EP1399425A1

EP1399425A1 - Dyeing composition for keratinous fibres comprising a particular dicationic diazo dye

Info

Publication number: EP1399425A1
Application number: EP02748945A
Authority: EP
Inventors: Laurent Vidal; Hervé David
Original assignee: LOreal SA
Current assignee: LOreal SA
Priority date: 2001-06-11
Filing date: 2002-06-10
Publication date: 2004-03-24
Also published as: CN1541207A; US20040244123A1; FR2825703A1; KR20040003063A; MXPA03011339A; JP2005501134A; FR2825703B1; US7001436B2; CN100429203C; MX247992B; WO2002100834A1; BR0210995A

Abstract

The invention concerns a dyeing composition for keratinous fibres, in particular human keratinous fibres and more particularly hair, comprising a dicationic diazo dye of formula (I), as well as the dyeing composition using same. The invention also concerns the novel compounds of formula (I).

Description

COMPOSITION FOR DYEING KERATINIC FIBERS COMPRISING A PARTICULARLY DIAZOIC DYE

The subject of the invention is a composition for dyeing keratin fibers, in particular human keratin fibers and more particularly hair, containing a particular dicationic diazo dye, as well as the process for dyeing keratin fibers using such a composition.

Another subject of the invention is new diazo dicationic 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 belonging to the class of benzene nitrates, anthraquinones, nitropyridines, azo, indoamines, azines or triarylmethanes.

The resulting colorings are colorations. particularly chromatic which are however temporary or semi-permanent because the nature of the interactions which bind the direct dyes to the keratinous fiber, and their desorption from the surface and or from the core of the fiber are responsible for their weak dyeing power and their bad behavior washing or sweating. 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 makes them generally 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 is not colored 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 a very wide range of colors, in particular very chromatic, without forgetting the so-called "fundamental" shades such as blacks and browns.

These aims are achieved with the present invention which relates to a composition for dyeing keratin fibers, in particular human keratin fibers such as the hair, comprising at least one diazo dicationic dye of formula (I) below:

Formula (I) in which n represents 0 or 1, - W- _! and W _5ι independently of one another, represent a heteroaromatic radical of / formulas (II) and (III) below:

(he) (III)

W ₃ represents an oxygen atom, a radical NR ₁ , a group -NR ₁₅ -W ₆ - NR ₁₆ -, a group -NR ₁₆ -W ₆ -O-, a group -OW ₆ -O-, a radical W ₆ , a carbonyl radical,

W ₂ and W ₄ represent, independently of one another, a carbon, pyridine or pyridazinyl aromatic group of formula (IV)

(IV)

W ₆ represents a 5 or 6-membered aromatic or heteroaromatic group of formula (V):

in which

- m represents 0 or 1, Xi represents a nitrogen atom or a CR ₅ radical,

- X ₂ represents a nitrogen atom or a CR ₆ radical,

- X ₃ represents a nitrogen, carbon atom or a CR ₁₈ radical,

- ₄ represents a nitrogen, carbon atom or a CR ₁₉ radical, - X ₅ represents a nitrogen, carbon atom or a CR ₂₀ radical,

- X ₆ represents a nitrogen, carbon atom or a CR ₂₁ radical,

Zi represents an oxygen or sulfur atom or an NR ₈ radical,

Z ₂ represents a nitrogen atom or a radical CR ₉ ,

- Z ₃ represents a nitrogen atom or a CR12 radical, - Z ₄ represents a nitrogen atom or a CR ₁₃ radical,

the bond a of the 5-membered cationic cycle of formula (II) is linked to the azo group of formula (I),

- the bond b of the 6-membered cationic cycle of formula (III) is linked to the azo group of formula (I), - it being understood that when X ₃ to X ₆ represent a carbon atom, then they are linked to W ₂ or W ₄ ,

- it being understood that formula (V) does not contain more than three nitrogen atoms,

- it being understood that when the formula (V) contains three nitrogen atoms, they are not contiguous, - Ri, R ₂ and R ₈ represent, independently of one another, a linear or branched d-Cs alkyl radical , optionally substituted by one or more radicals chosen from hydroxy, CC ₂ alkoxy, (poly) - C ₂ -C alkoxy, amino, (di) alkylamino CC ₂ , carboxy or sulfonic radicals; a phenyl radical optionally substituted by one or more radicals chosen from hydroxy, CC ₂ alkoxy, (poly) - C ₂ -C alkoxy, amino, (di) alkylamino CC ₂ , carboxy, sulfonic or an atom halogen such as chlorine, fluorine or bromine,

R3, R, R5, Rβ, R7, Rg, RlOi R11 »Rl2 _> l3 1 Rl _> Rl5, l6, Rl7ι is, 19, R20 e

R ₂₁ represent, independently of each other, a hydrogen atom, a linear or branched C Cι ₆ hydrocarbon chain, which may be saturated or unsaturated, one or more carbon atoms of the carbon chain of which may be replaced by an oxygen, nitrogen or sulfur atom or by an SO ₂ group, and the carbon atoms of which may be, independently of one another, substituted by one or more halogen atoms; R ₃ , R, R5, Rβ, R7, R9, R10, Ru, R12, 13, R14, R15, Rie, R ₁₇ , Ris, R ₁₉ , R ₂ 0 and R ₂ ι having no peroxide bond, nor diazo or nitroso radicals,

- R ₇ with R ₉ , R ₀ with Ru and R ₁₂ with R ₁₃ can form a carbon aromatic ring, such as a phenyl,

- X is an organic or mineral anion.

