FR2895243A1 - Composition, useful for dyeing keratin fibres, comprises in a dyeing medium tetraazapentamethine compound and direct dye containing exonuclear quaternary ammonium group - Google Patents

Abstract

Composition (A) for dyeing keratin fibres, comprises in a dyeing medium: at least one tetraazapentamethine compound (I); and at least one direct dye containing at least one exonuclear quaternary ammonium group. Composition (A) for dyeing keratin fibres, comprises in a suitable dyeing medium: at least one tetraazapentamethine compound (I) of formula (W1-N1=N-C(R0)=N-N2=W2); and at least one direct dye containing at least one exonuclear quaternary ammonium group. W1a cationic heteroaromatic radical of formula (II) or (III); W2a heteroaromatic radical of formula (IV) or (V); Z0radical CR2, N or a radical NR21; Z1O, S or NR9; Z2N or CR10; Z3N or CR11; Z4N or CR12; Z5N or CR13; Z6N or CR14; Z7O, S or CR15; Z8N or CR16; Z9N or CR17; Z10N or CR18; Z11N or CR19; Z12N or CR20; Z13CR6, N or NR22; R2, R6, R10, R16H, 1-4C alkyl (optionally substituted with 1-3 OH, 1-2C alkoxy, 2-4C (poly)hydroxyalkoxy, amino, 1-2C (di)alkylamino, carboxyl or sulfonic radicals), phenyl or sulfonylamino radical; R1, R4, R5, R7, R9, R15, R21, R221-8C alkyl (optionally substituted with 1-3 OH, 1-2C alkoxy, 2-4C (poly)hydroxyalkoxy, amino, 1-2C (di)alkylamino, carboxyl and sulfonic radicals); either R0, R3, R8, R11-R14, R17-R20H, 1-16C hydrocarbon-based chain, optionally saturated with 1-3 unsaturations and optionally substituted with 1-3 OH, 1-2C alkoxy, 2-4C (poly)hydroxyalkoxy, amino, 1-2C (di)alkylamino, carboxyl, sulfonic, sulfonylamino or 2-4C (poly)hydroxyalkylamino or halo ( Cl, F or Br), phenyl (optionally substituted with 1-3 OH, 1-2C alkoxy, 2-4C (poly)hydroxyalkoxy, amino, 1-2C (di)alkylamino, carboxyl, sulfonic, sulfonylamino or 2-4C (poly)hydroxy-alkylamino or halo (Cl, F or Br)), heteroaryl (pyrazolyl, pyrrolyl, imidazolyl, thiazolyl, oxazolyl, triazolyl, pyridyl, pyrimidinyl, triazinyl, pyrazinyl or pyridazinyl radicals), this hydrocarbon based chain interrupted with 1-2 O, N, S or SO2 radical (it is understood that R0, R3, R8, R11-R14, R17-R20 are peroxide bond, diazo or nitroso radicals); or R2+R10, R11+R12, R6+R16, R17+R185-6 membered carbon based aromatic ring, optionally substituted with 1-2 OH, amino, (di)(1-2C)alkylamino, 1-2C alkoxy or 2-4C (poly)hydroxyalkylamino radicals; and X : organic or mineral anion. Provided that the rings (II)-(IV) comprise not more than three N atoms and that two of the three N atoms be contiguous, the bond 5-membered cationic heteroaromatic radical (II) is linked to the N atom N1 of (I), the bond b of the 6-membered cationic heteroaromatic radical (III) is linked to the N atom N1 of (I), the double bond a1 of the 5-membered heteroaromatic radical (IV) is linked to the N atom N2 of (I), the double bond b1 of the 6-membered heteroaromatic radical (V) is linked to the N atom N2 of (I), the bond b, linking the cationic heteroaromatic radical (III) to the N atom N1 of (I) is in an ortho or para position relative to the N atom bearing the radical R4 when Z5 represents a radical CR13, the bond b is in ortho position relative to the N atom bearing the radical R4 when Z5 is N atom, the bond b1, linking the heteroaromatic radical (V) to N atom N2 of (I) is in ortho or para position relative to N bearing the radical R7 when Z11 is a radical CR19, the bond b1 is in ortho position relative to the N atom bearing the radical R7 when Z11 is N. Independent claims are included for: (1) process for dyeing keratin fibres, and in particular human keratin fibres such as the hair, comprising applying at least one dye composition (A) to the fibres to obtain the desired coloration without final rinsing or after which the fibres are rinsed, optionally washed with shampoo, rinsed again and dried; and (2) multi-compartment device or multi-compartment dyeing kit comprising: first compartment contains (A); and a second compartment comprising an oxidising agent. [Image].

Description

1 DYEING COMPOSITION FOR KERATIN FIBERS WITH DIRECT COLOR

  The invention relates to a dyeing composition for keratinous fibers, in particular for human keratinous fibers such as the hair, comprising, in a medium which is suitable for dyeing, at least one direct dye. cationic tetraazapenta-methine, and which is characterized in that it further contains at least one other particular direct dye. The invention also relates to dyeing processes and devices employing it. In the hair field, two types of coloration can be distinguished. The first is the semi-permanent or temporary coloring, or direct dyeing, which uses dyes capable of providing the natural color of the hair, a more or less marked color change possibly resistant to several shampoos. These dyes are called direct dyes; they can be used with or without an oxidizing agent. In the presence of oxidant, the goal is to obtain a lightening color. The lightening coloring is carried out by applying to the hair the extemporaneous mixture of a direct dye and an oxidant and makes it possible in particular to obtain, by lightening of the melanin of the hair, an advantageous effect such as a solid color. in the case of

  2 gray hair or bring out the color in the case of naturally pigmented hair. The second is permanent coloring or oxidation coloring. This is carried out with so-called "oxidation dyes" comprising the oxidation dye precursors and the couplers. The oxidation dye precursors, commonly called "oxidation bases", are initially colorless or weakly colored compounds that develop their dyeing power within the hair in the presence of oxidizing agents added at the time of use, while driving. the formation of colored and coloring compounds. The formation of these colored and coloring compounds results either from an oxidative condensation of "oxidation bases" on themselves, or from an oxidative condensation of "oxidation bases" on color-modifying compounds commonly called " couplers "and generally present in the dye compositions used in oxidation dyeing. To vary the shades obtained with said oxidation dyes, or to enrich them with reflections, It sometimes happens that they are added direct dyes.

  Among the cationic direct dyes available in the field of the dyeing of keratinous fibers, especially human fibers, the tetraazapenta-methine compounds, the structure of which is developed in the text that follows, are already known; nevertheless, these dyes lead to colorations which have characteristics still insufficient in terms of the power, of the homogeneity of the color distributed along the fiber, it is said that the coloring is too selective, and in terms of toughness, in terms of resistance to the various attacks that can be suffered by the hair (light, bad weather, shampoos).

  However, after extensive research conducted on the question, the applicant has now discovered that it is possible to obtain new compositions for dyeing keratinous fibers capable of leading to powerful and selectively selective colorations that otherwise resist well nevertheless to the various attacks that may be experienced by the hair, by combining at least one direct tetraazapenta-methine cationic dye known from the prior art and at least one other particular direct dye and formulas respectively defined below.

  This discovery is the basis of the present invention. The present invention therefore has for its first object a composition for dyeing keratinous fibers and in particular human keratin fibers such as the hair, containing in a medium suitable for dyeing, (i) at least one cationic direct dye whose structure meets to the formula (I) defined below, characterized in that it further contains (ii) at least one direct dye having at least one extranuclear quaternary ammonium group. --- NN C. 1 "-N W., 2 L, in which - W1 represents a cationic heteroaromatic radical of formula (II) or (III): R3 X- (II) (III) - W2 represents a heteroaromatic radical of formula (IV) R8 (V) in which: - ZO represents a radical CR2, a nitrogen atom or a radical NR21, - Z1 represents an oxygen atom, sulfur or a radical NR9, - Z2 represents a nitrogen atom or a CR10 radical, - Z3 represents a nitrogen atom or a CR11 radical, 15 - Z4 represents a nitrogen atom or a CR12 radical, - Z5 represents a nitrogen atom or a CR13 radical, - Z6 represents a nitrogen atom or a CR14 radical, - Z7 represents an oxygen atom, sulfur atom or an NR15 radical, 20 - Z8 represents a nitrogen atom or a CR16 radical, - Z9 represents a nitrogen atom or a radical CR17, or (V): 5 - Z10 represents a nitrogen atom or a radical CR18, - Z11 represents a nitrogen atom or a radical CR19, - Z12 represents a nitrogen atom or a radical CR20, - Z1 3 represents a CR6 radical, a nitrogen atom or an NR22 radical, it being understood that each of the rings of formulas (II), (III), (IV) and (V) do not contain more than three nitrogen atoms; and that two of the three nitrogen atoms may be contiguous, the link a of the cationic heteroaromatic 5-membered radical of the formula (II) being connected to the nitrogen atom N1 of the formula (I), the bond b of the cationic heteroaromatic 6-membered radical of the formula (III) being connected to the nitrogen atom N1 of the formula (I). the double bond to the 5-membered heteroaromatic radical of the formula (IV) being connected to the nitrogen atom N 2 of the formula (I), the double bond b 'of the heteroaromatic 6-membered radical of the formula (V) being connected to the nitrogen atom N2 of the formula (I), the bond b connecting the cationic heteroaromatic radical of the formula III to the nitrogen atom N1 of the formula (I) being located in the ortho or para position of the nitrogen atom carrying the radical R4 when Z5 represents a radical CR13; the bond b being located in the ortho position of the nitrogen atom carrying the radical R4 when Z5 represents a nitrogen atom, - the bond b ', connecting the heteroaromatic radical of the formula V to the nitrogen atom N2 of the formula (I) being located ortho or para position of the nitrogen atom carrying the radical R7 when Z11 represents a CR19 radical; the bond b 'being located in the ortho position of the nitrogen atom bearing the radical R7 when Z11 represents a nitrogen atom, - R2, R6, R10 and R16 represent, independently of one another, an atom hydrogen; a linear or branched C1-C4 alkyl radical, unsubstituted or substituted with one to three radicals chosen from hydroxyl, C1-C2 alkoxy, (poly) -hydroxyalkoxy C2-C4, amino, (di) alkylamino C1 radicals; -C2, carboxy or sulfonic; a phenyl radical which is unsubstituted or substituted with one or two radicals chosen from hydroxyl, C 1 -C 2 alkoxy, (C 2 -C 4) (poly) hydroxyalkoxy, amino, C 1 -C 2 (di) alkylamino radicals; a carboxy radical; a sulphonylamino radical; R1, R4, R5, R7, R9, R15, R21, and R22 represent, independently of one another, a linear or branched C1-C8 alkyl radical, unsubstituted or substituted with a three radicals selected from hydroxy, C1-C2 alkoxy, (C2-C4) poly (poly) hydroxyalkoxy, amino, C1-C2, di (C1-C2alkyl), carboxy or sulfonic; - RO, R3, R8, R11, R12, R13, R14, R17, R18, R19, and R20 represent, independently of one another, a hydrogen atom, a linear or branched C1-C16 hydrocarbon chain this chain may be saturated or unsaturated by one to three unsaturations, this chain being unsubstituted or substituted by one to three radicals chosen from hydroxyl, C 1 -C 2 alkoxy, (C 2 -C 4) (poly) -hydroxyalkoxy, amino radicals, (di) C1-C2 alkylcarbino, carboxy, sulfonic, sulfonylamino, (poly) -hydroxyalkylamino C2-C4 or a halogen atom such as chlorine, fluorine or bromine; a phenyl radical which is unsubstituted or substituted with one to three radicals chosen from hydroxyl, C 1 -C 2 alkoxy, C 2 -C 4 (poly) hydroxyalkoxy, amino, C 1 -C 2 (di) alkylamino, carboxy, sulphonic and sulphonylamino radicals; (C 2 -C 4) (poly) -hydroxyalkylamino or a halogen atom such as chlorine, fluorine or bromine; a heteroaryl radical chosen from pyrazolyl, pyrrolyl, imidazolyl, thiazolyl, oxazolyl, triazolyl, pyridinyl, pyrimidinyl, triazinyl, pyrazinyl and pyridazinyl radicals, in addition this hydrocarbon-based chain may be interrupted by one or two oxygen and nitrogen atoms, of sulfur or by a radical SO2, - being understood that RO, R3, R8, R11, R12, R13, R14, R17, R18, R19, and R20 do not comprise a peroxide bond, or diazo or nitroso radicals, -R2 with R10, R11 with R12, R6 with R16, and R17 with R18 being able to form independently of each other a 5- or 6-membered aromatic carbon ring unsubstituted or substituted by one or two hydroxy, amino, (di) alkyl (C1) radicals. -C2) amino, C1-C2 alkoxy, (poly) hydroxyalkyl C2-C4 amino, X is an organic or inorganic anion.

