EP1377264A1

EP1377264A1 - Dyeing composition for dyeing keratinous fibres comprising a cationic azo-dye

Info

Publication number: EP1377264A1
Application number: EP02724400A
Authority: EP
Inventors: Laurent Vidal; Aziz Fadli
Original assignee: LOreal SA
Current assignee: LOreal SA
Priority date: 2001-04-02
Filing date: 2002-04-02
Publication date: 2004-01-07
Also published as: JP3748856B2; FR2822693B1; JP2004529137A; US7022143B2; US20040107513A1; WO2002078659A1; FR2822693A1

Abstract

The invention concerns a novel dyeing composition for dyeing keratinous fibres, in particular human hair, comprising a cationic azo-dye of formula (I): W1-N=N-W2-W3, as well as the dyeing method using said composition and the novel compounds of formula (I).

Description

TINCTORIAL COMPOSITION FOR DYEING KERATINIC FIBERS COMPRISING A CATIONIC AZOIC DYE

The subject of the invention is a new dye composition for dyeing keratin fibers, in particular human hair, containing a particular cationic azo dye, as well as the process for dyeing keratin fibers using such a composition. The subject of the invention is also new azo cationic dyes. 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, 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.

This oxidation dyeing process consists in applying to the keratin fibers, oxidation bases or a mixture of oxidation bases and couplers with an oxidizing agent, for example hydrogen peroxide, to leave on, then to rinse the fibers. The resulting colorings are permanent, powerful, and resistant to external agents, in particular to light, bad weather, washing, perspiration and rubbing. Generally applied at basic pH, it makes it possible to obtain a dyeing and at the same time a lightening of the fiber which translates in practice by the possibility of obtaining a final coloration lighter than the original color. In addition, the lightening of the fiber has the advantageous effect of generating a solid color in the case of gray hair, and in the case of naturally pigmented hair, of bringing out the color, that is to say making it more visible. It is also known to dye keratin fibers by direct coloring. The method conventionally used in direct dyeing consists in applying to the keratin fibers direct dyes which are colored and coloring molecules having an affinity for the fibers, to allow to pause, then to rinse the fibers. It is known, for example, to use direct dyes of the nitro benzene, anthraquinone, nitropyridine type, dyes of the azo, xanthene, acridine azine type or triarylmethane dyes.

The resulting colorings are particularly chromatic colors which are however temporary or semi-permanent because the nature of the interactions which bind the direct dyes to the keratin fiber, and their desorption from the surface and / or from the core of the fiber are responsible for their low dye power and their poor resistance to washing or perspiration. These direct dyes are also generally sensitive to light due to the low resistance of the chromophore vis-à-vis photochemical attacks and lead over time to a fading of the coloring of the hair. In addition, their sensitivity to light is dependent on their uniform or aggregate distribution in the keratin fiber.

It is known to use direct dyes in combination with oxidizing agents. However, direct dyes are generally sensitive to the action of oxidizing agents such as hydrogen peroxide, and reducing agents such as sodium bisulfite, which generally make them difficult to use in lightening direct dye compositions based on hydrogen peroxide and based on an alkalizing agent or in oxidation dye compositions in combination with precursors of the oxidation base or coupler type.

For example, it has been proposed in patent applications FR-1,584,965 and JP-062,711,435 to dye the hair with dye compositions based on direct nitro dyes and / or disperse dyes azo and hydrogen peroxide ammonia by applying to the hair a mixture of said dyes and said oxidant, produced just before use. However, the colorings obtained have proved to be insufficiently tenacious and disappear with shampooing, revealing the lightening of the hair fiber. Such coloring becomes unsightly by evolving over time. It has also been proposed in patent applications JP-53 95693 and JP-55 022638 to dye the hair with compositions based on cationic direct dyes of the oxazine type and ammoniacal hydrogen peroxide, by applying to the hair, in a first step, ammoniacal hydrogen peroxide, then in a second step, a composition based on the direct oxazine dye. This coloration is not satisfactory, due to the fact that it requires a process made too slow by the pause times of the two successive stages. If, on the other hand, an extemporaneous mixture of the direct oxazine dye with ammonia hydrogen peroxide is applied to the hair, it does not color, or at least, a coloring of the hair fiber is obtained which is almost nonexistent.