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 ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₉ , R10, R11, R12 , Rι ₃ , R14, R15, Rie, R17, Rie, R19, R20 and R ₂₁ may 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 we can, for example, make the following transformations:

-CH— H can become r— o-H

can become

i - CH— CH ₃ can become S— 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. X is an organic or inorganic anion, for example chosen from a halide such as chloride, bromide, fluoride, iodide; a hydroxide; a sulfate; a hydrogen sulfate; an alkyl (CrC ₆ ) sulphate such as for example a methyl sulphate or an ethyl sulphate; an acetate; a tartrate; an oxalate; an alkyl (CC ₆ ) sulfonate such as methylsulfonate; an arylsulfonate substituted or unsubstituted by a dC ₄ alkyl radical such as for example a 4-toluylsulfonate.

R ₁₄ , R _{15 and} Rie represent, preferably and independently of one another, a hydrogen atom; a linear or branched CC ₆ alkyl radical, optionally substituted by one or more radicals chosen from hydroxy, CC ₂ alkoxy, (poly) hydroxy C ₂ -C alkoxy, amino, (di) alkylamino CC ₂ , ( poly) -hydroxya! kylamino, carboxy or sulfonic; a phenyl radical optionally substituted by one or more radicals chosen from hydroxy, C ₁ -C ₂ alkoxy, (poly) -C ₂ -C ₄ alkoxy, amino, (di) CC ₂ , carboxy, sulfonic or a d atom halogen such as chlorine, fluorine or bromine; a Cι-C ₄ alkylsulfonyl radical; an arylsulfonyl radical.

Rι, R ₁₅ and R ₁₆ represent, preferably and independently of one another, a hydrogen atom; a linear or branched CC ₃ alkyl radical, optionally substituted by one or more radicals chosen from hydroxy, C ₁ -C ₂ alkoxy, amino, CC ₂ (di) alkylamino, carboxy or sulphonic radicals; a phenyl radical optionally substituted by one or more radicals chosen from amino, (di) alkylamino C _r C ₂ or (poly) -hydroxyalkylamino radicals.

According to a particularly preferred embodiment, Rι, R ₁₅ and R ₁₆ represent, preferably and independently of one another, a hydrogen atom; a linear or branched C ₁ -C ₃ alkyl radical which may be substituted by alkoxy, amino, carboxy, sulfonyl such as methyl, ethyl, 2-hydroxyethyl, 2-aminoethyl; 1-carboxymethyl, 2-carboxyethyl, 2-sulfonylethyl, 2-methoxyethyl; a phenyl radical optionally substituted by one or more radicals chosen from amino, (di) alkylamino CC ₂ , (poly) -hydroxyalkylamino radicals. Rι, Rι ₅ and R ₆ are preferably chosen from a hydrogen atom; a methyl, 2-hydroxyethyl radical; a phenyl radical optionally substituted by an amino, (di) methylamino, (di) (2-hydroxyethyl) amino radical.

R ₃ , R ₄ , R ₅ , R ₆ , Rio, Ru, R12, R13, R17, is, ₁ 9, R20 and R ₂₁ represent, preferably and independently of one another, a hydrogen atom; a linear or branched CC ₄ alkyl radical, optionally substituted by one or more radicals chosen from hydroxy, CC ₂ alkoxy, (poly) hydroxy C ₂ -C ₄ alkoxy, amino, (di) alkylamino C _r C radicals ₂ , carboxy or sulfonic; a phenyl radical optionally substituted by one or more radicals chosen from hydroxy, C _r C ₂ alkoxy, (poly) hydroxy C ₂ -C ₄ alkoxy, amino, (di) C ₁ -C alkylamino C ₂ , carboxy, sulfonic or a halogen atom such as chlorine, fluorine or bromine; a carboxy radical; a sulfonylamino radical; a sulfonic radical; a C1-C2 alkoxy radical; a C ₂ -C ₄ (poly) hydroxyalkoxy radical; an amino radical; a CC ₂ (di) alkylamino radical; a C ₂ -C (poly) hydroxyalkylamino radical. More preferably, R ₃ , R ₄ , R ₅ , Re, Rio, Ru, Rι ₂ , R13, R17, Ris, R19, R20 and R ₂ represent a hydrogen atom, a CC ₄ alkyl radical optionally substituted by a or several radicals chosen from hydroxy, amino, (di) alkylamino Cι-C ₂ ; a carboxy radical; a CC ₂ alkoxy radical; an amino radical; a CC ₂ (di) alkylamino radical; a C ₂ -C ₄ (poly) hydroxyalkylamino radical.

According to a particularly preferred embodiment, R ₃ , R ₄ , R ₅ , R _6, R _10l R11, R12, R13, R17, Ris, R19, R20 and R ₂ ι represent a hydrogen atom, a methyl radical, phenyl, 2-hydroxymethyl, carboxy ,. a methoxy, ethoxy, 2-hydroxyethyloxy radical, an amino, methylamino, dimethylamino, 2-hydroxyethylamino radical. According to a particular embodiment, R ₇ and R ₉ represent, independently of one another, a hydrogen atom; a linear or branched C 1 -C ₄ alkyl radical, optionally substituted by one or more radicals chosen from hydroxy, C ₁ -C ₂ alkoxy, (poly) hydroxy C ₂ -C alkoxy, amino, (di) alkylamino CC ₂ , carboxy or sulfonic; a phenyl radical optionally substituted by one or more radicals chosen from hydroxy, Cι-C ₂ alkoxy, (poly) -hydroxy C ₂ -C ₄ alkoxy, amino, (di) alkylamino CC ₂ , carboxy, sulfonic or a halogen atom such as chlorine, fluorine or bromine; a carboxy radical; a sulfonylamino radical.