  By "branched hydrocarbon chain" within the meaning of the present application is meant a branched hydrocarbon chain which can also form one to five carbon rings comprising from 3 to 7 ring members, this chain possibly comprising one to three unsaturations, that is to say one to three double bonds and / or triple bonds.

  C2-C4 (poly) hydroxyalkoxy means a C2-C4 alkoxy group substituted with 1 to 2 hydroxyl groups, "C2-C4" (poly) hydroxyalkylamino, for the purposes of the present invention, means a group alkylamino substituted with 1 to 2 hydroxy groups.

  The expression according to which the hydrocarbon chain can be interrupted by one or more oxygen, nitrogen, sulfur atoms or by an SO 2 radical, or that this chain is unsaturated means that the carbon chain can be modified in the manner following: HCHZ H can become HOùH -0 can become I _ / \ / \ can become

  For the purposes of the present application, an organic or inorganic anion may for example be chosen from a halide such as chloride, bromide, fluoride or iodide; a hydroxide; sulphate; a hydrogen sulfate; a (C1-C6) alkyl sulphate such as, for example, a methyl sulphate or an o-ethyl sulphate; an acetate; tartrate; an oxalate; a (C1-C6) alkyl sulfonate such as methylsulfonate; an arylsulphonate which is unsubstituted or substituted with a C1-C4 alkyl radical such as, for example, a 4-toluylsulphonate.

  Preferably, RO represents a hydrogen atom; a linear or branched C1-C6 alkyl radical, unsubstituted or substituted with one to three radicals chosen from hydroxyl, C1-C2 alkoxy, (poly) -hydroxyalkoxy C2-C4, amino, (di) alkylamino C1 radicals; -C2, (poly) hydroxyalkylamino C2-C4, carboxy or sulfonic; a phenyl radical which is unsubstituted or substituted with one to three radicals chosen from hydroxyl, C 1 -C 2 alkoxy, C 2 -C 4 (poly) hydroxyalkoxy, amino, C 1 -C 2 (di) alkylamino, carboxyl or sulphonic acid radicals, or halogen atom such as chlorine, fluorine or bromine, an optionally cationic heteroaryl radical chosen from pyrazolyl, pyrrolyl, imidazolyl, thiazolyl, oxazolyl, triazolyl, pyridinyl, pyrimidinyletriazinyl, pyrazinyl and pyridazinyl radicals. More preferably, RO preferably represents a hydrogen atom; a linear or branched C1-C3 alkyl radical, unsubstituted or substituted with one to two radicals chosen from hydroxyl, C1-C2 alkoxy, amino, (di) C1-C2 alkyl, carboxy or sulphonic radicals; a phenyl radical which is unsubstituted or substituted with one to two radicals chosen from hydroxyl, amino, (di) alkylamino radicals with 1 to 2 carbon atoms or (poly) hydroxyalkylamino groups from 2 to 4 carbon atoms, an optionally cationic heteroaryl radical chosen from pyrazolyl radicals, pyrrolyl, imidazolyl, pyridinyl. According to a particularly preferred embodiment, RO represents a hydrogen atom; methyl, ethyl, propyl, butyl, 2-hydroxyethyl, 2-aminoethyl, 1-carboxymethyl, 2-carboxyethyl, 2-sulfonylethyl, 2-methoxyethyl; a phenyl radical which is unsubstituted or substituted with one to two radicals chosen from amino, (di) alkylamino radicals C1-C2, (poly) hydroxyalkylamino C2-C4, an optionally cationic heteroaryl radical chosen from the radicals pyrazolyl, pyrrolyl, imidazolyl, pyridinyl.

  RO is even more preferably a hydrogen atom; a methyl, ethyl, 2-methoxyethyl radical; a phenyl radical which is unsubstituted or substituted by an amino, (di) methylamino, (di) (2-hydroxyethyl) amino radical, an optionally cationic heteroaryl radical chosen from imidazolyl and pyridinyl radicals. R 2, R 6, R 10 and R 16 preferably represent a hydrogen atom, a phenyl radical or a C 1 -C 4 alkyl radical which is unsubstituted or substituted by one or two radicals chosen from the group consisting of hydroxy, amino and (di) alkylamino radicals. C2, carboxy. According to a particularly preferred embodiment, R2, R6, R10 and R16 preferably represent a hydrogen atom, a methyl, phenyl, 2-hydroxymethyl, a carboxy or a phenyl radical.

  R 1, R 4, R 5, R 7, R 9, R 15, R 21 and R 22 preferably represent a C 1 -C 4 alkyl radical which is unsubstituted or substituted by one or two radicals chosen from hydroxyl, C 1 -C 2 alkoxy, amino and (di) radicals; C1-C2 alkylamino, carboxy, sulfonic acid.

  According to a particularly preferred embodiment, R 1, R 4, R 5, R 7, R 9, R 15, R 21 and R 22 preferably represent a methyl, ethyl, 2-hydroxyethyl, 1-carboxymethyl, 2-carboxyethyl or 2-sulphonylethyl radical. R3, R8, R11, R12, R13, R14, R17, R18, R19, and R20 represent, preferably and independently of each other, a hydrogen atom; a linear or branched C1-C4 alkyl radical, unsubstituted or substituted with one to two radicals chosen from hydroxyl, C1-C2 alkoxy, (poly) -hydroxyalkoxy C2-C4, amino, (di) C1-alkylamino radicals; -C2, carboxy or sulfonic; a phenyl radical which is unsubstituted or substituted by one or two radicals chosen from hydroxyl, C 1 -C 2 alkoxy, (C 2 -C 4) (poly) hydroxyalkoxy, amino, C 1 -C 2 (di) alkylamino, carboxyl or sulphonic acid radicals, or a halogen atom such as chlorine, fluorine or bromine; a sulfonylamino radical; a C2-C4 (poly) -hydroxyalkylamino radical.