More recently, patent application FR 2 741 798 has described dye compositions containing direct dyes comprising at least one quaternized nitrogen atom of the azo or azomethine type, said compositions being to be mixed extemporaneously at basic pH with an oxidizing composition. These compositions make it possible to obtain colorings with homogeneous, tenacious and brilliant reflections. However, they do not make it possible to dye the keratin fibers with as much power as with oxidation coloring compositions.

There is therefore a real need to look for direct chromatic dyes which make it possible to dye keratin fibers as powerfully as oxidation dyes, which are as stable as they are in light, are also resistant to weathering, washing and perspiration, and moreover, sufficiently stable in the presence of oxidizing and reducing agents to be able to simultaneously obtain a lightening of the fiber either by the use of direct lightening compositions containing them, or by the use of oxidation coloring compositions containing them. There is also a real need to look for direct dyes which make it possible to dye keratin fibers in order to obtain a very wide range of colors, in particular very chromatic, without forgetting the so-called "fundamental" shades such as blacks and browns. These objects are achieved with the present invention which relates to a composition for dyeing keratin fibers and in particular fibers Human keratin such as the hair, comprising at least one azo cationic dye of formula (I) below:

W— N = N- jW ₃ in which

- W *, represents a cationic 5-membered aromatic heterocycle of formula (11) below

formula (II)

- W ₂ represents a divalent aromatic carbon or pyridine group of formulas (III) or (IV) below

formula (III) formula (IV)

W ₃ represents a 5 or 6-membered heterocycle of formula (V) below

formula (V)

formulas in which - ∑ _! represents an oxygen or sulfur atom or an NR ₁₂ radical,

- Z ₂ represents a nitrogen atom or a radical CR ^,

- R ₉ and R ₁₂ represent, independently of each other, a CC ₈ alkyl radical, optionally substituted by one or more radicals chosen from hydroxy, C | -C ₂ alkoxy, (poly) radical - C ₂ -C ₄ hydroxyalkoxy, amino, O | -C ₂ (di) alkylamino, carboxy, sulfonic; an optionally substituted phenyl radical,

- R ₁₀ and Ru represent, independently of one another, a hydrogen atom; a C ₁ -C ₄ alkyl radical, optionally substituted by one or more radicals chosen from a hydroxy, a C _r C ₂ alkoxy, a (poly) hydroxy C ₂ -C ₄ alkoxy radical, an amino, a (di ) C * -C ₂ alkylamino, carboxy, sulfonic; an optionally substituted phenyl radical; a carboxy radical; a sulfonylamino radical;

- R ₅ , R ₆ , R ₇ and R ₈ represent, independently of one another, a hydrogen atom; a chlorine atom; a bromine atom; a linear or branched C _r C ₆ hydrocarbon chain, which can form one or more carbon rings having 3 to 6 members, and which can be saturated or unsaturated, of which one or more carbon atoms of the carbon chain can be replaced by an atom oxygen, nitrogen or sulfur or with an SO ₂ group, and the carbon atoms of which may be, independently of one another, substituted by one or more halogen atoms; R ₅ , R ₆ , R ₇ and R ₈ having no peroxide bond, nor diazo or nitroso radicals,