Among these substituents, R ₇ and R ₉ preferably represent a hydrogen atom, a phenyl radical, a C _r C alkyl radical optionally substituted by one or more radicals chosen from hydroxy, amino, (di) alkylamino radicals CC ₂ , carboxy.

According to a preferred embodiment, R ₇ and R ₉ preferably represent a hydrogen atom, a methyl, phenyl, 2-hydroxymethyl radical, a carboxy.

Ri, R ₂ and R ₈ preferably represent a CC ₄ alkyl radical optionally substituted by one or more radicals, chosen from hydroxy, C _r C ₂ alkoxy, amino, (di) alkylamino CC ₂ , carboxy, sulfonic radicals. According to a particularly preferred embodiment Ri, R ₂ and R ₈ preferably represents a methyl, ethyl, 2-hydroxyethyl, 1-carboxy ethyl, 2-carboxyethyl, 2-sulfonylethyl radical.

Among the groups of formulas (II) and (III), Wi and W ₅ preferably represent, independently of one another, a cationic group imidazolium, triazolium, thiazolium, pyridinium.

Among the groups of formulas (IV), W ₂ and W preferably represent, independently of one another, a phenyl or pyridyl group.

Among the groups of formulas (V), W ₆ preferably represents a phenyl, pyridyl, triazinyl, pyrimidinyl group.

W ₃ preferably represents a radical NRι, a group NRι ₅ -W ₆ - NRιe, a group W ₆ , in which Rι ₄ , Rι ₅ , Rie and W ₆ are as defined above, in particular according to the preferred modes.

The concentration of diazo diazo dye of formula (I) can vary from 0.001 to 5% by weight approximately relative to the total weight of the dye composition, and preferably from approximately 0.05 to 2%.

Among the diazo dicationic dyes of formula (I) according to the present invention, mention may in particular be made of the following compounds:

1, 3-dimethyl-2- [4- (1, 3-dimethyl- (imidazol-1 -ium) -2-ylazo) phenylamino] -phenylazo] - imidazol-1-ium.

1,4-Dimethyl -3- [4- (1,4-dimethyl - (triazol-4-ium) -3-ylazo) phenylamino] -phenylazo] - triazol-3-ium. 1-methyl-2- [4- (1-methyl- (pyridin-1-ium) -2-ylazo) phenylamino] -phenylazo] - pyridin -1- ium.

1-methyl-3- [4- (1-methyl- (pyridin-1 -ium) -3-ylazo) phenylamino] -phenylazo] - pyridin -1 - ium.

1, 3-dimethyl-2- [4- (1, 3-dimethyl- (imidazol-1-ium) -2-ylazo) phenyloxy] -phenylazo] - imidazol-1-ium.

1, 4-dimethyl -3- [4- (1, 4-dimethyl - (triazol-4-ium) -3-ylazo) phenyloxy] -phenylazo] -triazol- 3-ium. 1-methyl-2- [4- (1-methyl- (pyridin-1-ium) -2-ylazo) phenyloxy] -phenylazo] - pyridin -1-ium. 1-methyl-3- [4- (1-methyl- (pyridin-1 -ium) -3-ylazo) phenyloxy] -phenylazoj- pyridin -1 -ium.

1,3-dimethyl-2- [4- [4- (1,3-dimethyl- (imidazol-1-ium) -2-ylazo) phenylamino] - phenylamino] -phenylazo] -imidazol-1-ium. 1, 4-dimethyl -3- [4- [4- (1, 4-dimethyl - (triazol-4-ium) -3-ylazo) phenylamino] -phenylamino] - phenylazo] -triazol-3-ium.

1-methyl-2- [4- [4- (1-methyl- (pyridin-1-ium) -2-ylazo) phenylamino] -phenylamino] - phenylazoj-pyridin -1-ium.

1-methyl-3- [4- [4- (1-methyl- (pyridin-1 -ium) -3-ylazo) phenylamino] -phenylamino] - phenylazo] - pyridin -1 -ium.

Synthesis of the compounds of the invention The methods for obtaining said compounds are based on reactions already well known in the literature and reported for example in the following documents: US-3 291788, GB-1186 753, US-3271 383, EP-0757 083 and US-5708 151.

- A first synthetic principle consists of starting from an amino heterocycle with 5 or 6 members, such as 2-aminoimidazole, 3-aminotriazole, 2-aminothiazole, 3-aminothiadiazole, 2-aminopyridine or 2-aminopyridazine , which is reacted with sodium nitrite in a polar protic acid solvent, such as acetic acid or hydrochloric acid, at a temperature generally between -

10 ° C and 50 ° C, to generate the corresponding diazonium salt. This then reacts with an aromatic derivative of formulas (A) or (B) described below and in which W3, X1, X2 have the meanings previously described according to the invention.

