them with couplers or color modifiers, the latter being chosen in particular from aromatic metadiamines, metaaminophenols, metadiphenols and certain heterocyclic 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 present good resistance to external agents (light, bad weather, washing, permanent waving, perspiration, friction).

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 can be differently sensitized effect (ie damaged) between its tip and its root.

In the field of hair coloring, it has long been known to use paraphenylenediamine or paratoluenediamine as oxidation bases in order to obtain permanent coloring. These bases make it possible to obtain various nuances with oxidation couplers.

For many years, there has been a constant need to develop new oxidation bases, (also called developers) making it possible to obtain a richer range of shades and improve the resistance of the color to external agents.

US Patent 5,851,237 thus proposes the use of 1- (4-aminophenyl) pyrrolidine derivatives optionally substituted on the benzene nucleus in order to replace paraphenylenediamine. As such, the same patent very preferably proposes the use of 1- (4-aminophenyl) pyrrolidine as a substitute for paraphenylenediamine.

However, it is known in the literature that 1- (4-aminophenyl) pyrrolidine has a highly allergenic activity (R.L. Bent et al., J.A.C.S. 73, 3100, 1951). US Patent 5,993,491 proposes the use of N- (4-aminophenyl) derivatives -

2-hydroxymethylpyrrolidine optionally substituted on the benzene nucleus and on the pyrrolidine heterocycle in position 4 by a hydroxy radical in order to replace paraphenylenediamine. As preferred compounds, said patent proposes N- (4-aminophenyl) -2- (hydroxymethyl) -pyrrolidine substituted by a hydrogen atom or a methyl radical in position 3. However, it is clearly established that these compounds do not allow to give the hair a coloration of quality equivalent to that obtained with para-phenylenediamine or with paratoluenediamine due to a lack of intensity and uniformity of color.

Patent application JP 11158048 proposes hair coloring compositions offering good spreading properties, ease of application and resistance to shampoo. These compositions contain at least one compound chosen from paraphenylenediamine derivatives optionally substituted on the benzene ring and one of the nitrogen atoms of which is included in a 5- to 7-membered carbon ring

In terms of coloring power, ease of application, uniformity of color and shampoo resistance, this patent application demonstrates that the N- (3-isopropyloxy-4-aminophenyl) -2,5-dimethylpyrrolidine derivatives , 1- (3-methyl 4-Amino-phenyl) 2,5- dihydroxyethyl-pyrrolidine, N- (3-methyl-4-aminophenyl) -3- (2-hydroxyethyloxy) pyrrolidine, and N- (3-methyl- 4-aminophenyl) -2-methyl-4-hydroxypyrrolidine behave like oxidation bases equivalent to paraphenylenediamine derivatives whose nitrogen atom is included in a functionalized piperidine 6-membered ring.

However, it is known that when one of the nitrogen atoms of the paraphenylenediamine derivatives is included in a 6-membered ring, in particular piperidine, the activation energy to lead to the corresponding oxidized quinonimine form is among the highest from the series of paraphenylenediamine N, N- disubstituted. Consequently, the oxidative condensation reactions of such bases with or without couplers are kinetically and energetically disadvantaged and the dye compositions containing such oxidation bases give the hair insufficient properties in terms of intensity and uniformity of the color. color compared to those containing para-phenylenediamine or paratoluenediamine.

The object of the present invention is to develop new compositions for dyeing keratin fibers containing an oxidation base which does not have the drawbacks of the prior art. In particular, the object of the invention is to provide dyeing compositions giving the hair excellent properties of color intensity, variety of shades, color uniformity and tenacity with respect to the various external aggressions. that can suffer the hair, as well as good safety. This object is achieved with the present invention which relates to a composition for the oxidation dyeing of keratin fibers, and in particular human keratin fibers such as the hair, characterized in that it comprises, in a medium suitable for dyeing,