- n is an integer equal to 0 or 1,

-R ₀ , Ri, R ₂ , R ₃ and R ₄ represent, independently of one another, a hydrogen atom, a hydroxy radical; amino; acetoxy; a group -NR ₁₃ R ₁₄ , R ₁₃ and R ₁₄ independently of one another representing a hydrogen atom, a CC ₄ alkyl radical substituted by one or more radicals chosen from a halogen atom, a radical hydroxy, C 1 -C ₂ alkoxy, amino or amino (di) C _r C ₂ alkyl; a sulfonylamino radical; a carboxy radical; a carboxamido radical; an amido radical; a mono or di alkylamido radical; halogen; a CC ₆ alkyl radical substituted by one or more radicals chosen from a hydroxy radical, C ^ Cs alkoxy, (poly) - C ₂ -C ₄ alkoxy, amino, (di) C ₁ -C ₂ alkylamino, being understood that at least one of the groups R ₀ , R. ,, R ₂ , R ₃ and R ₄ is different from hydrogen, - X is an organic or mineral anion.

In the context of the present invention, the term "alkyl" means, unless otherwise indicated, an alkyl radical comprising from 1 to 10 carbon atoms, preferably from 1 to 6 carbon atoms, which may be linear or branched. The term alkoxy means alkyl-O-, the term alkyl having the preceding meaning.

According to the invention, when it is indicated that one or more of the carbon atoms of the hydrocarbon chain defined for the radicals R ₅ to R ₈ can be replaced by an oxygen, nitrogen or sulfur atom or by an SO ₂ group, and / or that these hydrocarbon chains are unsaturated, this means that the following transformations can be carried out, for example:

OH

I ι - CHr 2-H can become '-

-CH— CH ₃ can become * - O-CH,

In particular, the term "branched hydrocarbon chain" means a chain which can form one or more carbon rings comprising from 3 to 6 members. The term “unsaturated hydrocarbon chain” is understood to mean a chain which can comprise one or more double bonds and / or one or more triple bonds, this hydrocarbon chain being able to lead to aromatic groups.

The asymmetric carbons substituted by the radicals R ₀ , Ri, R ₂ , R ₃ , R ₄ can be of configuration (R) and / or (S). According to the invention, R _0, _R,, R _2, R _3, R ₄ preferably represent a hydroxyl group, acetoxy, amino, methylamino, dimethylamino, 2-hydroxyethylamino, carboxy, carboxamido, amido, mono or di alkylamido. According to a particular embodiment, R ₀ , R * ,, R ₂ , R ₃ , R ₄ and n are chosen from the following combinations:

Preferably, R ₀ , R., R ₂ , R ₃ , R ₄ are chosen from the following combinations:

The radicals R ₅ , R ₆ , R ₇ and R ₈ are preferably chosen from a hydrogen atom, a methyl, ethyl, isopropyl, methoxymethyl, hydroxymethyl, 1-carboxymethyl, 1-aminomethyl, 1-aminoethyl, 2- radical. carboxyethyl, 2-hydroxyethyl, 3-hydroxypropyl, 1, 2-dihydroxyethyl, 1-hydroxy-2-aminoethyl, 2-hydroxy-1-aminoethyl, methoxy, ethoxy, 3-hydroxyethyloxy, 3-aminoethyloxy,, amino, methylamino, dimethylamino , 2-hydroxyethylamino ,. According to a preferred embodiment, R ₅ , R ₆ , R ₇ and R ₈ are chosen from a hydrogen atom, a methyl, hydroxymethyl, 2-hydroxyethyl, 1,2-dihydroxyethyl, methoxy, 2-hydroxyethoxy, amino radical. , 2-hydroxyethylamino, more preferably a hydrogen atom, a methyl radical, a methoxy, amino radical.

According to the invention, R ₉ and R ₁₂ preferably represent a C ₁ -C ₄ alkyl radical, optionally substituted by one or more radicals chosen from hydroxy, C * -C ₂ alkoxy, amino, (di ) C 1 -C ₂ alkylamino, a carboxyl, a sulfonic, a phenyl, more preferably a methyl, ethyl, 2-hydroxyethyl, 1-carboxymethyl, 2-carboxyethyl, 2-sulfonylethyl radical.