These aromatic derivatives are obtained by applying the conventional reactions of the literature SNAr (aromatic nucleophilic substitution), SN1 (nucleophilic substitution 1) and SN2 (nucleophilic substitution 2). The resulting condensation product then reacts with an alkylating agent such as a dialkyl sulfate or an alkyl halide in a polar solvent and at a temperature between 0 ° C and 150 ° C, preferably between 20 ° C and 100 ° C. The 5- or 6-membered heterocyclic part is thus quarternized and the azo obtained is cationic. With a 5-link heterocycle

With a 6-member heterocycle

- A second synthesis principle consists in reacting a quarternized heterocyclic azo 2 on one of the nitrogen atoms of the heterocycle in series 4-methoxyphenylazo with an aniline derivative or a heteroaromatic amine 3 in a protic solvent at a temperature comprised between 25 ° C and 150 ° C. In particular, the quarternary heterocycle can be an imidazolium, triazolium, thiazolium, thiadiazolium, oxazolium. The same synthesis principle can be applied in a 6-membered heterocyclic series, such as pyridinium or pyridazinium, which makes it possible to obtain the compounds of formula 5 ^ from Pazoic.

protic solvent

The cationic azo derivative 4 then reacts with a diazonium salt derived from a 5- or 6-membered heterocycle (vacuum above) at a temperature between -10 ° C and 25 ° C to yield the intermediate mono-cationic di-azo compound which reacts with an alkylating agent such as a dialkyl sulfate or an alkyl halide in a polar solvent and at a temperature between 0 ° C and 150 ° C, preferably between 20 ° C and 100 ° C to lead to the di-cationic di-azo compound 5. The same synthesis principle can be applied in a 6-membered heterocyclic series, starting from the compound _ to arrive at the compound 5 \ In the formulas of the synthetic scheme, Me denotes a CH3 radical.

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 neutral benzenic direct dyes, acid or cationic, neutral azo direct dyes which are acidic or cationic , quinone direct dyes and in particular neutral, acidic or cationic anthraquinone dyes, azine direct dyes, methine direct dyes, triarylmethane direct dyes, indoamine direct dyes and natural direct dyes.

Among the benzenic direct dyes which can be used according to the invention, mention may be made in particular of the following compounds:

-1, 4-diamino-2-nitrobenzene

-1-amino-2 nitro-4-β- hydroxyethylaminobenzene '

-1-2-amino-nitro-4-bis (β-hydroxyethyl) -aminobenzene

-1,4-Bis (β-hydroxyethylamino) -2-nitrobenzene

-1-β-hydroxyethylamino-2-nitro-4-bis- (β-hydroxyethylamino) -benzene

-1-β-hydroxyethylamino-2-nitro-4-aminobenzene

-1-β-hydroxyethylamino-2-nitro-4- (ethyl) (β-hydroxyethyl) -aminobenzene

-1-amino-3-methyl-4-β-hydroxyethylamino-6-nitrobenzene

-1-amino-2-nitro-4-β-hydroxyethylamino-5-chlorobenzene

-1, 2-Diamino-4-nitrobenzene

-1-amino-2-β-hydroxyethylamino-5-nitrobenzene

-1,2-Bis- (β-hydroxyethylamino) -4-nitrobenzene

-1-amino-2-tris (hydroxymethyl) methylamino-5-nitrobenzene

-1-Hydroxy-2-amino-5-nitrobenzene

-1-Hydroxy-2-amino-4-nitrobenzene

-1-Hydroxy-3-nitro-4-aminobenzene

-1-Hydroxy-2-amino-4,6-dinitrobenzene

-1-β-hydroxyethyloxy-2-β-hydroxyethylamino-5-nitrobenzene

-1-Methoxy-2-β-hydroxyethylamino-5-nitrobenzene

-1 ~ β-hydroxyethyloxy-3-methylamino-4-nitrobenzene

-1-β, γ-dihydroxypropyloxy-3-methylamino-4-nitrobenzene -1-β-hydroxyethylamino-4-β, γ-dihydroxypropyloxy-2-nitrobenzene -1-β, γ-dihydroxypropylamino-4-trifluoromethyl-2-nitrobenzene -1-β-hydroxyethylamino-4-trifluoromethyl-2-nitrobenzene -1 -β-hydroxyethylamino-3-methyl-2-nitrobenzene -1 -β-aminoethylamino-5-methoxy-2-nitrobenzene -1-Hydroxy-2-chloro-6-ethylamino-4-nitrobenzene -1-Hydroxy-2-chloro -6-amino-4-nitrobenzene -1-Hydroxy-6-bis- (β-hydroxyethyl) -amino-3-nitrobenzene -1 -β-hydroxyethylamino-2-nitrobenzene -1-Hydroxy-4-β-hydroxyethylamino-3 nitrobenzene.

Among the azo direct dyes which can be used according to the invention, mention may be made of the cationic azo dyes described in patent applications WO 95/15144, WO-95/01772 and EP-714954, the content of which forms an integral part of the invention. Among these compounds, the following dyes may be particularly mentioned: 1,3-dimethyl-2 chloride - [[4- (dimethylamino) phenyl] azo] -1H-lmidazolium, 1,3-dimethyl-2- chloride [(4-aminophenyl) azo] -1 H-lmidazolium, - 1-methyl-4-methyl sulfate - [(methylphenylhydrazono) methyl] -pyridinium.

One can also cite among the azo direct dyes the following dyes, described in the COLOR INDEX INTERNATIONAL 3 ^rd edition:

-Disperse Red 17

-Acid Yellow 9

-Acid Black 1 -Basic Red 22

-Basic Red 76

-Basic Yellow 57

-Basic Brown 16

-Acid Yellow 36 -Acid Orange 7

-Acid Red 33

-Acid Red 35

-Basic Brown 17 -Acid Yellow 23 -Acid Orange 24 -Disperse Black 9.

Mention may also be made of 1- (4'-aminodiphenylazo) -2-methyl-4bis- (β-hydroxyethyl) aminobenzene and 4-hydroxy-3- (2-methoxyphenylazo) -1-naphthalene sulfonic acid.