  More preferably, R3, R8, R11, R12, R13, R14, R17, R18, R19, and R20 represent a hydrogen atom, a C1-C4 alkyl radical, unsubstituted or substituted by one to two radicals chosen from hydroxy radicals, a C1-C2 alkoxy radical; an amino radical; a C1-C2 (di) alkylamino radical; a carboxy radical; a C2-C4 (poly) -hydroxyalkylamino radical. According to a particularly preferred embodiment R3, R8, R11, R12, R13, R14, R17, R18, R19, and R20 represent independently of each other a hydrogen atom, a methyl radical, 2-hydroxymethyl, carboxy, methoxy, ethoxy, 2-hydroxyethyloxy, amino, methylamino, dimethylamino, 2-hydroxyethylamino. In a first preferred variant, the compounds of formula I are chosen from the family defined by the compounds for which W 1 is a 2-pyridinium radical and W 2 is a 2-pyridine radical. Even more preferably, these are the following compounds - 2- [5- (N-methyl-2-pyridinylidene) -1-formazano] -N-methylpyridinium chloride - 2- [5- (N-methyl) 2-pyridinylidene) -3-methyl-1-formazano] -N-methylpyridinium - 2- [5- (N-methyl-2-pyridinylidene) -3-ethyl-1-formazano] -N-methylpyridinium chloride 2- [5- (N-methyl-2-pyridinylidene) -3-isopropyl-1-formazano] -N-methylpyridinium - 2- [5- (N-methyl-2-pyridinylidene) -3-phenyl] chloride -formazano] -N-methylpyridinium 2- [5- (N-methyl-2-pyridinylidene) -3- (4'-methoxyphenyl) -1-formazano] -N-methylpyridinium chloride - 2- [5- N-methyl-2-pyridinylidene) -3- (4'-hydroxyphenyl) -1-formazano] -N-methylpyridinium - 2- [5- (N-methyl-2-pyridinylidene) -3- (4'-hydroxy) chloride) N, N-dimethylaminophenyl) -1-formazano] -N-methylpyridinium - 2- [5- (4-pyrrolidino-N-methyl-2-pyridinylidene) -1-formazano] -4-pyrrolidino-N-methylpyridinium chloride - 2- [5- (4-Pyrrolidino-N-methyl-2-pyridyl chloride) Nylidene) -3-methyl-1-formazano] -4-pyrrolidino-N-methylpyridinium - 2- [5- (4-pyrrolidino-N-methyl-2-pyridinylidene) 3-ethyl-1-formazano] chloride -Pyrrolidino-N-methylpyridinium - 2- [5- (4-pyrrolidino-N-methyl-2-pyridinylidene) -3-isopropyl-1-formazano] -4-pyrrolidino-N-methylpyridinium chloride - 2- [ 5- (4-Pyrrolidino-N-methyl-2-pyridinylidene) 3-phenyl-1-formazano] -4-pyrrolidino-N-methylpyridinium - 2- [5- (4-pyrrolidino-N-methyl) -2-chloro] chloride pyridinylidene) -3- (4'-methoxyphenyl) -1-formazano] -4-pyrrolidino-N-methylpyridinium - 2- [5- (4-pyrrolidino-N-methyl-2-pyridinylidene) -3- (4-pyridinylidene) chloride 1-hydroxyphenyl) -1-formazano] -4-pyrrolidino-N-methylpyridinium-2- [5- (4-Pyrrolidino-N-methyl-2-pyridinylidene) -3- (4'-N, N-dimethylaminophenyl) chloride ) -1-formazano] -4-pyrrolidino-N-methylpyridinium-2- [5- (N-Hydroxyethyl-2-pyridinylidene) -1-formazano] -N-hydroxyethylpyridinium chloride - 2- [5- (N) -N -hydroxyethyl-2-pyridinylidène) -3-methyl-1-fo rmazano] -N-hydroxyethylpyridinium - 2- [5- (N-hydroxyethyl-2-pyridinylidene) -3-ethyl-1-formazano] -N-hydroxyethyl-pyridinium chloride - 2- [5- (N-hydroxyethyl) chloride -2-pyridinylidene) -3-phenyl-1-formazano] -N-hydroxyethyl-pyridinium. 2- [5- (N-Hydroxyethyl-2-pyridinylidene) -3-isopropyl-1-formazano] -N-hydroxyethyl-pyridinium chloride - 2- [5- (N-hydroxyethyl-2-pyridinylidene) -3-hydroxychloride (4'-Methoxyphenyl) -1-formazano] -N-hydroxyethylpyridinium - 2- [5- (N-hydroxyethyl-2-pyridinylidene) -3- (4'-hydroxyphenyl) -1-formazano] -N-hydroxyethyl chloride -Pyridinium - 2- [5- (N-hydroxyethyl-2-pyridinylidene) -3- (4'N, N-dimethylaminophenyl) -1-formazano] -N-hydroxyethylpyridinium chloride 2- [5- ( N-carboxyethyl-2-pyridinylidene) -1-formazano] -N-carboxyethylpyridinium - 2- [5- (N-carboxyethyl-2-pyridinylidene) -3-methyl-1-formazano] -N-carboxyethylpyridinium chloride 2- [5- (N-carboxyethyl-2-pyridinylidene) -3-ethyl-1-formazano] -N-carboxyethylpyridinium 2- [5- (N-carboxyethyl-2-pyridinylidene) -3-phenyl] chloride 1-formazano] -N-carboxyethylpyridinium-2- [5- (N-carboxyethyl-2-pyridinylidene) -3-isopropyl-1-formazano] -N-carboxyethylpyridini chloride 2- [5- (N-carboxyethyl-2-pyridinylidene) -3- (4'-methoxyphenyl) -1-formazano] -N-carboxyethylpyridinium chloride - 2- [5- (N-carboxyethyl) chloride 2-pyridinylidene) -3- (4'-hydroxyphenyl) -1-formazano] -N-carboxyethylpyridinium - 2- [5- (N-carboxyethyl) -2-pyridinylidene) -3- (4'-N) chloride N, N-dimethylaminophenyl) -1-formazano] -N-carboxynethyl-pyridinium B. In a second preferred variant, the compounds of formula I are chosen from the family defined by the compounds for which W 1 is a 4-pyridinium radical and W 2 is a radical. 4- pyridine. Even more preferably, they are the following compounds - 4- [5- (N-methyl-4-pyridinylidene) -1-formazano] -N-methylpyridinium chloride 4- [5- (N-methyl-4) chloride -pyridinylidene) -3-methyl-1-formazano] -N-methylpyridinium - 4- [5- (N-methyl-4-pyridinylidene) -3-ethyl-1-formazano] -N-methylpyridinium chloride - chloride of 4 - [5- (N-methyl-4-pyridinylidene) -3-isopropyl-1-formazano] -N-methylpyridinium - 4- [5- (N-methyl-4-pyridinylidene) -3-phenyl] -lchloride formazano] -N-methylpyridinium - 4- [5- (N-Methyl-4-pyridinylidene) -3- (4'-methoxyphenyl) -1-formazano] -N-methylpyridinium Chloride - 4- [5- N-methyl-4-pyridinylidene) -3- (4'-hydroxyphenyl) -1-formazano] -N-methylpyridinium - 4- [5- (N-methyl-4-pyridinylidene) -3- (4'-chlorophenyl) chloride N, N-dimethylaminophenyl) -1-formazano] -N-methylpyridinium - 4- [5- (N-hydroxyethyl-4-pyridinylidene) -1-formazano] -N-hydroxyethylpyridinium chloride - 4- [5- ( N-hydroxyethyl-4-pyridinylidène) -3-me thyl-1-formazano] -N-hydroxyethylpyridinium - 4- [5- (N-hydroxyethyl-4-pyridinylidene) -3-ethyl-1-formazano] -N-hydroxyethyl-pyridinium chloride - 4- [5- (N-Hydroxyethyl-4-pyridinylidene) -3-phenyl-1-formazano] -N-hydroxyethyl-pyridinium-4- [5- (N-hydroxyethyl-4-pyridinylidene) -3-isopropyl-1-formazano] chloride N-hydroxyethylpyridinium 4- [5- (N-hydroxyethyl-4-pyridinylidene) -3- (4'-methoxyphenyl) -1-formazano] -N-hydroxyethylpyridinium chloride - 4- [5- (N-) -N-hydroxyethyl-pyridinium chloride hydroxyethyl -4-pyridinylidene) -3- (4'-hydroxyphenyl) -1-formazano] -N-hydroxyethylpyridinium - 4- [5- (N-hydroxyethyl-4-pyridinylidene) -3- N, N-Dimethylaminophenyl) -1-formazano] -N-hydroxyethylpyridinium-4- [5- (N-carboxyethyl-4-pyridinylidene) -1-formazano] -N-carboxyethylpyridinium chloride - 4- [5-chloro] chloride (4- (N-carboxyethyl-4-pyridinylidene) -3-methyl-1-formazano] -N-carboxyethylpyridinium-4- [5- (N-carboxyethyl-4-pyridinylidene) chloride) 