According to the invention, R ₁₀ and R- _I - _I preferably represent a hydrogen atom, a C _r C ₄ alkyl radical optionally substituted by one or more radicals chosen from hydroxy, amino, (di) alkylamino in C ₁ -C ₂ , carboxy, phenyl, more preferably, R ₁₀ and R *, ** represent a hydrogen atom, a methyl, ethyl, 2-hydroxyethyl, carboxy, 1-carboxymethyl, 2 - carboxyethyl, 2-sulfonylethyl.

According to the present invention, the composition comprises an azo dye of formula (I) as defined above in which Z1 is -NR ₁₂ and W2 is a divalent group of formula (III).

According to a preferred embodiment, the composition of the present invention comprises an azo dye of formula (I) as defined above in which Z1 is -NR ₁₂ , W2 is a divalent group of formula (III), Z ₂ is CR ^ . The mineral or organic anion X can be chosen from a halide such as chloride, bromide, fluoride, iodide; a hydroxide; a sulfate; a hydrogen sulfate; a (C ₁ -C ₆ ) alkyl sulphate such as for example a methyl sulphate or an ethyl sulphate; an acetate; a tartrate; an oxalate; a (C * -C ₆ ) alkyl sulfonate such as methylsulfonate; an arylsulfonate substituted or unsubstituted by a C _r C ₄ alkyl radical such as for example a 4-toluylsulfonate.

The concentration of azo cationic dye of formula (I) can vary between 0.001 and 5% by weight approximately relative to the total weight of the dye composition, and preferably between approximately 0.05 and 2%. The composition of the invention may also comprise an oxidizing agent.

This oxidizing agent can be any oxidizing agent conventionally used for bleaching keratin fibers. The oxidizing agent is preferably chosen from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulfates. The use of hydrogen peroxide is particularly preferred.

The composition according to the invention can also comprise an oxidation base. This oxidation base can be chosen from the oxidation bases conventionally used in oxidation dyeing, for example paraphenylenediamines, bis-phenylalkylenediamines, para-aminophenols, ortho-aminophenols and heterocyclic bases.

Among the paraphenylenediamines, there may be more particularly 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, NN- 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 - (ethyl, β-hydroxyethyl) paraphenylenediamine, N- (Β, γ- dihydroxypropyl) para-phenylenediamine, N- (4'-aminophenyl) para-phenylenediamine, N-phenyl para-phenylenediamine, 2-β-hydroxyethyloxy para-phenylenediamine, 2-β-acetylaminoethyloxy para-phenylenediamine, para-phenylenediamine, para-phenylenediamine, pyrrolidine, 2 thienyl paraphenylene diamine, 2-β hydroxyethylamino 5-amino toluene 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 para-phenylenediamine, 2,3-dimethyl para-phenylenediamine, N, N-bis- (β-hydroxyethyl) para-phenylenediamine, 2-chloro para-phenylenediamine, 2-β-acetylaminoethyloxy para-phenylenediamine, and their addition salts with an acid are particularly preferred . Among the bis-phenylalkylenediamines that 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, 2,4-dihydroxy 5,6-diaminopyrimidine, 2,5,6-triaminopyrimidine, and pyrazolo-pyrimidine 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-3J-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) - aminoj-ethanol, 2 - [(7-amino-pyrazolo [1 , 5-a] pyrimidin-3-yl) - (2-hydroxy-ethyl) -amino] - ethanol, 5,6-dimethyl pyrazolo- [1,5-a] -pyrimidine-3J-diamine, 2, 6-dimethyl pyrazolo- [1, 5-a] -pyrimidine-3J-diamine, la 2, 5, N 7, N 7-tetramethyl pyrazolo- [1, 5-a] - pyrimidine-3,7-diamine, la 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-methylamino pyrazole, 3,5 -diamino 4- (β-hydroxyethyl) amino 1-methyl pyrazole, and their addition salts with an acid. The composition according to the invention may also contain one or more couplers conventionally used for dyeing keratin fibers. Among these couplers, mention may in particular be made of metaphenylenediamines, metaaminophenols, metadiphenols, naphthalene couplers 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, 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, -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 with an acid.