Among the quinone direct dyes, the following dyes may be mentioned:

-Disperse Red.15 -Solvent Violet 13 -Acid Violet 43

-Disperse Violet 1

-Disperse Violet 4

-Disperse Blue 1

-Disperse Violet 8 -Disperse Blue 3

-Disperse Red 11

-Acid Blue 62

-Disperse Blue 7

-Basic Blue 22 -Disperse Violet 15

-Basic Blue 99 as well as the following compounds:

-1-N-4-hydroxyanthraquinone méthylmorpholiniumpropylamino-

-1-Aminopropylamino-4-methylaminoanthraquinone -1-Aminopropylaminoanthraquinone

-5-β-hydroxyethyl-1,4-diaminoanthraquinone

-2-Aminoéthylaminoanthraquinone

-1,4-Bis- (β, γ-dihydroxypropylamino) anthraquinone.

Among the azine dyes, the following compounds may be mentioned: -Basic Blue 17 -Basic Red 2. Among the triarylmethane dyes which can be used according to the invention, the following compounds may be mentioned: -Basic Green 1 -Acid blue 9 -Basic Violet 3 -Basic Violet 14 -Basic Blύe 7 -Acid Violet 49 -Basic Blue 26 -Acid Blue 7

Among the indoamine dyes which can be used according to the invention, mention may be made of the following compounds: -2-β-hydroxyethlyamino-5- [bis- (β-4'-hydroxyethyl) amino] anilino-1,4-benzoquinone -2-β -hydrpxyethylamino-5- (2'-methoxy-4'-amino) anilino-1, 4-benzoquinone

-3-N (2'-Chloro-4'-hydroxy) phenyl-acetylamino-6-methoxy-1, 4-benzoquinone imine -3-N (3 ^, -Chloro-4'-methylamino) phenyl-ureido-6- methyl-1,4-benzoquinone imine -3- [4'-N- (Ethyl, carbamylmethyl) -amino] -phenyl-ureido-6-methyl-1,4-benzoquinone imine.

Among the natural direct dyes which can be used according to the invention, mention may be made of lawsone, juglone, alizarin, purpurin, carminic acid, kermesic acid, purpurogallin, protocatechaldehyde, indigo, isatin , curcumin, spinulosin, apigenidine. It is also possible to use extracts or decoctions containing these natural dyes and in particular poultices or extracts based on henna.

The additional direct dye (s) different from those of formula (I) of the present invention preferably represent from 0.001 to 20% by weight approximately of the total weight of the composition and even more preferably from 0.005 to 10% by weight approximately.

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 among hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulfates, peracids and enzymes among which there may be mentioned peroxidases, 2-electron oxidoreductases such than uricases and 4-electron oxygenases like laccases. 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, 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-methylenediamine , N- (ethyl, β-hydroxyethyl) paraphenylenediamine, the N- (β, γ- dihydroxypropyl) paraphenylenediamine, N- (4'-aminophenyl) paraphenylenediamine, N-phenyl paraphenylenediamine, 2-β-hydroxyethyloxy paraphenylenediamine, 2-β-acetylaminoethyloxy paraphenylenedaphenylenediamine methoxyethyl) paraphenylenediamine, 4-aminophenyl 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 para-phenylenediamine, 2,6-dimethyl para-phenylenediamine, 2,6-diethyl para-phenylenediamine, 2,3-dimethyl para-phenylenediamine, N, N-bis- (β-hydroxyethyl) para-phenylenediamine, 2-chloro para-phenylenediamine, 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. Among the pyrimidine derivatives, mention may be made of the compounds described, for example, in patents DE 2359399; JP 88-169571; 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 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-3,7-diamine; pyrazolo- [1,5-a] -pyrimidine-3,5-diamine; 2,7-dimethyl pyrazolo- [1,5-a] -pyrimidin-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-3,7-diamine, 2,6-dimethyl pyrazθιθ- [1,5-a] -pyrimidine-3,7-diamine, la 2, 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 3 843 892, DE 4 133957 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-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, meta- aminophenols, 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, α-naphthol, 2 methyl-1-naplTιθl, 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 ranging from 0.001 to 10% by weight approximately of the total weight of the dye composition and more preferably from 0.005 to 6%. The oxidation base or bases are present in an amount preferably ranging from 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 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 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 organic solvents may be present in proportions ranging preferably from 1 to 40% by weight approximately relative to the total weight of the dye composition, and even more preferably from 5 to 30% by weight approximately.

The 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, mineral or organic thickening agents, and in particular anionic, cationic, nonionic and amphoteric associative polymers, 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.

The adjuvants mentioned above 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 dye composition according to the invention are not, or not substantially, affected by the or the additions 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 and their derivatives, sodium or potassium hydroxides and the compounds of formula (III) below:

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

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 used in the presence of an oxidizing agent which causes discoloration of the fiber (direct lightening dye). 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.

The invention also relates to an oxidation dyeing process 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.

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 oxidation dyeing or lightening 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 approximately 5 to 30 minutes, 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-2586 913 in the name of the applicant.

Finally, the invention also relates to the dicationic diazo dyes of formula (I) as defined above.

The example which follows serves to illustrate the invention without, however, being limiting in nature.