3-ethyl-1-formazano] -N-carboxyethylpyridinium 4- [5- (N-carboxyethyl-4-pyridinylidene) -3-phenyl-1-formazano] -N-carboxyethylpyridinium chloride 4- [4- 5- (N-carboxyethyl-4-pyridinylidene) -3-isopropyl-1-formazano] -N-carboxyethylpyridinium 4- [5- (N-carboxyethyl-4-pyridinylidene) -3- (4'-methoxyphenyl) chloride ) 1-formazano] -N-carboxyethylpyridinium - 4- [5- (Ncarboxyethyl-4-pyridinylidene) -3- (4'-hydroxyphenyl) -1-formazano] -N-carboxyethylpyridinium chloride - 4- [5- 5- (N-carboxyethyl-4-pyridinylidene) -3- (4'-N, N-dimethylaminophenyl) -1-formazano] -N-carboxyethylpyridinium C. In a third preferred variant, the compounds of formula I are chosen in the family defined by the compounds for which W 1 is a 2-imidazolium radical and W 2 is a 2-imidazole radical. Even more preferably, they are the following compounds: - 2- [5- (1,3-dimethyl-2-imidazolidene) -1-formazano] -1,3-dimethylimidazolium chloride - 2- [ 5- (1,3-Dimethyl-2-imidazolidene) -3-methyl-1-formazano] -1,3-dimethylimidazolium-2- [5- (1,3-dimethyl-2-imidazolidene)] chloride 3-ethyl-1-formazano] -1,3-dimethylimidazolium - 2- [5- (1,3-dimethyl-2-imidazolidene) -3-isopropyl-1-formazano] -1,3-dimethyl chloride -imidazolium - 2- [5- (1,3-dimethyl-2-imidazolidene) -3-phenyl-1-formazano] -1,3-dimethylimidazolium chloride - 2- [5- 2-dimethyl-2-imidazolidene) -3- (4'-methoxyphenyl) -1-formazano] -1,3-dimethylimidazolium - 2- [5- (1,3-dimethyl-2-imidazolidene) -3-chloride - (4'-Hydroxyphenyl) -1-formazano] -1,3-dimethylimidazolium - 2- [5- (1,3-dimethyl-2-imidazolidene) -3- (4'-N, N-) chloride dimethylaminophenyl) -1-formazano] -1,3-dimethylimidazolium - 2- [5- (1,3-dihydroxyethyl-2-imidazolidene) -1-formazano] chloride -1,3 -dihydroxyethylimidazolium - 2- [5- (1,3-dihydroxyethyl-2-imidazolidene) -3-methyl-1-formazano] -1,3-dihydroxyethylimidazolium chloride - 2- [5- (1,3-dihydroxyethyl) chloride 2-Imidazolidene) -3-ethyl-1-formazano] -1,3-dihydroxyethylimidazolium - 2- [5- (1,3-dihydroxyethyl-2-imidazolidene) -3-phenyl-1-formazano] chloride -1,3-Dihydroxyethyl-imidazolium-2- [5- (1,3-dihydroxyethyl-2-imidazolidene) -3-isopropyl-1-formazano] -1,3-dihydroxyethyl imidazolium chloride - 2- [5-chloro] chloride - (1,3-dihydroxyethyl-2-imidazolidene) -3- (4'-methoxyphenyl) -1-formazano] -1,3-dihydroxyethylimidazolium - 2- [5- (1,3-dihydroxyethyl) -2-dihydroxyethyl chloride imidazolidene) -3- (4'-hydroxyphenyl) -1-formazano] -1,3-dihydroxyethylimidazolium - 2- [5- (1,3-dihydroxyethyl-2-imidazolidene) -3- (4 ') chloride N, N-dimethylaminophenyl) -1-formazano] -1,3-dihydroxyethylimidazolium-2- [5- (1,3-dicarboxyethyl-2-imidazolidene) -1-formazano] -1,3-dicarboxyethyl chloride imidazolium - Chloride 2- [5- (1,3-dicarboxyethyl-2-imidazolidene) -3-methyl-1-formazano] -1,3-dicarboxyethylimidazolium 2- [5- (1,3-dicarboxyethyl-2-imidazolidene) -3-ethyl] chloride -1-formazano] -1,3-dicarboxyethyl-imidazolium-2- [5- (1,3-dicarboxyethyl-2-imidazolidene) -3-phenyl-1-formazano] -1,3-dicarboxyethylimidazolium chloride 2- [5- (1,3-Dicarboxyethyl-2-imidazolidene) -3-isopropyl-1-formazano] -1,3-dicarboxyethyl imidazolium chloride - 2- [5- (1,3-dicarboxyethyl) -2-dichlorobenzyl chloride imidazolidene) -3- (4'-methoxyphenyl) -1-formazano] -1,3-dicarboxyethylimidazolium-2- [5- (1,3-dicarboxyethyl) -2-imidazolidene) -3- (4 ') chloride -hydroxyphenyl) -1-formazano] -1,3-dicarboxyethylimidazolium - 2- [5- (1,3-dicarboxyethyl) -2-imidazolidene) -3- (4'-N, N-dimethylaminophenyl) chloride In a fourth preferred variant, the compounds of formula I are chosen from the family defined by the compounds for which W 1 is a 5-pyrazo radical. lium and W2 is a 5-pyrazole radical. Even more preferably, they are the following compounds: - 5- [5- (1,2-dimethyl-5-pyrazolidene) -1-formazano] -1,2-dimethyl-pyrazolinium chloride - 5- (1,2-Dimethyl-5-pyrazolidene) -3-methyl-1-formazano] -1,2-dimethyl-pyrazolinium - 5- [5- (1,2-dimethyl-5-pyrazolidene) -3- chloride ethyl-1-formazano] -1,2-dimethyl-pyrazolinium - 5- [5- (1,2-dimethyl-5-pyrazolidene) -3-isopropyl-1-formazano] -1,2-dimethyl-pyrazolinium chloride - 5- [5- (1,2-Dimethyl-5-pyrazolidene) -3-phenyl-1-formazano] -1,2-dimethyl-pyrazolinium chloride - 5- [5- (1,2-dimethyl) chloride 5-pyrazolidene) -3- (4'-methoxyphenyl) -1-formazano] -1,2-dimethylpyrazolinium - 5- [5- (1,2-dimethyl-5-pyrazolidene) -3- ( 4'-hydroxyphenyl) -1-formazano] -1,2-dimethyl-pyrazolinium - 5- [5- (1,2-dimethyl-5-pyrazolidene) -3- (4'-N, N-dimethylaminophenyl) chloride) -1-formazano] -1,2-dimethyl-pyrazolinium - 5- [5- (1,2-dihydroxyethyl-5-pyrazolidene) -1-formazano] -1,2-dihydrochloride ydroxyethylpyrazolinium - 5- [5- (1,2-dihydroxyethyl-5-pyrazolidene) -3-methyl-1-formazano] -1,2-dihydroxyethylpyrazolinium chloride - 5- [5- (1,2-dihydroxyethyl) chloride 5-pyrazolidene) -3-ethyl-1-formazano] -1,2-dihydroxyethylpyrazolinium-5- [5- (1,2-dihydroxyethyl-5-pyrazolidene) -3-phenyl-1-formazano] chloride 1,2-Dihydroxyethyl-pyrazolinium-5- [5- (1,2-dihydroxyethyl-5-pyrazolidene) -3-isopropyl-1-formazano] -1,2-dihydroxyethyl pyrazolinium chloride - 5- [5- [5- (1,2-Dihydroxyethyl-5-pyrazolidene) -3- (4'-methoxyphenyl) -1-formazano] -1,2-dihydroxyethylpyrazolinium - 5- [5- (1,2-dihydroxyethyl) -5- chloride pyrazolidene) -3- (4'-hydroxyphenyl) -1-formazano] -1,2-dihydroxyethylpyrazolinium - 5- [5- (1,2-dihydroxyethyl-5-pyrazolidene) -3- N, N-dimethylaminophenyl) -1-formazano] -1,2-dihydroxyethyl pyrazolinium -5- [5- (1,2-dicarboxyethyl-5-pyrazolidene) -1-formazano] -1,2-dicarboxyethylpyrazolinium chloride - Chloride of 5- [5- (1, 2-dicarboxyethyl-5-pyrazolidene) -3-methyl-1-formazano] -1,2-dicarboxyethylpyrazolinium-5- [5- (1,2-dicarboxyethyl-5-pyrazolidene) -3-ethyl-1-chloride -formazano] -1,2-dicarboxyethyl-pyrazolinium-5- [5- (1,2-dicarboxyethyl-5-pyrazolidene) -3-phenyl-1-formazano] -1,2-dicarboxyethyl-pyrazolinium chloride 5-Chloride - [5- (1,2-dicarboxyethyl-5-pyrazolidene) -3-isopropyl-1-formazano] -1,2-dicarboxyethyl pyrazolinium - 5- [5- (1,2-dicarboxyethyl) -5-pyrazolidene chloride] 3- [4- (4'-methoxyphenyl) -1-formazano] -1,2-dicarboxyethylpyrazolinium - 5- [5- (1,2-dicarboxyethyl) -5-pyrazolidene) -3- (4'-hydroxyphenyl) chloride -1-formazano] -1,2-dicarboxyethylpyrazolinium. 5- [5- (1,2-dicarboxyethyl-5-pyrazolidene) -3- (4'-N, N-dimethylaminophenyl) -1-formazano] -1,2-dicarboxyethyl pyrazolinium chloride