A first oxidation base chosen from paraphenylenediamine derivatives containing a pyrrolidinyl group of formula (I) below, and their addition salts with an acid:

in which: - Ri represents a halogen atom; a Cι-C ₇ carbon chain, saturated or which may contain one or more double bonds and / or one or more triple bonds, linear or branched, which may be in the form of a ring having 3 to 6 members, one or more carbon atoms of the chain being able to be replaced by an oxygen, nitrogen or sulfur atom, by an SO ₂ group or by a halogen atom, the radical Ri not comprising a peroxide bond, nor of diazo, nitro or nitroso radicals ;

- R ₂ represents a hydroxyl radical, an -OR group in which R. represents a linear or branched C1-C4 alkyl radical substituted by one or more substituents chosen from the group consisting of a halogen atom, C1-C2 alkoxy, amino, and C1-C2 aminoalkyl, or a C3- radical C4 substituted with one or more hydroxyl radicals; a group -NR'R "in which R 'and R" represent, independently of one another, a hydrogen atom, a linear or branched C1-C4 alkyl radical substituted by one or more radicals chosen from the group consisting of a halogen atom, a hydroxyl radical, C1-alkoxy -C2, amino and C1-C2 aminoalkyl; an acetoxy group or an acetomido group,

- n is 0, 1 or 2, it being understood that when n is equal to 2 then the radicals R1 can be identical or different,

A second oxidation base chosen from the paraphenylenediamines of formula (II) below, and their addition salts with an acid:

in which

- R3 represents a halogen atom; a carbon chain of CrC ₇ , saturated or which may contain one or more double bonds and / or one or more triple bonds, linear or branched, which may be in the form of a ring having 3 to 6 members, one or more carbon atoms of the chain may be replaced by an oxygen, nitrogen or sulfur atom, by an SO ₂ group or by a halogen atom, the radical R3 not comprising a peroxide bond, nor of diazo, nitro or nitroso radicals;

- m is equal to 0, 1 or 2, it being understood that when m is equal to 2 then the radicals R3 can be identical or different,

• at least one 1,3-dihydroxybenzene coupler which can be substituted on the benzene ring by one or more substituents chosen from alkyl, alkoxy, amino, monoalkylamino, dialkylamino, halogen, -CO ₂ H or SO ₃ H groups, these radicals being able to be substituted by one or more hydroxyl radicals, or their addition salt with an acid or a base.

When n is equal to zero, the compound of formula (I) is a 4-aminophenyl pyrrolidine substituted on the pyrrolidine ring.

When m is zero, the compound of formula (II) is paraphenylenediamine.

Unless otherwise indicated, all the radicals, chains or groups defined in the present invention are linear or branched. The term alkyl alone or in a group means an alkyl radical comprising 1 to 4 carbon atoms, unless otherwise indicated.

The composition of the invention surprisingly makes it possible to obtain a powerful and tenacious coloring which does not have the drawbacks linked to the use of the para-phenylenediamine bases known from the prior art, one of the nitrogen forms a 5-membered ring.

According to a preferred variant of the invention, the first oxidation base of formula (I) is such that R2 represents a radical chosen from hydroxyl radicals and NR'R ", R 'and R" being as defined above. Preferably, R2 represents a hydroxyl, amino, mono- or di-alkylamino radical which can be substituted by a hydroxyl. By way of example, R2 represents a hydroxyl, amino, methylamino, dimethylamino, hydroxyethylamino radical.

In formula (I), when it is indicated that one or more of the carbon atoms of the radical R1 can be replaced by an oxygen, nitrogen, or sulfur atom or by an SO ₂ group, and / or that said radical R1 may contain one or more double bonds and / or one or more triple bonds, this means that the following transformations can be made, for example:

'- CH _j - H can become! ° ^H

In particular, R1 may represent a radical chosen from hydroxyl radicals; vinyl; allyl; C1-C4 alkyl which may be substituted by one or more hydroxyl groups, C1-C4 alkoxy, amino or carboxy; C1-C4 alkoxy substituted by hydroxyl, C1-C4 alkoxy, amino or carboxy. For example, R1 can be a chlorine or bromine atom, a methyl, ethyl, isopropyl, vinyl, allyl, methoxymethyl, hydroxymethyl, 1-carboxymethyl, 1-aminomethyl, 2-carboxyethyl, 2-hydroxyethyl, 3 radical. -hydroxypropyl, 1, 2-dihydroxyethyl, 1-hydroxy-2-aminoethyl, 1-amino-2-hydroxyethyl!, 1,2-diaminoethyl, methoxy, ethoxy, allyloxy, 2-hydroxyethyloxy. Preferably, the first base of formula (I) is such that n is equal to 0. The second oxidation base of formula (II) is preferably such that m is equal to 0 or m is equal to 1 and R3 represents an alkyl radical in C1-C4, preferably in Cl

The coupler 1, 3-dihydroxybenzene is preferably chosen from resorcin, 2-methyl resorcin, 4-chlororesorcin, 2-chlororesorcin, 2-methyl 5,6-dichlororesorcin.

A particularly preferred composition according to the invention comprises a first oxidation base of formula (I) in which n is equal to 0 and R2 represents a hydroxyl or amino radical, a second oxidation base of formula (11) in which m is 0 or 1 and R3 represents a C1-C4 alkyl group, and 1,3-dihydroxybenzene as a coupler.

The composition according to the invention may be such that the first oxidation base, the second oxidation base and the coupler are each present in an amount of between 0.001 and 10% by weight relative to the total weight of the composition, preferably between 0.005 and 6%.

The composition of the invention is preferably such that the molar ratio between the second oxidation base of formula (II) and the first oxidation base of formula (I) is greater than 2 and / or the molar ratio between the coupler of type 1, 3-dihydroxybenzene and the first oxidation base of formula (I) is greater than 2. In formula (I), the asymmetric carbon substituted by the radical R2 can be of configuration (R) and / or (S).

The composition of the invention may comprise one or more additional bases chosen from the oxidation bases conventionally used in oxidation dyeing, but different from the oxidation bases of formulas (I) or (II) defined above. These bases are for example paraphenylenediamines, bisphenylalkylenediamines, para-aminophenols, ortho-aminophenols and heterocyclic bases.

Among the paraphenylenediamines, there may be mentioned by way of example, 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, 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-N-β-hydroxyethylamino-5-toluene and their addition salts with an acid.

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.

Among the pyrimidine derivatives, mention may be made of the compounds described for example in patents DE 2,359,399; JP 88-169,571; JP 05 163 124; EP 0 770 375 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, the

2,4-dihydroxy 5,6-diaminopyrimidine, 2,5,6-triaminopyrimidine, and pyrazolopyrimidine derivatives such as those mentioned in patent application FR-A-2 750 048 and among which may be mentioned 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 acid addition salts 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 3 843 892, DE 4 133 957 and patent applications WO 94/08969, WO 94/08970, FR-A-2 733 749 and DE 195 43 988 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-diamino 3-methyl 1-isopropyl pyrazole, 4- amino 5- (2'-aminoethyl) amino 1, 3-dimethyl pyrazole, 3,4,5-triamino pyrazole, 1-methyl 3,4,5-triamino pyrazole, 3,5-diamino 1-methyl 4 -methylamiho pyrazole, 3,5-diamino 4- (β-hydroxyethyl) amino 1-methyl pyrazole, and their addition salts with an acid.

The additional oxidation base (s) are for example present in an amount of between 0.001 and 10%, preferably between 0.005 and 6%, by weight of the total weight of the composition. The composition according to the invention can contain one or more additional couplers. conventionally used for dyeing keratin fibers other than t, 3-dihydroxybenzene. Among these couplers, mention may in particular be made of metaphenylenediamines, meta-aminophenols and heterocyclic couplers. 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, 2,4-diamino 1- (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-naphthol , 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.

When they are present, the additional coupler (s) preferably represent from 0.001 to 10% by weight approximately of the total weight of the dye composition and even more preferably from 0.05 to 6%.