EXAMPLE This example illustrates the preparation of a compound according to the invention of the following formula:

This-

Ci) (2)

6 g of compound (1), 4.3 ml of 12 N hydrochloric acid, 1.9 ml of lactic acid, 11 ml of a mixture consisting of ice and water were loaded into a fully equipped flask. The reaction medium was then cooled to 0 ° C. A solution consisting of 4.3 ml of water and 1.22 g of sodium nitrite was then added dropwise slowly over a period of 20 minutes. The reaction medium was left for one hour at 0 ° C. with stirring. In 20 minutes, a solution consisting of 6.4 ml of water and 1.2 g of imidazole was added. The reaction mixture was then left at room temperature for 2 hours. The pH of the reaction medium was brought to 7.8 with a 6N sodium hydroxide solution. The reaction mixture was then filtered through sintered glass. The precipitate was washed with methanol. The colored solution was then concentrated, and the solid obtained chromatographed on a column of silica gel (eluent MeOH / Dichloromethane / buffer mixture: 9/1/1). The powder obtained after chromatography was taken up with a few milliliters of water and then dried. After purification, a bright dark green powder was obtained.

The UV absorption characteristics of this product are as follows: UV (H ₂ O / MeOH / AcO ^" NH ₄ ⁺ ) λ _ma χ = 538 nm Analyzes :

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

4.07 (s-6H); 7.27 (s-2H); 7.31 (d-2H, J = 9 Hz); 7.40 (d-2H, J = 8.78 Hz); 7.59 (s-

2H); 7.93 (d-2H, J = 8.74 Hz); 7.99 (d-2H, J = 8.96 Hz).

iante

(D

2 HCOO-

0.094 g of compound (1), 2 ml of DMF and 0.92 ml of dimethyl sulphate were charged at room temperature overnight in a fully equipped flask. The reaction medium was then concentrated under vacuum and then purified by semi-preparative liquid chromatography. After purification, a bright dark green powder was obtained.

The UV absorption characteristics of this product are as follows: UV (H ₂ O / MeOH / AcO ^" NH ₄ ⁺ ) λ _m a _χ = 568 nm

Analyzes :

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

4.15 (s-9H); 7.52 (d-4H, J = 8.96 Hz); 7.72 (s-4H); 8.16 (d-4H, J = 8.93 Hz)

The dye obtained dyed the hair in a purple shade.

Claims

1. Composition for dyeing keratin fibers, in particular human keratin fibers and more particularly hair, comprising at least one dicationic diazo dye of formula (I) below:

in which

-. n represents 0 or 1,

- Wi and W ₅ , independently of one another, represent a heteroaromatic radical of formulas (II) and (III) below:

(II) (III)

W ₃ represents an oxygen atom, a radical NRι ₄ , a group -NRι ₅ -W ₆ - NRιe-, a group -NR ₁₆ -W ₆ -O-, a group -OW ₆ -O-, a radical W ₆ , a carbonyl radical,

(IV)

in which

- m represents 0 or 1, - Xi represents a nitrogen atom or a CR ₅ radical,

- X ₂ represents a nitrogen atom or a CR ₆ radical,

- X ₃ represents a nitrogen, carbon atom or a CR ₁₈ radical,

- X ₄ represents a nitrogen, carbon atom or a CR ₁₉ radical,

- X ₅ represents a nitrogen, carbon atom or a CR ₂₀ radical, - X ₆ represents a nitrogen, carbon atom or a CR ₂ ι radical,

Zi represents an oxygen or sulfur atom or an NR ₈ radical,

Z ₂ represents a nitrogen atom or a CRg radical,

Z ₃ represents a nitrogen atom or a CRι ₂ radical,

- Z ₄ represents a nitrogen atom or a CRι ₃ radical, - the bond a of the 5-membered cationic cycle of formula (II) is linked to the azo group of formula (I),

- bond b of the 6-membered cationic cycle of formula (III) is linked to the azo group of formula (I),

- it being understood that when X ₃ to X ₆ represent a carbon atom, then they are linked to W ₂ or W,

- it being understood that when the formula (V) contains three nitrogen atoms, they are not contiguous,

- RL R ₂ and R ₈ independently of one another represent a Cι-C ₈ alkyl radical, linear or branched, optionally substituted by one or more radicals chosen from hydroxy, CC ₂ alkoxy (poly) radicals - C ₂ -C ₄ hydroxyalkoxy, amino, (di) alkylamino CC ₂ , carboxy or sulfonic; a phenyl radical optionally substituted by one or more radicals chosen from hydroxy, CC ₂ alkoxy, (poly) - C ₂ -C ₄ hydroxyalkoxy, amino, CC ₂ (di) alkylamino, carboxy, sulfonic or a halogen atom,

R ₃ , R ₄ , Rβ, Rβ, R7, R9, R10, R11, R12, 13, R14, R15, Rie, R17, Rie, R19, R20 and R ₂ ι represent, independently of one another, a hydrogen atom, a linear or branched C Cι ₆ hydrocarbon chain, which may be saturated or unsaturated, one or more carbon atoms of the carbon chain of which may be replaced by an oxygen, nitrogen or sulfur atom or by an SO ₂ group, the carbon atoms of which may be, independently of one another, substituted by one or more halogen atoms; R ₃ , R, R ₅ , R ₆ , R7, R9, R10, Ru, R12, R13, Rι ₄ , R15, Rtβ,

R ₁₇ , Ris, R19, R ₂ o and R ₂₁ containing no peroxide bond, nor diazo or nitroso radicals, - R ₇ with R ₉ , R1 ₀ with Ru and Rι ₂ with Rι ₃ can form a carbon aromatic ring , such as a phenyl, - X is an organic or inorganic anion.