  E. In a fifth preferred variant, the compounds of formula I are chosen from the family defined by the compounds for which W 1 is a 2-benzimidazolium radical and W 2 is a 2-pyridine radical. Even more preferably, they are the following compounds - 2- [5- (N-methyl-2-pyridinylidene) -1-formazano] -1,3-dimethylbenzimidazolium chloride - 2- [5- (N-methyl) -2- methyl-2-pyridinylidene) -3-methyl-1-formazano] -1,3-dimethylbenzimidazolium - 2- [5- (N-methyl-2-pyridinylidene) -3-ethyl-1-formazano] chloride 1,3-dimethylbenzimidazolium - 2- [5- (N-methyl-2-pyridinylidene) -3-isopropyl-1-formazano] -1,3-dimethylbenzimidazolium chloride - 2- [5- ( N-methyl-2-pyridinylidene) -3-phenyl-1-formazano] -1,3-dimethylbenzimidazolium 2- [5- (N-methyl-2-pyridinylidene) -3- (4'-methoxyphenyl) chloride -1-formazano] -1,3-dimethyl-benzimidazolium - 2- [5- (N-methyl-2-pyridinylidene) -3- (4'-hydroxyphenyl) -1-formazano] -1,3-dimethyl chloride -benzimidazolium - 2- [5- (N-methyl-2-pyridinylidene) -3- (4'-N, N-dimethylaminophenyl) -1-formazano] -1,3-dimethylbenzimidazolium chloride. 2- [5- (N-hydroxyethyl-2-pyridinylidene) -1-formazano] -1,3-dihydroxyethylbenzimidazolium chloride - 2- [5- (N-hydroxyethyl-2-pyridinylidene) -3-methyl] chloride 1-formazano] -1,3-dihydroxyethylbenzimidazolium - 2- [5- (N-hydroxyethyl-2-pyridinylidene) -3-ethyl-1-formazano] -1,3-dihydroxyethylbenzimidazolium chloride - 2- 5- (N-Hydroxyethyl-2-pyridinylidene) -3-phenyl-1-formazano] -1,3-dihydroxyethylbenzimidazolium-2- [5- (N-hydroxyethyl-2-pyridinylidene) -3-isopropyl] chloride 1-formazano] -1,3-dihydroxyethylbenzimidazolium - 2- [5- (N-hydroxyethyl-2-pyridinylidene) -3- (4'-methoxyphenyl) -1-formazano] -1,3-dihydroxyethyl chloride - benzimidazolium - 2- [5- (N-hydroxyethyl-2-pyridinylidene) -3- (4'-hydroxyphenyl) -1-formazano] -1,3-dihydroxyethylbenzimidazolium chloride - 2- [5- (N) -chloride 2-hydroxy-2-pyridinylidene) -3- (4'-N, N-dimethylaminophenyl) -1-formazano] -1,3-dihydroxyethylbenzimidazolium - 2- [5- (N-carboxyethyl) -2-hydroxychloride pyridinylidene) -1-formazano] -1,3-dicarboxyethylbenzimidazolium - 2- [5- (N-carboxyethyl-2-pyridinylidene) -3-methyl-1-formazano] -1,3-dicarboxyethylbenzimidazolium chloride - 2- [5- (N-carboxyethyl-2-pyridinylidene) -3-ethyl-1-formazano] -1,3-dicarboxyethylbenzimidazolium chloride - 2- [5- (N-carboxyethyl-2-pyridinylidene) chloride 3-phenyl-1-formazano] -1,3-dicarboxyethylbenzimidazolium-2- [5- (N-carboxyethyl-2-pyridinylidene) -3-isopropyl-1-formazano] -1,3-dicarboxyethyl chloride benzimidazolium - 2- [5- (N-carboxyethyl-2-pyridinylidene) -3-4'methoxyphenyl) -1-formazano] -1,3-dicarboxyethylbenzimidazolium chloride - 2- [5- (N-carboxyethyl) chloride 2-pyridinylidene) -3- (4'-hydroxyphenyl) -1-formazano] -1,3-dicarboxyethylbenzimidazolium-2- [5- (N-carboxyethyl-2-pyridinylidene) -3- (4 ') chloride N, N-dimethylaminophenyl) -1-formazano] -1,3-dicarboxyethyl benzimidazolium. F. In a sixth preferred variant, the compounds of formula I are chosen from the family defined by the compounds for which W 1 is a 2-benzimidazolium radical and W 2 is a 4-pyridine radical. Even more preferably, they are the following compounds: - 2- [5- (N-methyl-4-pyridinylidene) -1-formazano] -1,3-dimethylbenzimidazolium chloride - 2- [5- (N) chloride 4-methyl-4-pyridinylidene) -3-methyl-1-formazano] -1,3-dimethylbenzimidazolium - 2- [5- (N-methyl-4-pyridinylidene) -3-ethyl-1-formazano] chloride 1, 3-dimethylbenzimidazolium - 2- [5- (N-methyl-4-pyridinylidene) -3-isopropyl-1-formazano] -1,3-dimethylbenzimidazolium chloride - 2- [5- (N-methyl-4-pyridinylidene) -3-phenyl-1-formazano] -1,3-dimethylbenzimidazolium - 2- [5- (N-methyl-4-pyridinylidene) -3- methoxyphenyl) -1-formazano] -1,3-dimethylbenzimidazolium - 2- [5- (N-methyl-4-pyridinylidene) -3- (4-hydroxyphenyl) -1-formazano] chloride dimethylbenzimidazolium - 2- [5- (N-methyl-4-pyridinylidene) -3- (4'-N, N-dimethylaminophenyl) -1-formazano] -1,3-dimethylbenzimidazolium chloride - chloride of 2 - [5- (N-hydroxyethyl-4-pyridinylidene) -1-formazano] -1,3 -dihydroxyethylbenzimidazolium - 2- [5- (N-hydroxyethyl-4-pyridinylidene) -3-methyl-1-formazano] -1,3-dihydroxyethylbenzimidazolium chloride - 2- [5- (N-hydroxyethyl) -4-pyridinylidene chloride ) -3-ethyl-1-formazano] -1,3-dihydroxyethyl-benzimidazolium - 2- [5- (N-hydroxyethyl-4-pyridinylidene) -3-phenyl-1-formazano] -1,3-dihydroxyethyl chloride -benzimidazolium - 2- [5- (N-hydroxyethyl-4-pyridinylidene) -3-isopropyl-1-formazano] -1,3-dihydroxyethylbenzimidazolium chloride - 2- [5- (N-hydroxyethyl) -4-hydroxychloride -pyridinylidene) -3- (4'-methoxyphenyl) -1-formazano] -1,3-dihydroxyethylbenzimidazolium - 2- [5- (N-hydroxyethyl-4-pyridinylidene) -3- (4'-hydroxyphenyl) chloride ) -1-formazano] -1,3-dihydroxyethylbenzimidazolium - 2- [5- (N-hydroxyethyl-4-pyridinylidene) -3- (4'-N, N-dimethylaminophenyl) -1-formazano] chloride 1,3-dihydroxyethylbenzimidazolium - 2- [5- (N-carboxyethyl-4-pyridinylidene) -1-formazano] -1,3-dicarboxyethylbenzimidazolium chloride - Ch 2- [5- (N-carboxyethyl-4-pyridinylidene) -3-methyl-1-formazano] -1,3-dicarboxyethylbenzimidazolium chloride - 2- [5- (N-carboxyethyl-4-pyridinylidene) chloride 3-ethyl-1-formazano] -1,3-dicarboxyethylbenzimidazolium - 2- [5- (N-carboxyethyl-4-pyridinylidene) -3-phenyl-1-formazano] -1,3-dicarboxyethyl chloride benzimidazolium - 2- [5- (N-carboxyethyl-4-pyridinylidene) -3-isopropyl-1-formazano] -1,3-dicarboxyethylbenzimidazolium chloride - 2- [5- (N-carboxyethyl) -4- pyridinylidene) -3- (4'-methoxyphenyl) -1-formazano] -1,3-dicarboxyethylbenzimidazolium - 2- [5- (N-carboxyethyl-4-pyridinylidene) -3- (4'-hydroxyphenyl) chloride -1-formazano] -1,3-dicarboxyethylbenzimidazolium. 2- [5- (N-carboxyethyl-4-pyridinylidene) -3- (4'-N, N-dimethylaminophenyl) -1-formazano] -1,3-dicarboxyethylbenzimidazolium chloride. In a seventh preferred variant the compounds of formula I are chosen from the family defined by the compounds for which W 1 is a 2-imidazolium radical and W 2 is a 2-pyridine radical. Even more preferably, they are the following compounds: 2- [5- (N-methyl-2-pyridinylidene) -1-formazano] -1,3-dimethylimidazolium chloride-2- [5- N-methyl-2-pyridinylidene) -3-methyl-1-formazano] -1,3-dimethylimidazolium - 2- [5- (N-methyl-2-pyridinylidene) -3-ethyl-1-formazano chloride ] -1,3-dimethylimidazolium - 2- [5- (N-methyl-2-pyridinylidene) -3-isopropyl-1-formazano] -1,3-dimethylimidazolium chloride - 2- [5-chloro] chloride - (N-methyl-2-pyridinylidene) -3-phenyl-1-formazano] -1,3-dimethylimidazolium - 2- [5- (N-methyl-2-pyridinylidene) -3- (4 ') chloride -methoxyphenyl) -1-formazano] -1,3-dimethylimidazolium-2- [5- (N-methyl-2-pyridinylidene) -3- (4'-hydroxyphenyl) -1-formazano] -1 chloride 3-dimethylimidazolium-2- [5- (N-methyl-2-pyridinylidene) -3- (4'-N, N-dimethylaminophenyl) -1-formazano] -1,3-dimethylimidazolium chloride. - 2- [5- (N-hydroxyethyl-2-pyridinylidene) -1-formazano] -1,3-dihydroxyethylimidazolium chloride - 2- [5- (N-hydroxyethyl-2-pyridinylidene) -3-methyl] chloride 1-formazano] -1,3-dihydroxyethylimidazolium - 2- [5- (N-hydroxyethyl-2-pyridinylidene) -3-ethyl-1-formazano] -1,3-dihydroxyethylimidazolium chloride - 2- 5- (N-hydroxyethyl-2-pyridinylidene) -3-phenyl-1-formazano] -1,3-dihydroxyethylimidazolium-2- [5- (N-hydroxyethyl-2-pyridinylidene) -3-isopropyl] chloride 1-formazano] -1,3-dihydroxyethylimidazolium 2- [5- (N-hydroxyethyl-2-pyridinylidene) -3- (4'-methoxyphenyl) -1-formazano] -1,3-dihydroxyethylimidazolium Chloride 2- [5- (N-hydroxyethyl-2-pyridinylidene) -3- (4'-hydroxyphenyl) -1-formazano] -1,3-dihydroxyethylimidazolium - 2- [5- (N-hydroxyethyl) -2- 2-pyridinylidene) -3- (4'-N, N-dimethylaminophenyl) -1-formazano] -1,3-dihydroxyethyl imidazolium-2- [5- (N-carboxyethyl-2-pyridinylidene) -1-formazano chloride ] -1,3-d icarboxyethyl-imidazolium - 2- [5- (N-carboxyethyl-2-pyridinylidene) -3-methyl-1-formazano] -1,3-dicarboxyethyl imidazolium chloride - 2- [5- (N-carboxyethyl) chloride 2-pyridinylidene) -3-ethyl-1-formazano] -1,3-dicarboxyethylimidazolium - 2- [5- (N-carboxyethyl-2-pyridinylidene) -3-phenyl-1-formazano] -1 chloride 3-dicarboxyethylimidazolium - 2- [5- (N-carboxyethyl-2-pyridinylidene) -3-isopropyl-1-formazano] -1,3-dicarboxyethylimidazolium chloride - 2- [5- (N-) carboxyethyl-2-pyridinylidene) -3- (4'-methoxyphenyl) -1-formazano] -1,3-dicarboxyethylimidazolium - 2- [5- (N-carboxyethyl-2-pyridinylidene) -3- -hydroxyphenyl) -1-formazano] -1,3-dicarboxyethylimidazolium - 2- [5- (N-carboxyethyl-2-pyridinylidene) -3- (4'-N, N-dimethylaminophenyl) -1- formazano] -1,3-dicarboxyethylimidazolium H. In an eighth preferred variant, the compounds of formula I are chosen from the family defined by the compounds for which W1 is a 2-imidazolium radical and W2 is a 4-pyridine radical. Even more preferably, they are the following compounds - 2- [5- (N-methyl-4-pyridinylidene) -1-formazano] -1,3-dimethylimidazolium chloride - 2- [5- ( N-methyl-4-pyridinylidene) -3-methyl-1-formazano] -1,3-dimethylimidazolium - 2- [5- (N-methyl-4-pyridinylidene) -3-ethyl-1-formazano chloride ] -1,3-dimethylimidazolium - 2- [5- (N-methyl-4-pyridinylidene) -3-isopropyl-1-formazano] -1,3-dimethylimidazolium chloride - 2- [5-chloro] chloride - (N-methyl-4-pyridinylidene) -3-phenyl-1-formazano] -1,3-dimethylimidazolium - 2- [5- (N-methyl-4-pyridinylidene) -3- (4 ') chloride methoxyphenyl) -1-formazano] -1,3-dimethylimidazolium-2- [5- (N-methyl-4-pyridinylidene) -3- (4'-hydroxyphenyl) -1-formazano] -1 chloride 3-Dimethyl-imidazolium - 2- [5- (N-methyl-4-pyridinylidene) -3- (4'-N, N-dimethylaminophenyl) -1-formazano] -1,3-dimethylimidazolium chloride - Chloride 2- [5- (N-hydroxyethyl-4-pyridinylidene) -1-formazano] -1,3-dihydroxyethylimidazolium - C 2- [5- (N-Hydroxyethyl-4-pyridinylidene) -3-methyl-1-formazano] -1,3-dihydroxyethylimidazolium chloride - 2- [5- (N-Hydroxy-4-yl) pyridinylidene) chloride 1-ethyl-1-formazano] -1,3-dihydroxyethylimidazolium - 2- [5- (N-hydroxyethyl-4-pyridinylidene) -3-phenyl-1-formazano] -1,3-dihydroxyethylimidazolium chloride 2- [5- (N-Hydroxyethyl-4-pyridinylidene) -3-isopropyl-1-formazano] -1,3-dihydroxyethylimidazolium chloride - 2- [5- (N-hydroxyethyl-4-pyridinylidene) chloride 3- [4- (4'-methoxyphenyl) -1-formazano] -1,3-dihydroxyethylimidazolium - 2- [5- (N-hydroxyethyl-4-pyridinylidene) -3- (4'-hydroxyphenyl)] chloride -formazano] -1,3-dihydroxyethylimidazolium - 2- [5- (N-hydroxyethyl-4-pyridinylidene) -3- (4'-N, N-dimethylaminophenyl) -1-formazano] -1.3 chloride -dihydroxyethyl imidazolium - 2- [5- (N-carboxyethyl-4-pyridinylidene) -1-formazano] -1,3-dicarboxyethylimidazolium chloride - 2- [5- (N-carboxyethyl-4-pyridinylidene) chloride -3-methyl-1-for mazano] -1,3-dicarboxyethylimidazolium - 2- [5- (N-carboxyethyl-4-pyridinylidene) -3-ethyl-1-formazano] -1,3-dicarboxyethylimidazolium chloride - 2- 5- (N-carboxyethyl-4-pyridinylidene) -3-phenyl-1-formazano] -1,3-dicarboxyethylimidazolium - 2- [5- (N-carboxyethyl-4-pyridinylidene) -3-isopropyl] chloride 1-formazano] -1,3-dicarboxyethylimidazolium - 2- [5- (N-carboxyethyl-4-pyridinylidene) -3- (4'-methoxyphenyl) -1-formazano] -1,3-dicarboxyethylimidazolium chloride 2- [5- (N-carboxyethyl-4-pyridinylidene) -3- (4'-hydroxyphenyl) -1-formazano] -1,3-dicarboxyethylimidazolium chloride - 2- [5- (N-) -N carboxyethyl-4-pyridinylidene) -3- (4'-N, N-dimethylaminophenyl) -1-formazano] -1,3-dicarboxyethylimidazolium.