In the composition of the present invention, the coupler (s) are generally present in an amount between 0.001 and 10% by weight approximately of the total weight of the dye composition and more preferably from 0.005 to 6%. The oxidation base (s) are present in an amount preferably between 0.001 to 10% by weight approximately of the total weight of the dye composition, and more preferably from 0.005 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 in particular chosen from hydrochlorides, hydrobromides, sulfates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates.

The dye composition in accordance with the invention may also contain direct dyes different from those of formula (I), these dyes being able in particular to be chosen from nitro dyes of the benzene series, cationic direct dyes, azo direct dyes, methine 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 C 1 -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 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 contain various adjuvants conventionally used in compositions for dyeing the hair, such as anionic, cationic, nonionic, amphoteric, zwitterionic surfactants or mixtures thereof, anionic polymers, cationic, nonionic, amphoteric, zwitterionic or mixtures thereof, inorganic or organic thickening agents, and in particular associative anionic, cationic, nonionic and amphoteric polymeric thickeners, 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 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 (III) below:

in which W is a propylene residue optionally substituted by a hydroxyl group or a C * -C ₄ alkyl radical; R ₆ , R ₇ , R ₈ and R ₉ , identical or different, represent a hydrogen atom, a C ₁ -C ₄ alkyl or 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 direct dyeing process which comprises the application of a dye composition containing a dye of formula (I) as defined above on keratin fibers. After a pause, the keratin fibers are rinsed leaving colored fibers to appear. The application to the fibers of the dye composition containing the azo cationic dye of formula (I) can be implemented in the presence of an oxidizing agent which causes discoloration of the fiber. This oxidizing agent can be added to the composition containing the cationic azo dye at the time of use or directly on the keratin fiber. According to a particular embodiment, the composition containing the azo cationic dye of formula (I) is free from oxidation base and from coupler.

The invention also relates to a process for permanent oxidation dyeing which comprises applying to the fibers a dye composition which comprises a dye of formula (I), at least one oxidation base and optionally at least one coupler, in the presence of an oxidizing agent.

The oxidation base, the coupler and the oxidizing agent are as defined above.

In the context of the permanent oxidation dye, it is also possible to use as oxidizing agent enzymes among which there may be mentioned peroxidases, 2-electron oxidoreductases such as uricases and 4-electron oxygenases such as laccases.

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 to the fibers simultaneously or sequentially to the dye composition.

In the case of permanent oxidation dyeing or direct dyeing, the dye composition 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 an amount sufficient to develop a coloration. The mixture obtained is then applied to the keratin fibers. After a pause time of approximately 3 to 50 minutes, preferably 5 to 30 minutes approximately, the keratin fibers are rinsed, washed with shampoo, rinsed again and then dried.

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 "kit" for dyeing in which a first compartment contains the dye composition of the invention 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.

Finally, the subject of the invention is also the cationic azo dyes of formula (I) as defined above. These compounds can be obtained from the preparation methods described for example in documents EP 810824, GB 9619573, RO 106572, J. Chem. Res .., Synop. (1998), (10), 648-649, DE 19721619, US 5852179, Synth. Common 1999, 29 (13), 2271-2276.

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

Example 1: Preparation of a compound of formula:

2- [4 (3 hydroxypyrrolidine -1-yl) -phenylazo) -1,3-dimethyl-3H-imidazol-1- ium perchlorate.

2.5 g (7.6 mmol) of 2- (4-methoxy-phenylazo) -1, 3-dimethyl-3H-imidazol-1-ium perchlorate and 50 ml of 2-propanol are loaded into a fully equipped flask. The mixture is brought to 60 ° C. 1.3 g (15.2 mmol) of pyrrolidine are added. This mixture is brought with stirring to reflux of the solvent for 3 hours.