2. Composition according to claim 1 in which R _i4> R _i5 and R ₁₆ represent, independently of one another, a hydrogen atom; a linear or branched Cι-C ₆ alkyl radical, optionally substituted by one or more radicals chosen from hydroxy, C ^ - ₂ alkoxy, (poly) -hydroxy C ₂ -C alkoxy, amino, (di) alkylamino in CC ₂ , (poly) -hydroxyalkylamino, carboxy or sulfonic; a phenyl radical optionally substituted by one or more radicals chosen from hydroxy, C ₁ -C ₂ alkoxy, (poly) -C ₂ -C ₄ alkoxy, amino, (di) C ₁ -C ₂ alkylamino, carboxy, sulfonic or an atom halogen such as chlorine, fluorine or bromine; a CC ₄ alkylsulfonyl radical; an arylsulfonyl radical.

3. Composition according to claim 2 in which Rι, Rι ₅ and Rι ₆ represent, independently of one another, a hydrogen atom; a linear or branched C _r C ₃ alkyl radical, optionally substituted by one or more radicals chosen from hydroxy, C _r C ₂ alkoxy, amino, CC ₂ (di) alkylamino, carboxy or sulphonic radicals; a phenyl radical optionally substituted by one or more radicals chosen from amino, (di) alkylamino in CC ₂ or (poly) - hydroxyalkylamino radicals.

4. Composition according to claim 3 wherein Rι ₄ , R ₁ and R ₆ represent, independently of one another, a hydrogen atom; a linear or branched CC ₃ alkyl radical, which can be substituted by an alkoxy, amino, carboxy, sulfonyl; a phenyl radical optionally substituted by one or more radicals chosen from amino, (di) alkylamino CC ₂ , (poly) -hydroxyalkylamino radicals.

5. Composition according to claim 4 in which R, Rι ₅ and R ₁₆ are chosen from a hydrogen atom, a methyl, ethyl, 2-hydroxyethyl, 2-aminoethyl radical; 1-carboxymethyl, 2-carboxyethyl, 2-sulfonylethyl , 2-methoxyethyl; a phenyl radical optionally substituted by an amino, (di) methylamino, (di) (2-hydroxyethyl) amino radical.

6. Composition according to claim 5 in which Rι ₄ , R15 and Rι ₆ are chosen from a hydrogen atom; a methyl radical, 2-hydroxyethyl; a phenyl radical optionally substituted by an amino, (di) methylamino, (di) (2-hydroxyethyl) amino radical.

7. Composition according to any one of claims 1 to 6 wherein R ₃ , R ₄ , R ₅ , R ₆ , R o, Ru, R12, R13, R17, Ris, R19, R20 and R ₂ ι represent, independently one from the other, a hydrogen atom; a linear or branched CC ₄ alkyl radical, optionally substituted by one or more radicals chosen from hydroxy, Cι-C ₂ alkoxy, (poly) -hydroxy C ₂ -C ₄ alkoxy, amino, (di) alkylamino Cι radicals -C ₂ , carboxy or sulfonic; a phenyl radical optionally substituted by one or more radicals chosen from hydroxy, CC ₂ alkoxy, (poly) hydroxy C ₂ -C ₄ alkoxy, amino, (di) alkylamino CC ₂ , carboxy, sulfonic or an atom d halogen such as chlorine, fluorine or bromine; a carboxy radical; a sulfonylamino radical; a sulfonic radical; a C1-C2 alkoxy radical; a C ₂ -C (poly) hydroxyalkoxy radical; an amino radical; a dC ₂ (di) alkylamino radical; a C ₂ -C ₄ (poly) hydroxyalkylamino radical.

8. Composition according to Claim 7, in which R ₃ , R ₄ , R ₅ , R _6, Rι ₀ , Ru, Rι ₂ , Rι ₃ , R17, Rie, R19, R20 and R ₂ ι represent a hydrogen atom, a CC ₄ alkyl radical optionally substituted by one or more radicals chosen from hydroxy, amino, (di) alkylamino radicals CC ₂ ; a carboxy radical; a C1-C2 alkoxy radical; an amino radical; a CC ₂ (di) alkylamino radical; a C ₂ -C (poly) hydroxyalkylamino radical.

9. Composition according to claim 8, in which R ₃ , R, R ₅ , R _6, R ₁₀ ,

R11, R12, R13, R17, is, R19, R20 and R ₂₁ represent a hydrogen atom, a methyl, phenyl, 2-hydroxymethyl radical, a carboxy, a methoxy, ethoxy, 2-hydroxyethyloxy radical, an amino radical, methylamino, dimethylamino, 2-hydroxyethylamino.

10. Composition according to any one of the preceding claims, in which R ₇ and R ₉ represent, independently of one another, an atom. hydrogen; a linear or branched C _r C ₄ alkyl radical, optionally substituted by one or more radicals chosen from hydroxy, Cι-C ₂ alkoxy, (poly) -hydroxy C ₂ -C ₄ alkoxy, amino, (di) alkylamino radicals C ₂ , carboxy or sulfonic; a phenyl radical optionally substituted by one or more radicals chosen from hydroxy, CC ₂ alkoxy, (poly) hydroxy C ₂ -C ₄ alkoxy, amino, (di) alkylamino CC ₂ , carboxy, sulfonic or an atom d 'halogen; a carboxy radical; a sulfonylamino radical.

11. The composition as claimed in claim 10 in which R ₇ and R ₉ represent a hydrogen atom, a phenyl radical, a CC alkyl radical optionally substituted by one or more radicals chosen from hydroxy, amino and (di) alkylamino radicals. C ₁ -C2, carboxy.