  In a ninth preferred variant, the compounds of formula I are chosen from the family defined by the compounds for which W 1 is a 2-benzimidazolium radical and W 2 is a 2-benzimidazole radical. Even more preferably, it is the compounds following:

  2- [5- (1,3-Dimethyl-2-benzimidazolidene) -1-formazano] -1,3-dimethylbenzimidazolium chloride - 2- [5- (1,3-dimethyl-2-benzimidazolidene) chloride ) -3-methyl-1-formazano] -1,3-dimethyl-benzimidazolium - 2- [5- (1,3-dimethyl-2-benzimidazolidene) -3-ethyl-1-5-formazano] -1-chloride, 3-dimethylbenzimidazolium - 2- [5- (1,3-dimethyl-2-benzimidazolidene) -3-isopropyl-1-formazano] -1,3-dimethylbenzimidazolium chloride - 2- [5- ( 1,3-dimethyl-2-benzimidazolidene) -3-phenyl-1-formazano] -1,3-dimethylbenzimidazolium 2- 2- [5- (1,3-Dimethyl-2-benzimidazolidene) -3- chloride (4'-Methoxyphenyl) -1-formazano] -1,3-dimethylbenzimidazolium - 2- [5- (1,3-dimethyl-2-benzimidazolidene) -3- (4'-hydroxyphenyl) -1- formazano] -1,3-dimethylbenzimidazolium - 2- [5- (1,3-dimethyl-2-benzimidazolidene) -3- (4'-N, N-dimethylaminophenyl) -1-formazano] chloride -1,3- dimethylbenzimidazolium - 2- [5- (1,3-dihydroxyethyl-2-benzimidazolidene) -1-formazano] chloride, 3-Dihydroxyethylbenzimidazolium - 2- [5- (1,3-dihydroxyethyl-2-benzimidazolidene) -3-methyl-1-formazano] -1,3-dihydroxyethylbenzimidazolium chloride 2- [5- (1,3-dihydroxyethyl) benzyl) chloride 1-dihydroxyethyl-2-benzimidazolidene) -3-ethyl-1-formazano] -1,3-dihydroxyethylbenzimidazolium-2- [5- (1,3-dihydroxyethyl-2-benzimidazolidene) -3-phenyl] -lchloride formazano] -1,3-dihydroxyethylbenzimidazolium - 2- [5- (1,3-dihydroxyethyl-2-benzimidazolidene) -3-isopropyl-1-formazano] -1,3-dihydroxyethylbenzimidazolium chloride - Chloride 2- [5- (1,3-Dihydroxyethyl-2-benzimidazolidene) -3- (4'-methoxyphenyl) -1-formazano] -1,3-dihydroxyethylbenzimidazolium - 2- [5- (1,3-dihydroxyethyl) -2-benzimidazolidene) -3- (4'-methoxyphenyl) -1-formazano] -1,3-dihydroxyethylbenzimidazolium chloride -dihydroxyethyl-2-benzimidazolidene) -3- (4'-hydroxyphenyl) -1-formazano] -1,3-dihydroxyethyl-benzimidazolium

  2- [5- (1,3-dihydroxyethyl-2-benzimidazolidene) -3- (4'-N, N-dimethylaminophenyl) -1-formazano] -1,3-dihydroxyethylbenzimidazolium chloride - 2- [2- [2-benzimidazolidene]] chloride 5- (1,3-dicarboxyethyl-2-benzimidazolidene) -1-formazano] -1,3-dicarboxyethylbenzimidazolium chloride; 2- [5- (1,3-dicarboxyethyl-2-benzimidazolidene) -3-methyl] chloride; 1-formazano] -1,3-dicarboxyethylbenzimidazolium - 2- [5- (1,3-dicarboxyethyl-2-benzimidazolidene) -3-ethyl-1-formazano] -1,3-dicarboxyethylbenzimidazolium chloride - Chloride 2- [5- (1,3-dicarboxyethyl-2-benzimidazolidene) -3-phenyl-1-formazano] -1,3-dicarboxyethylbenzimidazolium - 2- [5- (1,3-dicarboxyethyl) -2-dichlorobenzene benzimidazolidene) -3-isopropyl-1-formazano] -1,3-dicarboxyethylbenzimidazolium - 2- [5- (1,3-dicarboxyethyl-2-benzimidazolidene) -3- (4'-methoxyphenyl) -lchloride -formazano] -1,3-dicarboxyethylbenzimidazolium - 2- [5- (1,3-dicarboxyethyl-2-benzimidazolidene) -3- (4'-hydroxyphenyl) -1-formazano] -1,3-dicarboxyethyl chloride -benzimidazolium - 2- [5- (1,3-dicarboxyethyl-2-benzimidazolidene) -3- (4'-N, N-dimethylaminophenyl) -1-formazano] -1,3-dicarboxyethylbenzimidazolium chloride. Among all the compounds described above, the compounds of family A (first variant) will be particularly preferred.

  In the compositions of the invention the compound or compounds of formula (I) are preferably present in a concentration ranging from 0.001 to 10% and preferably from 0.005 to 5% and even more preferably from 0.01 to 2% by weight relative to to the total weight of the composition. The compounds of formula (I) may in particular be obtained by a process in which at least two equivalents of at least one hydrazone chosen from the hydrazones of formula A and the hydrazones of formula B are reacted. ## STR2 ## in which Z14, Z15, Z16, R25 have the same meanings respectively as Z7, Z8, Z13, R5 of the formula IV, Y being an organic or inorganic anion, x being an integer from 1 to 3, Z17, Z18, Z19, Z20, R26, R27 have the same meanings respectively as Z9, Z10, Z11, Z12, R8, R7 of the formula V, Y 'being an organic or inorganic anion, x' being an integer ranging from 1 to 3, with an equivalent an aldehyde of formula R23CHO, R23 having the same meaning as Ro of formula I. It is thus possible to react two equivalents of the same hydrazone or of two different hydrazones. According to a preferred variant, the aldehyde of formula R23CHO is generated in the reaction medium from an aldehyde precursor of formula R'23CH2OH in the presence of an oxidizing system, R'23 then has the same meaning as Ro of formula I. This oxidizing system may be a chemical oxidant or a biocatalytic oxidant such as an enzyme. In particular, the process for preparing the compound of formula (I) according to the present invention can be carried out in the presence of an aldehyde precursor of formula R'23CH2OH and at least one enzyme capable of generating a aldehyde from the aldehyde precursor of formula R'23CH2OH. The method for synthesizing the compounds of formula (I) enzymatically defined above is carried out by reacting at least two equivalents of at least one hydrazone chosen from hydrazones of formula A and hydrazones of formula B in which Z14 , Z15, Z16, R25 have the same meanings respectively as Z7, Z8, Z13, R5 of formula IV, Y being an organic or inorganic anion, x being an integer ranging from 1 to 3, Z17, Z18, Z19, Z20, R26, R27 have the same meanings respectively as Z9, Z10, Z11, Z12, R8, R7 of the formula V, Y 'being an organic or inorganic anion, x' being an integer from 1 to 3, with an equivalent of an aldehyde of formula R23CHO, R23 having the same meaning as R0 of formula I. Depending on the reagents used, the reaction is carried out with or without an oxidizing system, with or without a cofactor for the enzyme, with or without a cofactor regeneration system .

  For the purposes of the present application, the term "without oxidizing system" means that no oxidizing system other than atmospheric oxygen is used. Preferably, the reaction is carried out in an aerobic medium at a pH of between 3 and 11 and at a temperature of between 6 ° C. and 80 ° C.