In general, the addition salts with an acid which can be used in the context of the dye compositions of the invention for the oxidation bases and the couplers are especially chosen from hydrochlorides, hydrobromides, sulfates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates. The addition salts with a base which can be used in the context of the invention are for example chosen from addition salts with soda, potassium hydroxide, 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 of the benzene series, cationic direct dyes, azo direct dyes, methinic direct dyes. 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 CC ₄ alkanols, such as ethanol and isopropanol; glycerol; glycols and glycol 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 may be 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 comprise various adjuvants conventionally used in compositions for dyeing the hair, such as anionic, cationic, nonionic, amphoteric, zwitterionic surfactants or mixtures thereof, anionic polymers, cationic, non-ionic, amphoteric, zwitterionic or their mixtures, mineral or organic thickening agents, associative or not antioxidant agents, penetration 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, preserving agents, opacifying agents.

These adjuvants are generally present in an amount for each of them of between 0.001 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 (III) below:

^Rβ \

N W - N (III)

R ₇ R ₉ in which W is a propylene residue optionally substituted by a hydroxyl group or a CC ₄ alkyl radical; R ₆ , R, Rs and R ₉ , identical or different, represent a hydrogen atom, a CC ₄ alkyl radical or a CC ₄ hydroxyalkyl radical.

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. 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 composition according to the present invention as defined above is applied to the fibers, the color being revealed using an oxidizing agent. The color can be revealed at acidic, neutral or alkaline pH and the oxidizing agent can be added to the composition of the invention just at the time of use or it can be used from an oxidizing composition containing it , applied simultaneously or sequentially to the composition of the invention.

According to a particular embodiment, the composition according to the present invention is mixed, preferably at the time of use, with a composition containing, in a medium suitable for dyeing, at least one oxidizing agent, this oxidizing agent being present in enough to develop color. The mixture obtained is then applied to the keratin fibers. After an exposure time of 3 to 50 minutes approximately, preferably 5 to 30 minutes approximately, the keratin fibers are rinsed, washed with shampoo, rinsed again and then dried. The oxidizing agents conventionally used for the oxidation dyeing of keratin fibers are, for example, hydrogen peroxide, urea peroxide, alkali metal bramates, persalts such as perborates and persulfates, peracids and enzymes among which may be mentioned peroxidases, oxidoreductases with 2 electrons such as uricases and oxygenases with 4 electrons such as laccases. Hydrogen peroxide is particularly preferred.

The oxidizing composition may also contain various adjuvants conventionally used in compositions for dyeing the hair and as defined above. The pH of the oxidizing composition containing the oxidizing agent is such that after mixing with the dye composition, the pH of the resulting composition applied to the keratin fibers preferably varies between 3 and 12 approximately, and even more preferably between 5 and 11 It can be adjusted to the desired value by means of acidifying or basifying agents usually used in dyeing keratin fibers and as defined above.

The composition which is finally applied to the keratin fibers 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. Another object of the invention is a device with several compartments or

Dye "kit" in which a first compartment contains the dye composition defined above and a second compartment contains the oxidizing composition. This device 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.

The following examples are intended to illustrate the invention.

EXAMPLES OF DYEING IN AN ALKALINE MEDIUM

Example I

The following dye compositions were prepared in accordance with the invention (in grams):

(*) Common dye support

- Polyglycerolated oleic alcohol with 2 moles of glycerol 4 g

- Polyglycerolated oleic alcohol with 4 moles of glycerol, 78% 5.69 g M.A active ingredients (M.A.)

- Oleic acid 3.0 g

- Oleic amine with 2 moles of ethylene oxide sold under the 7.0 g trade name ETHOMEEN O12 ® by the company AKZO

- Laurylamino diethylaminopropyl succinamate, sodium salt 3.0 g M.A. at 55% M.A.

- Oleic alcohol 5.0 g

- Oleic acid diethanolamide 12.0 g

- Propylene glycol 3.5 g

- Ethyl alcohol 7.0 g

- Dipropylene glycol 0.5 g

- Propylene glycol monomethyl ether 9.0 g

- Sodium metabisulfite in aqueous solution, 35% of M.A. 0.455 g M.A

- Ammonium acetate 0.8 g Antioxidant, sequestrant qs • Perfume, preservative qs Ammonia with 20% NH ₃ 10.2 g

At the time of use, each dye composition was mixed with an equal amount of an oxidizing composition consisting of a solution of hydrogen peroxide at 20 volumes (6% by weight) and having a pH of approximately 3.