With stirring, the mixture is allowed to return to ambient temperature and a red solid is isolated by filtration, the latter is washed 3 times with diisopropyl ether. After drying under vacuum at 30 ° C., 2.6 g of 2- [4 (3 hydroxy pyrrolidine -1-yl-phenylazo) -1,3-dimethyl-3H-imidazol-1-ium perchlorate are recovered. red powder.

The characteristics of this product are as follows:

ESI + mass: m / z = 327 [M ^{+ l}

1 H NMR: (400MHz-DMSO) ppm:

1.88 (m-1H); 2.27 (m-1H); 3.18 (m-1H); 3J2 (m-2H); 4.25 (m-1H) pyrrolidine 3.91 (s-6H) -NCH ₃ ;

6.61 (d-2H); 7.75 (d-2H) phenyl 7.47 (s-2H) imidazole this gives a dye giving a burgundy red dye

Example No. 2: Preparation of a compound of formula

2- [4 (3-acetamidopyrrolidine -1-yl) -phenylazo) -1, 3-dimethyl-3H-imidazol-1-ium perchlorate.

1.25 g (3.8 mmol) of 2- (4-methoxy-phenyleazo) -1,3-dimethyl-3H-imidazol-1-ium perchlorate and 15 ml of 2-propanol are charged into a fully equipped reactor. The mixture is brought to 60 ° C. 0.96 g (7.6 mmol) of acetamidopyrrolidine is added. This mixture is brought with stirring to reflux of the solvent for 3 hours.

With stirring, the mixture is allowed to return to ambient temperature and the red solid is isolated by filtration. This is washed 3 times with diisopropyl ether. After drying under vacuum at 30 ° C to constant weight, 0.5 g of

2- [4 (3-Acetamidopyrrolidine -1-yl) -phenylazo) -1,3-dimethyl-3H-imidazol- perchlorate

1-ium chloride.

Analysis: ESI + mass: m / z = 327 [M ⁺¹

1H NMR: (400MHz-CD3OD) ppm:

2.1 (s-3H); 2.12 (m-1H); 3.18 (m-1H); 2.34 (m-1H); 3.47 (m-1H) pyrrolidine 3.95 (s-6H) -NCH ₃ ;; 6J8 (d-2H); 7.96 (d-2H) phenyl 7.39 (s-2H) imidazole

A dye is thus obtained giving a red dye. Example n: 3: preparation of a compound of formula

2- [4- (4-Hydroxy-piperidin-1 -yl) -phenylazo] -1, 3-dimethyl-3H-imidazol-1 -ium; perchlorate

Using the same procedure as that of Example 2, the above compound is obtained.

Analyzes :

ESI + mass: m / z = 300 [M ^+]

1 H NMR: (400MHz-CD3OD) ppm: 1.27 (m-2H); 1.66 (m-2H); 3.19 (m-2H); 3J4 (m-1H); 4.66 (m-1H); 4.16 (m-1H) piperidine 3J4 (s-6H) -NCH ₃ ; 6.95 (d-2H); 7.80 (d-2H) phenyl 7.49 (s-2H) imidazole

A dye is thus obtained giving a purple red dye.

DYEING EXAMPLES

The following dye compositions were prepared:

The composition is mixed with 20 volumes cream oxidant (1/1, 5 m / m) so that the final concentration of dye is 0.5%. The mixture is applied to locks of natural and permanent hair 90% white. 10 g of composition are applied to 1 g of wick. After 35 minutes of laying at room temperature, the locks are rinsed, shampooed, rinsed again and dried.

Each lock is evaluated before and after dyeing in the L * a * b * system, using a CM 2002 MINOLTA® spectrophotometer (Illuminant D65). In space L * a ^* b *, clarity is indicated by the value L ^* on a scale from 0 to 100 while the chromatic coordinates are expressed by a * and b * which indicate two axes of color, a ^* l 'red-green axis and b ^* yellow-blue axis.

According to this system, the higher the value of L, the lighter and less intense the color. Conversely, the lower the value of L, the darker or very intense the color.

The following dye results were obtained.