12. Composition according to claim 11 in which R and R ₉ represent a hydrogen atom, a methyl, phenyl, 2-hydroxymethyl radical, a carboxy.

13. Composition according to any one of the preceding claims, in which Ri, R ₂ and R ₈ represent a CC ₄ alkyl radical optionally substituted by one or more radicals chosen from hydroxy, C ₁ -C ₂ alkoxy, amino, (di) radicals. CC ₂ alkylamino, carboxy, sulfonic.

14. Composition according to Claim 13, in which R, R ₂ and R ₈ represent a methyl, ethyl, 2-hydroxyethyl, 1-carboxymethyl, 2-carboxyethyl, 2-sulfonylethyl radical.

15. Composition according to any one of the preceding claims, in which \ N ^ and W ₅ represent, independently of one another, a cationic group imidazolium, triazolium, thiazolium, pyridinium.

16. Composition according to any one of the preceding claims, in which W ₂ and W ₄ represent, independently of one another, a phenyl or pyridyl group.

17. Composition according to any one of the preceding claims, in which W ₆ represents a phenyl, pyridyl, triazinyl or pyrimidinyl group.

18. Composition according to any one of the preceding claims, in which W ₃ represents an NR radical _. , a group NR ₁₅ -W ₆ -NR ₆ , a group W ₆ .

19. Composition according to any one of the preceding claims, characterized in that the diazo diazo dyes of formula (I) are chosen from the group formed by the following compounds: 1,3-dimethyl-2- [4- (1,3-dimethyl- (imidazol-1-ium) -2-ylazo) phenylamino] -phenylazo] - imidazol-1-ium.

1,4-dimethyl -3- [4- (1,4-dimethyl - (triazol-4-ium) -3-ylazo) phenylamino] -phenylazo] - 'triazol-3-ium. 1-methyl-2- [4- (1-methyl- (pyridin-1 -ium) -2-ylazo) phenylamino] -phenylazo] - pyridin -1 - ium.

1,4-dimethyl -3- [4- (1,4-dimethyl - (triazol-4-ium) -3-ylazo) phenyloxy] -phenylazo] -triazol-

3-ium.

1-methyl-2- [4- (1-methyl- (pyridin-1 -ium) -2-ylazo) phenyloxy] -phenylazo] - pyridin -1 -ium. 1-methyl-3- [4- (1-methyl- (pyridin-1-ium) -3-ylazo) phenyloxy] -phenylazo] - pyridin -1-ium.

1, 3-dimethyl-2- [4- [4- (1, 3-dimethyl- (imidazol-1 -ium) -2-ylazo) phenylamino] - phenylamino] -phenylazo] -imidazol-1-ium.

1, 4-dimethyl -3- [4- [4- (1, 4-dimethyl - (triazol-4-ium) -3-ylazo) phenylamino] -phenylamino] - phenylazoj-triazol-3-ium.

1-methyl-3- [4- [4- (1-methyl- (pyridin-1-ium) -3-ylazo) phenylamino] -phenylamino] - phenylazo] -? pyridin -1-ium.

20. Composition according to any one of the preceding claims, in which the dicationic diazo dye (s) of formula (I) are present at a concentration ranging from 0.001 to 5% and preferably from 0.05 to 2% by weight relative to the total weight of the composition.

21. Composition according to any one. of claims 1 to 20 further comprising an oxidation base.

22. Composition according to Claim 21, in which the oxidation base is chosen from paraphenylenediamines, bis- phenylalkylenediamines, para-aminophenols, ortho-aminophenols, heterocyclic bases, and their addition salts with an acid.

23. Composition according to any one of claims 21 or 22 in which the oxidation base or bases are present in an amount ranging from 0.001 to 10%, preferably from 0.005 to 6%.

24. Composition according to any one of claims 1 to 23 comprising at least one coupler.

25. The composition as claimed in claim 24 in which the coupler is chosen from metaphenylenediamines, meta-aminophenols, metadiphenols, naphthalene couplers and heterocyclic couplers and their addition salt with an acid.

26. Composition according to any one of the preceding claims, further comprising at least one direct dye different from those of formula (I), chosen from neutral benzenic, acid or cationic direct dyes, neutral azo acid or cationic direct dyes, quinone direct dyes and in particular neutral, acidic or cationic anthraquinone dyes, azine direct dyes, meth / nique direct dyes, triarylmethane direct dyes, indoamine direct dyes and natural direct dyes.

27. Composition according to any one of the preceding claims, further comprising an oxidizing agent, preferably hydrogen peroxide.

28. A process for dyeing 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 to 20 is applied to the fibers.

29. The method of claim 28 wherein the dye composition contains an oxidizing agent.

30. The method of claim 29 wherein the oxidizing agent is mixed at the time of use with the dye composition.

31. A method according to any one of claims 29 or 30 in which the oxidizing agent is applied to the fibers in the form of an oxidizing composition simultaneously or sequentially with the dye composition.

32. 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 20, further comprising at least one oxidation base and optionally at least one coupler, in the presence of an oxidizing agent.

33. The method of claim 32 wherein the oxidizing agent is mixed at the time of use with the dye composition.

34. The method of claim 32 wherein the oxidizing agent is applied to the fibers in the form of an oxidizing composition simultaneously or sequentially with the dye composition.

35. 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 26 and a second compartment contains an oxidizing composition.

36. Dicationic diazo compounds of formula (I) as defined according to any one of claims 1 to 19.