Each mixture obtained had a pH of approximately 9.5 and was applied to locks of natural gray hair containing 90% white hairs. After 30 min, the locks of hair were then rinsed, washed with a standard shampoo, rinsed and then dried.

The locks of hair were dyed in the shades shown in the table below:

Example II

(*) Common dye support: identical to that described above At the time of use, each dye composition was mixed with an equal amount of an oxidizing composition consisting of a solution of hydrogen peroxide at 20 volumes (6% by weight) and having a pH of approximately 3.

The locks of hair were dyed in the shades shown in the table below:

Claims

1. Composition for the oxidation dyeing of keratin fibers, and in particular human keratin fibers such as the hair, characterized in that it comprises, in a medium suitable for dyeing,

in which :

- Ri represents a halogen atom; a Cι-C ₇ carbon chain, saturated or which may contain one or more double bonds and / or one or more triple bonds, linear or branched, which may be in the form of a ring having 3 to 6 members, one or more carbon atoms of the chain being able to be replaced by an oxygen, nitrogen or sulfur atom, by an SO ₂ group or by a halogen atom, the radical Ri not comprising a peroxide bond, nor of diazo, nitro or nitroso radicals ;

R ₂ represents a hydroxyl radical, an -OR group in which R represents a linear or branched C1-C4 alkyl radical substituted by one or more substituents chosen from the group consisting of a halogen atom, C1-C2 alkoxy, amino, and C1-C2 aminoalkyl, or a C3-C4 radical substituted by one or more hydroxyl radicals; a group -NR'R "in which R 'and R" represent, independently of one another, a hydrogen atom, a linear or branched C1-C4 alkyl radical substituted by one or more radicals chosen from the group consisting of a halogen atom, a hydroxyl radical, C1-C2 alkoxy, amino and C1-C2 aminoalkyl; an acetoxy group; an acetamido group,

- n is equal to 0, 1 or 2, it being understood that when n is equal to 2 then the radicals R1 can be identical or different, • a second oxidation base chosen from the paraphenylenediamines of formula (II) below, and their addition salts with an acid:

in which

- R3 represents a halogen atom; a C-ι-C ₇ carbon chain, saturated or which may contain one or more double bonds and / or one or more triple bonds, linear or branched, which may be in the form of a ring having 3 to 6 members, one or more atoms of carbon in the chain which can be replaced by an oxygen, nitrogen or sulfur atom, by an SO ₂ group or by a halogen atom, the radical R3 not comprising a peroxide bond, nor of diazo or nitro radicals or nitroso;

• at least one 1,3-dihydroxybenzene coupler which can be substituted on the benzene ring by one or more substituents chosen from alkyl, alkoxy, amino, monoalkylamino, dialkylamino, halogen, -CO ₂ H, -SO ₃ H groups, these radicals may be substituted by one or more hydroxyl radicals, or their addition salt with an acid or a base.

2. Composition according to claim 1 in which the first oxidation base of formula (I) is such that R1 represents a radical chosen from hydroxyl radicals; vinyl; allyl; C1-C4 alkyl which may be substituted by one or more hydroxyl groups, C1-C4 alkoxy, amino or carboxy; C1-C4 alkoxy substituted by hydroxyl, C1-C4 alkoxy, amino or carboxy, halogen.

3. Composition according to any one of claims 1 or 2 in which the first oxidation base of formula (I) is such that R1 represents a bromine or chlorine atom, a methyl, ethyl, isopropyl, vinyl, allyl radical. , methoxymethyl, hydroxymethyl, 1-carboxymethyl, 1-aminomethyl, 2-carboxyethyl, 2-hydroxyethyl, 3-hydroxypropyl, 1, 2-dihydroxyethyl, 1-hydroxy-2-aminoethyl, methoxy, ethoxy, allyloxy, or 3-hydroxyethyloxy.