Claims

1. Composition for dyeing keratin fibers and in particular human keratin fibers such as the hair, comprising at least one cationic azo dye of formula (I) below

W— N = NW ₂ -W ₃ in which

- W-, represents a cationic 5-membered aromatic heterocycle of formula (II) below

formula (II)

formula (III) formula (IV)

W ₃ represents a 5 or 6-membered heterocycle of formula (V) below

formula (\ ') formulas in which

- Z ** represents an oxygen or sulfur atom or an NR ₁₂ radical,

- Z ₂ represents a nitrogen atom or a radical CR ^, - R ₉ and R ₁₂ independently of one another represent a C ^ alkyl radical

C ₈ , optionally substituted by one or more radicals chosen from a hydroxy, a C | -C ₂ alkoxy, a (poly) hydroxy C ₂ -C ₄ alkoxy radical, an amino, a C | -C (di) alkylamino C ₂ , carboxy, sulfonic; an optionally substituted phenyl radical,

- R ₁₀ and R ***, represent, independently of one another, a hydrogen atom; a C | -C alkyl radical, optionally substituted by one or more radicals chosen from a hydroxy, a C * | -C ₂ alkoxy, a (poly) hydroxy C ₂ -C ₄ alkoxy radical, an amino, a ( di) C * -C ₂ alkylamino, carboxy, sulfonic; an optionally substituted phenyl radical; a carboxy radical; a sulfonylamino radical;

- R ₅ , R ₆ , R ₇ and R ₈ represent, independently of one another, a hydrogen atom; a chlorine atom; a bromine atom; a hydrocarbon chain in

C * | -C ₆ linear or branched, which can form one or more carbon rings having from 3 to 6 links, and which can be saturated or unsaturated, of which one or more carbon atoms of the carbon chain can be replaced by an atom of oxygen, nitrogen or sulfur or with an SO ₂ group, and the carbon atoms of which may be, independently of one another, substituted by one or more halogen atoms; R ₅ , R ₆ , R ₇ and R ₈ having no peroxide bond, nor diazo or nitroso radicals,

- N is an integer equal to 0 or 1, -R ₀ , R- ,, R ₂ , R ₃ and R ₄ represent, independently of one another, a hydrogen atom, a hydroxy radical; amino; acetoxy; a group -NR ₁₃ R ₁₄ , R ₁₃ and R ₁₄ independently of one another representing a hydrogen atom, a C 1 -C alkyl radical substituted by one or more radicals chosen from a halogen atom, hydroxy, C _r C ₂ alkoxy, amino or amino (di) alkyl CC ₂ ; a sulfonylamino radical; a carboxy radical; a carboxamido radical; an amido radical; a mono or di alkylamido radical; halogen; a C * -C ₆ alkyl radical substituted by one or more radicals chosen from a hydroxy, C _r C ₂ alkoxy, (poly) - C ₂ -C ₄₎ alkoxy, amino, (di) C ₁ -C alkylamino radical, it being understood that at least one of the groups R ₀ , R. ,, R ₂ , R ₃ and R ₄ is different from hydrogen,

- X is an organic or mineral anion.

2. Composition according to claim 1 wherein R _0, R _*, R _2, R _3, R ₄ independently of one another a hydroxy group, acetoxy, amino, methylamino, dimethylamino, 2-hydroxyethylamino, carboxy , carboxamido, amido, mono or di alkylamido.

3. Composition according to claim 1 or 2 wherein R _0, _R,, R _2, R _3, R ₄ and n are chosen from the following combinations:

4. Composition according to claim 3 in which R ₀ , R _1t R ₂ , R ₃ , R are chosen from the following combinations:

5. Composition according to any one of claims 1 to 4 in which R ₅ , R ₆ , R ₇ and R ₈ are chosen from a hydrogen atom, a methyl, ethyl, isopropyl, methoxymethyl, hydroxymethyl, 1-carboxymethyl radical. , 1- aminomethyl, 1-aminoethyl, 2-carboxyethyl, 2-hydroxyethyl, 3-hydroxypropyl, 1, 2- dihydroxyethyl, 1-hydroxy-2-aminoethyl, 2-hydroxy-1-aminoethyl, methoxy, ethoxy, 3-hydroxyethyloxy , 3-aminoethyloxy, amino, methylamino, dimethylamino, 2-hydroxyethylamino.