  More generally, the aldehyde precursor that can be used to prepare the compound of formula (I) can be chosen from primary alcohols, sarcosine, 4-hydroxymandelate, N6-methyl-lysine, dimethylglycine, methylglutamate, 2-oxoacids for example 2-oxo-acid pyruvate, benzoylformate, phenylpyruvate, threonine. Preferably, it will be selected from primary alcohols. The enzymes capable of generating an aldehyde from this aldehyde precursor can be chosen from alcohol dehydrogenases EC 1.1.1.1, alcohol dehydrogenases EC 1.1.1.2, alcohol dehydrogenases EC 1.1.1.71, aromatic alcohol dehydrogenases EC 1.1.1.90 also referred to as aryl alcohol dehydrogenases, aromatic alcohol dehydrogenases EC 1.1.1.97, alcohol 3-hydroxybenzyl dehydrogenases EC 1.1.1.97, alcohol coniferylic dehydrogenases EC 1.1.1.194, cinnamyl alcohol dehydrogenases EC 1.1.1.195, methanol dehydrogenases EC 1.1.1.244, the aromatic alcohol oxidases EC 1.1.3.7 also called aryl alcohol oxidases, the alcohol oxidases EC 1.1.3.13, the 4-hydroxymandelate oxidases EC 1.1.3.19, the long chain alcohol hydrocarbon oxidases EC 1.1.3.20, the methanol oxidases EC 1.1.3.31, alcohol dehydrogenases EC 1.1.99.20, sarcosinase oxidases EC 1.5.3.1, N6-methyl-lysine oxidases EC 1. 5.3.4, dimethylglycine oxidases EC 1.5.3.10, sarcosine dehydrogenases EC 1.5.99.1, dimethylglycine dehydrogenases EC 1.5.99.2, methylglutamate dehydrogenases EC 1.5.99.5, 2-oxoacids decarboxylases EC 4.1.1.1, benzoylformate decarboxylases EC 4.1.1.7, phenylpyruvate decarboxylases EC 4.1.1.43, threonine aldolase EC 4.1.2.5. Mention may also be made of the following enzymes capable of generating an aldehyde whose preferred substrate is specified between parentheses: N-methyl L amino acid oxidase EC 1.5.3.2 (N-methyl-L-amino acid), trimethylamine dehydrogenase EC 1.5. 99.7 (trimethylamine), dimethylamine dehydrogenase EC 1.5.99.10 (dimethylamine), nitroethane oxidase EC 1.7.3.1 (nitroethane), indole 2,3-dioxygenase EC 1.13.11.17 (indole), taurine dioxygenase EC 1.14.11.17 (taurine), acetoin ribose 5 phosphate transaldolase EC 2.2.1.4 (3-hydroxybutan-2-one), diamine aminotransferase EC 2.6.1.29 (alpha omega diamine + 2-oxoglutate), alkenylglycerophosphocholine hydrolase EC 3.3.2.2 (alkenylglycerophosphocholine), alkenylglycerophosphoethanolamine hydrolase EC 3.3.2.5 (alkenylglycerophosphocholine), alkylalidase EC 3.8.1.1 (halomethane), phosphonoacetaldehyde hydrolase EC 3.11.1.1 (phosphonoacetaldehyde), indolepyruvate decarboxylase EC 4 .1.1.74 (3-indol-3-yl pyruvate), mandelonitrile lyase EC 4.1.2.10 (mandelonitrile), hydroxymandelonitrile lyase EC 4.1.2.11 (hydroxymandelonitrile), ketopantoaldolase EC 4.1.2.12 (2-hydroxy-2-isopropylbutanedioate ), dimethylaniline-N-oxide aldolase EC 4.1.2.24 (dimethylaniline-N-oxide), phenylserine aldolase EC 4.1.2.26 (phenylserine), sphinganine-1-phosphate aldolase EC 4.1.2.27 (sphinganine-1-phosphate) , 17-alpha hydroxyprogesterone aldolase EC 4.1.2.30 (17-alpha hydroxyprogesterone), trimethylamine oxide aldolase EC 4.1.2.23 (trimethylamine oxide), fucosterol epoxide lyase EC 4.1.2.23 (fucosterol epoxide), (3E) -4- ( 2-carboxyphenyl) -2-oxobut-3enoate aldolase EC 4.1.2.34 ((3E) -4- (2-carboxyphenyl) -2-oxobut-3-enoate), lactate aldolase EC 4.1.2.36 (lactate), benzoin aldolase EC 4.1.2.38 (benzoin), octoamine dehydratase EC 4.2.1.87 (1- (4-hydroxyphenyl) 2-aminoethanol), synephrine dehydratase EC 4.2.1.88 (1- (4-hydroxyphene) nyl) -2- (methylamino) ethanol), ethanol-aminephosphate phospholase EC 4.2.3.2 (ethanolamine phosphate), ethanolamine ammonia-lyase EC 4.3.1.7 (ethanolamine), dichloromethane dehalogenase EC 4.5.1.3 (dichloromethane), styrene oxide isomerase EC 5.3.99.7 (styrene oxide) The enzyme capable of generating an aldehyde from the aldehyde precursor used in the dyeing composition according to the invention may be derived from an extract of plants, animals, microorganisms (bacterium, fungus, yeast, microalgae) or viruses, differentiated or dedifferentiated cells, obtained in vivo or in vitro, modified or non-modified genetically, or synthetic (obtained by chemical or biotechnological synthesis). By way of examples of useful enzymes, mention may in particular be made of the genera Plectranthus, Pinus, Gastropoda, Manduca, Pichia, Candida, Pleurotus, Pseudomonas, and even more particularly the following species: Plectranthus colleoides, Pinus strobus which is a species of plant origin, Gastropod mollusc, Manduca sexta which are of animal origin, Pichia pastoris and Candida boidinii which are yeasts, Pleurotus pulmonarius which is a fungus, and Pseudomonas pseudoalcaligenes which is a bacterium.

  The choice of enzyme is a function of the nature of the aldehyde precursor. For example, when the aldehyde precursor is an alcohol, then the enzyme is selected from the enzymes capable of generating an aldehyde from that alcohol. When the aldehyde precursor is methylglutamate, then the enzyme is a methylglutamate dehydrogenase. According to a preferred variant, the aldehyde precursor is a primary alcohol and the enzyme is an enzyme capable of generating the aldehyde from an alcohol. For example, when the primary alcohol is a C 1 to C 6 aliphatic alcohol, then the enzyme capable of generating the aldehyde is selected from alcohol oxidases, alcohol dehydrogenases, methanol dehydrogenases, methanol oxidases. When the primary alcohol is benzyl alcohol, 4-tert-butyl benzyl alcohol, 3-hydroxy-4-methoxybenzyl alcohol, veratryl alcohol, 4-methoxybenzyl alcohol, cinnamic alcohol, 2,4-hexadien-1 -ol, aryl alcohol oxidases or aromatic alcohol dehydrogenases can be used as aldehyde precursors. For enzymes dehydrogenases, it is essential to include the cofactor (s) necessary for their activity, more specifically NAD + or NADP + or other molecules that can suck electron acceptor. The addition of a cofactor regeneration system can be used for reaction or economic reasons. This regeneration system can be enzymatic, chemical or electrochemical.

  The most diverse oxidants are used for the implementation of this process: hydrogen peroxide, organic peracids such as peracetic acid, persalts such as permanganate, perborate, persulfates, chromates or dichromates, hypochlorites , hypobromites, ferricyanides, peroxides such as manganese or lead oxides. Preferably oxygenated water will be used. The substrate concentration of the enzyme (aldehyde precursor) may be between 0.01M and 6M, preferably between 0.1M and 4M.

  The reaction can be carried out between pH 3 and pH 11, preferably between pH 5 and pH 9.5. The temperature for the reaction may be between 10 ° C. and 80 ° C., preferably between 20 ° C. and 65 ° C.

  The concentration of the hydrazone reaction medium is between 0.01M and 3M, preferably between 0.1M and 1M. The cofactor content for said enzymes may be between 0.01mM and 1M, preferably 0.1MM and 10mM. When carrying out the synthesis of the compounds of formulas (I), the reagents: the hydrazone (s), the enzyme (s), the substrate for the said enzyme, and / or the cofactor for the said enzyme, and / or oxidant and / or the cofactor regeneration system are mixed, the pH and temperature are adjusted. The compounds of formula I can also be obtained by a process in which a compound of formula (F1) or (F 2) is reacted with formula F R 26 Z 19 Z 20 Z 20 Z 17 I, R 11 Z14, Z15, Z16, Ro, R24, R25 for the formula F1 and Z17, Z18, Z19, Z20, Ro, R24, R26 for the formula F2 have the meanings described above, in the presence of an equivalent of a hydrazone of formula (A) or (B). According to a preferred variant, the compounds of formula (F1) or (F2) can be obtained by reaction of a compound of formula R "23C (OR24) 3 and a hydrazone of formula (A) or (B) in the presence or not of a protic solvent whose boiling point varies between 66 C and 180 C. R "23 has the same meaning as Ro of the formula (I) and R24 represents a radical chosen from methyl and ethyl groups.

  Preferably, the reaction is carried out in the presence of triethylorthoformate and trimethylorthoacetate at a temperature between 0 C and 150 C for a period of between 30 minutes and 12 hours.

  Preferably, the protic solvent is selected from H2O, ethanol, and methanol. (ii) extranuclear quaternary ammonium direct dye.

  For the purposes of the present invention, the term "direct cationic dye with extranuclear quaternary ammonium group" means a dye capable of dyeing keratinous fibers in the absence of any oxidizing agent and which has in its structure at least one N (+) R1R2R3 group. not included in a ring, R1, R2, R3 denoting independently of each other an optionally substituted C1-C30 alkyl radical or an optionally substituted phenyl radical. The optional substituents of the alkyl groups are preferably chosen from halogen atoms, the hydroxyl, amino, mono- or dihydroxyalkylC 1 -C 4 amino groups, any aryl groups of the aryl groups are preferably chosen from halogen atoms, alkyl groups, C.sub.1 -C.sub.30, hydroxyl groups, amino, mono- or dialkylC1-4amino, mono- or dihydroxyalkylC1-4amino, cyano, nitro, C2C acyl.

  Preferably, R 1, R 2 and R 3 all denote a C 1 -C 4 alkyl group. Even more preferentially, R1, R2 and R3 denote a methyl group. The extranuclear ammonium group may be attached to an aliphatic chain and in particular to an alkyl chain.

  The extranuclear ammonium group may also be attached to an aromatic carbon ring and in particular to a phenyl or naphthyl ring. mono or dialkylClC4amino, C6C30, cyano. Substituents

  As the cationic direct dye with an extranuclear quaternary ammonium group that may be used in the context of the present invention, mention may be made of the Basic Blue 22 anthraquinone dye and the nitrobenzene dyes described in US Pat. No. 5,256,823 and US Pat. No. 5,169,403. extranuclear quaternary ammonium group is chosen from those of formulas (VI), (VII) and (VIII): ## STR1 ##

  formulas (VI) to (VIII) in which: R1 represents a hydrogen atom or an amino radical; R2 represents a hydrogen atom or a nitro group; R3 represents a hydrogen atom, a nitro group or a C1-C4 alkoxy radical; R4 represents a C1-C4 alkyl radical; R5 represents a hydrogen atom or a paratrialkylCI-C4 ammoniophenyl group; R6 represents a bromine atom or a C1-C4 NH-paratrialkyl ammoniophenyl group; X represents an anion preferably selected from chloride, methyl sulfate and acetate. According to the present invention, the compounds corresponding to the mesomeric forms of the structures (VI) to (VIII) can also be used. Examples of compounds of formula (VI) that may be mentioned include Basic Brown 16, Basic Red 76, Basic Brown 17 and Basic Red 118 dyes. Examples of compounds of formula (VII) include Basic yellow dye 57. By way of example of compounds of formula (VIII), mention may be made of the Basic Blue 99 dye. X

  35 These color index names cover the following chemical structures (in the form of chlorides):. 8 - [(4-aminophenyl) azo] -7-hydroxy-2-trimethylammonio-naphthalene, 8 - [(2-methoxyphenyl) azo] -7-hydroxy-2-trimethylammonio-naphthalene, 8 - [(4- amino-3-nitrophenyl) azo] -7-hydroxy-2-trimethylammonionaphthalene, 8 - [(4-amino-2-nitrophenyl) azo] -7-hydroxy-2-trimethylammonionaphthalene, 3 - [(3-methyl) -2- 5-hydroxy-1-phenyl-pyrazol-4-yl) azo] -trimethylammonio-benzene, 3 - [(4-amino-6-bromo-5,8-dihydro-1-hydroxy-8-imino-5- oxo-2-naphthalenyl) -amino] -trimethylammonio-benzene, 3 - [(3,7-dibromo-5,8-dihydro-4-hydroxy-5-imino-8-oxo-1-naphthalenyl) -amino] -triméthylammonio-benzene.