4. Composition according to claim 1 in which the first oxidation base of formula (I) is such that n is equal to 0.

5. Composition according to any one of claims 1 to 4 wherein the first oxidation base of formula (I) is such that R2 represents a hydroxyl radical or NR'R ".

6. Composition according to any one of claims 1 to 5 in which the first oxidation base of formula (I) is such that R2 represents a radical chosen from hydroxyl, amino, mono- or di-alkylamino radicals which can be substituted by a hydroxyl.

7. Composition according to claim 6 in which R2 represents a radical chosen from hydroxy, amino, methylamino, dimethylamino, hydroxyethylamino radicals.

8. Composition according to any one of claims 1 to 7 in which the second oxidation base of formula (II) is such that R3 represents a C1-C4, preferably C1-C2 alkyl radical.

9. Composition according to any one of claims 1 to 8 in which the second oxidation base of formula (II) is such that m is equal to 1.

10. Composition according to any one of claims 1 to 7 in which the second oxidation base of formula (II) is such that m is equal to 0.

11. Composition according to any one of claims 1 to 10 in which the coupler 1, 3-dihydroxybenzene is chosen from resorcin, 2-methyl resorcin, 4-chlororesorcin, 2-chlororesorcin, 2-methyl 5, 6 dichlororesorcin.

12. Composition according to claim 1 in which the first oxidation base of formula (I) is such that n is equal to 0 and R2 represents a hydroxyl or amino radical, the second oxidation base of formula (II) is such that m is 0 or m is equal to 1 and R3 represents a C1-C4 alkyl group, and the coupler is 1, 3-dihydroxybenzene.

13. Composition according to any one of the preceding claims, in which the first oxidation base, the second oxidation base and the coupler are each present in an amount of between 0.001 and 10% by weight relative to the total weight of the composition.

14. Composition according to any one of the preceding claims, comprising one or more additional couplers chosen from metaphenylenediamines, meta-aminophenols, and heterocyclic couplers.

15. The composition as claimed in claim 14 in which the additional coupler (s) represent from 0.001 to 10% by weight of the total weight of the composition.

16. Composition according to any one of the preceding claims, further comprising one or more additional oxidation bases chosen from paraphenylenediamines other than those of formula (I) or (II) defined above, bis-phenylalkylenediamines, para-aminophenols, ortho-aminophenols, heterocyclic bases, and their addition salts with an acid.

17. The composition as claimed in claim 16 in which the additional oxidation base or bases are present in an amount between 0.001 and 10%, preferably between 0.005 and 6%, by weight of the total weight of the composition.

18. Composition according to any one of the preceding claims, further comprising a direct dye.

19. Composition according to any one of the preceding claims, in which the molar ratio between the second oxidation base of formula (II) and the first oxidation base of formula (I) is greater than 2.

20. Composition according to any one of the preceding claims, in which the molar ratio between the type 1, 3-dihydroxybenzene coupler and the first oxidation base of formula (I) is greater than 2.

21. Process for the oxidation dyeing of keratin fibers and in particular human keratin fibers such as the hair, characterized in that at least one composition as defined in any one of claims 1 to 20 is applied to the fibers , and reveal the color using an oxidizing agent.

22. The method of claim 21 wherein the oxidizing agent is selected from hydrogen peroxide, urea peroxide, alkali metal bramates, persalts such as perborates and persulfates, peracids and oxidase enzymes.

23. Method according to one of claims 21 or 22 in which the oxidizing agent is mixed at the time of use with the composition as defined according to any one of claims 1 to 20.

24. Method according to any one of claims 21 or 22 in which the oxidizing agent is applied in the form of an oxidizing composition simultaneously or sequentially to the composition as defined according to any one of claims 1 to 20 on the fibers.

25. Multi-compartment device or multi-compartment dye "kit", in which a first compartment contains a composition as defined in any one of claims 1 to 20 and a second compartment contains an oxidizing composition.