6. Composition according to claim 5 in which R ₅ , R ₆ , R ₇ and R ₈ are chosen from a hydrogen atom; a methyl radical; hydroxymethyl; 2- hydroxyethyl; 1, 2-dihydroxyethyl; methoxy; 2-hydroxyethoxy, preferably a hydrogen atom, a methyl radical, a methoxy, amino radical.

7. Composition according to any one of claims 1 to 6 in which R ₉ and R ₁₂ independently of one another represent a C *, - C ₄ alkyl radical, optionally substituted by one or more radicals chosen from hydroxy, C ₁ -C ₂ alkoxy, amino, CC ₂ (di) alkylamino, carboxyl, sulfonic, phenyl radical, preferably a methyl, ethyl, 2-hydroxyethyl, 1-carboxymethyl radical, 2- carboxyethyl, 2-sulfonylethyl.

8. Composition according to any one of the preceding claims, in which R ₁₀ and R **. * Represent a hydrogen atom or a C _| -C ₄ optionally substituted by one or more radicals chosen from hydroxy, amino, C (-C ₂ ) (di) alkylamino, carboxy; a phenyl radical, preferably a hydrogen atom, a methyl, ethyl, 2-hydroxyethyl, carboxy, 1-carboxymethyl, 2-carboxyethyl, 2-sulfonylethyl radical.

9. Composition according to any one of the preceding claims, in which Z1 is -NR ₁₂ , W2 is a divalent group of formula (III).

10. Composition according to claim 9, in which Z ₂ is CR *,. *.

11. Composition according to any one of claims 1 to 10 further comprising an oxidation base.

12. Composition according to claim 11, in which the oxidation base is chosen from paraphenylenediamines, bisphenylalkylenediamines, para-aminophenols, ortho-aminophenols, heterocyclic bases, and their addition salts with an acid.

13. Composition according to any one of claims 11 or 12 in which the oxidation base or bases are present in an amount between 0.001 and 10%, preferably between 0.005 and 6%.

14. Composition according to any one of claims 1 to 13 comprising at least one coupler.

15. Composition according to claim 14, in which the coupler is chosen from metaphenylenediamines, meta-aminophenols, metadiphenols, naphthalene couplers and heterocyclic couplers and their addition salt with an acid.

16. Composition according to any one of claims 1 to 15 further comprising an oxidizing agent, preferably hydrogen peroxide.

17. Oxidation dyeing process for keratin fibers and in particular human keratin fibers such as the hair, characterized in that at least one dye composition as defined in any one of claims 1 is applied to the fibers 10.

18. The method of claim 17 wherein the dye composition contains an oxidizing agent.

19. The method of claim 18 wherein the oxidizing agent is mixed at the time of use with the dye composition.

20. Method according to any one of claims 17 or 18 in which the oxidizing agent is applied to the fibers in the form of an oxidizing composition simultaneously or sequentially with the dye composition.

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 dye composition as defined according to one is applied to the fibers any of claims 1 to 10, further comprising at least one oxidation base and optionally at least one coupler, in the presence of an oxidizing agent.

22. The method of claim 21 wherein the oxidizing agent is mixed at the time of use with the dye composition.

23. The method of claim 21 wherein the oxidizing agent is applied to the fibers in the form of an oxidizing composition simultaneously or sequentially with the dye composition.

24. Multi-compartment device or "kit" for multi-compartment dyeing, in which a first compartment contains a composition as defined in any one of claims 1 to 15 and a second compartment contains an oxidizing composition.

25. Azo cationic compounds of formula (I) as defined according to any one of claims 1 to 10.