  Said compounds of formulas (VI) to (VIII) are found alone or in combination in the products corresponding to the trade names proposed by WARNER JENKINSON, the following: -ARIANOR MAHOGANY; ARIANOR STEEL BLUE; ARIANOR MADDER RED; ARIANOR SIENNA BROWN; ARIANOR STRAW YELLOW; ARIANOR BORDEAUX. The direct dye (s) with an extranuclear quaternary ammonium group used according to the invention preferably represent from 0.001 to 10% by weight of the total weight of the dyeing composition and even more preferably from 0.005 to 5% by weight of this dyeing composition. weight.

  The medium suitable for dyeing (or support) is usually water or a mixture of water and at least one organic solvent to solubilize compounds that are not sufficiently soluble in water. As organic solvent, there may be mentioned for example lower alkanols C1-C4, such as ethanol and isopropanol; aromatic alcohols such as benzyl alcohol, as well as similar products 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 pH of the dyeing composition according to the invention is generally between 2 and 11 approximately, and preferably between 5 and 10 approximately. It can be adjusted to the desired value by means of acidifying or alkalizing agents usually used for dyeing keratinous fibers.

  Among the acidifying agents, mention may be made, by way of example, of mineral or organic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid, lactic acid, sulphonic acids.

  Among the alkalinizing agents that may be mentioned, by way of example, are ammonia, alkaline carbonates, alkanolamines such as mono-, di- and triethanolamines and their derivatives, sodium or potassium hydroxides and following formula (IX):

  Wherein W is a propylene moiety optionally substituted with a hydroxyl group or a C1-C6 alkyl radical; R3-R5N-W-N-R4; R3, R4, R5 and R6, which may be identical or different, represent a hydrogen atom, a C1-C6 alkyl radical or a C1-C6 hydroxyalkyl radical.

  The dyeing composition in accordance with the invention may, in addition to the direct dyes of the invention defined above, contain one or more additional additional direct dyes which may for example be chosen from nitrobenzene dyes, anthraquinone dyes, naphthoquinone dyes, triarylmethane dyes, xanthene dyes, non-cationic azo dyes.

  When it is intended for the oxidation dyeing, the dyeing composition in accordance with the invention contains, in addition to the cationic direct dye (s) (i) and (ii), one or more oxidation bases chosen from among the bases of oxidation conventionally used for oxidation dyeing and among which include paraphenylenediamines, bis-phenylalkylenediamines, paraaminophenols, ortho-aminophenols and heterocyclic bases. Among these oxidation bases, mention may especially be made of:

  (I) the para-phenylenediamines of the following formula (X) and their addition salts with an acid: NH 2 in which: R 1 represents a hydrogen atom, a C 1 -C 4 alkyl, C 1 -C 4 monohydroxyalkyl or polyhydroxyalkyl radical; C2-C4, (C1-C4) alkoxy (C1-C4) alkyl, C1-C4 alkyl substituted by nitrogen, phenyl or 4'-aminophenyl; R 2 represents a hydrogen atom, a C 1 -C 4 alkyl, C 1 -C 4 monohydroxyalkyl or C 2 -C 4 polyhydroxyalkyl radical, C 1 -C 4 alkoxy (C 1 -C 4) alkyl radical or C 1 -C 4 alkyl substituted by a grouping nitrogen; R 1 and R 2 may also form, with the nitrogen atom carrying them, a 5- or 6-membered nitrogenous heterocycle optionally substituted with one or more alkyl, hydroxyl or ureido groups; R3 represents a hydrogen atom, a halogen atom such as a chlorine atom, a C1-C4 alkyl, sulfo, carboxy, C1-C4 monohydroxyalkyl or C1-C4 hydroxyalkoxy, C1-C4 acetylaminoalkoxy radical; C 1 -C 4 mesylaminoalkoxy or C 1 -C 4 carbamoylaminoalkoxy, R 4 represents a hydrogen atom, a halogen atom or a C 1 -C 4 alkyl radical.

  Among the nitrogen groups of the formula (X) above, mention may be made in particular of amino, monoalkyl (C 1 -C 4) amino, dialkyl (C 1 -C 4) amino, trialkyl (C 1 -C 4) amino, monohydroxyalkyl (C 1 -C 4) alkyl radicals. C4) amino, imidazolinium and ammonium.

  Among the paraphenylenediamines of formula (X) above, there may be mentioned paraphenylenediamine, paratoluylenediamine, 2-chloro-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,5-dimethyl-para-phenylenediamine, N, N-dimethyl-para-phenylenediamine, N, N-diethyl-para-phenylenediamine, N, N-dipropyl-para-phenylenediamine, 4-amino-N, N diethyl-3-methyl-aniline, N, N-bis-03-hydroxyethyl) -paraphenylenediamine, 4-N, N-bis (13-hydroxyethyl) amino-2-methyl-aniline, 4-N, N-bis-03-hydroxyethyl) amino-2-chloroaniline, 2-13-hydroxyethyl-para-phenylenediamine, 2-fluoro-para-phenylenediamine, 2-isopropyl-para-phenylenediamine, N-O-hydroxypropyl) -paraphenylenediamine, 2-hydroxymethyl-para-phenylenediamine, N, N-dimethyl-3-methyl-para-phenylenediamine, N, N- (ethyl, 13-hydroxyethyl) -paraphenylenediamine, N- (13'-dihydroxypropyl) -paraphenylenediamine, N- (4'-aminophenyl) -paraphenylenediamine, N-phenyl-para-phenylenediamine, 2-13-hydroxyethyloxy-para-phenylenediamine, 2-13-acetylaminoethyloxy-para-phenylenediamine, N-O-methoxyethyl) -paraphenylenediamine, 2-methyl-1-N-13-hydroxyethylparaphenylenediamine, and their addition salts with an acid.

  Among the paraphenylenediamines of formula (X) above, para-phenylenediamine, paratoluylenediamine, 2-isopropyl-para-phenylenediamine, 2- (3-hydroxyethyl-para-phenylenediamine, 2-hydroxyethyloxy-para-phenylenediamine, 6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, N, N-bis - ((3-hydroxyethyl) -paraphenylenediamine, 2-chloro-para-phenylenediamine, and their addition salts with an acid 40 - (II) According to the invention, the term "double bases" is intended to mean compounds containing at least two aromatic rings bearing amino and / or hydroxyl groups.

  Among the double bases that can be used as oxidation bases in the dyeing compositions in accordance with the invention, there may be mentioned the compounds corresponding to the following formula (XI), and their addition salts with an NR9R10 NR11 R12 Y acid. In which - Z 1 and Z 2, which may be identical or different, represent a hydroxyl radical or - NH 2 may be substituted by a C 1 -C 4 alkyl radical or by a Y-linking arm; - the linking arm Y represents an alkylene chain comprising 1 to 14 carbon atoms, linear or branched may be interrupted or terminated by one or more nitrogen groups and / or by one or more heteroatoms such as oxygen, sulfur or nitrogen, and optionally substituted with one or several hydroxyl or C1-C6 alkoxy radicals; R5 and R6 represent a hydrogen or halogen atom, a C1-C4 alkyl, C1-C4 monohydroxyalkyl, C2-C4 polyhydroxyalkyl, C1-C4 aminoalkyl radical or a Y linkage arm;

  R7, R8, R9, Rio, R11 and R12, which may be identical or different, represent a hydrogen atom, a linker Y or a C1-C4 alkyl radical; it being understood that the compounds of formula (XI) have only one Y linker per molecule. Among the nitrogen groups of formula (XI) above, mention may be made in particular of amino, monoalkyl (C 1 -C 4) amino, dialkyl (C 1 -C 4) amino, trialkyl (C 1 -C 4) amino, monohydroxyalkyl (C 1 -C 4) C4) amino, imidazolinium and ammonium. Among the double bases of formulas (XI) above, mention may be made more particularly of N, N'-bis ((3-hydroxyethyl) -N, N'-bis (4'-aminophenyl) -1, 3-diamino-propanol, N, N'-bis - ((3-hydroxyethyl) -N, N'-bis- (4'-aminophenyl) -ethylenediamine, N, N'-bis- (4-aminophenyl) Tetramethylenediamine, N, N'-bis - ((3-hydroxyethyl) -N, N'-bis (4-aminophenyl) tetramethylenediamine, N, N'-bis- (4-methylaminophenyl) - tetramethylenediamine, N, N'-bis- (ethyl) -N, N'-bis- (4'-amino-3'-methylphenyl) -ethylenediamine, 1,8-bis- (2,5-diaminophenoxy) - 3,5-dioxaoctane, and their addition salts with an acid. Among these double bases of formula (XI), N, N'-bis - ((3-hydroxyethyl) -N, N'-bis- ( 4'-aminophenyl) -1,3-diamino-propanol, 1,8-bis- (2,5-diaminophenoxy) -3,5-dioxaoctane or one of their acid addition salts are particularly preferred (III) para-aminophenols corresponding to the following formula (XII), and their addition salts with an acid: 25 OH NH 2 wherein: R 13 represents a hydrogen atom, a halogen atom such as fluorine, a C 1 -C 4 alkyl, C 1 -C 4 monohydroxyalkyl, C 1 -C 4 alkoxy (C 1 -C 4) alkyl or aminoalkyl radical; C1-C4, or hydroxyalkyl (CIC4) C1-C4 aminoalkyl. R 14 represents a hydrogen atom or a halogen atom such as fluorine, a C 1 -C 4 alkyl, C 1 -C 4 monohydroxyalkyl, C 2 -C 4 polyhydroxyalkyl, C 1 -C 4 aminoalkyl, C 1 -C 4 cyanoalkyl or alkoxy (CI-C4) alkyl (Ci-C4).

  Among the para-aminophenols of formula (XII) above, mention may be made more particularly of para-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluoro-phenol and 4-amino. 3-hydroxymethylphenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol , 4-amino-2-β-hydroxyethylaminomethyl) phenol, and their addition salts with an acid. (IV) ortho-aminophenols which can be used as oxidation bases in the context of the present invention, are especially chosen from 2-amino-phenol, 2-amino-1-hydroxy-5-methyl- benzene, 2-amino-1-hydroxy-6-methyl-benzene, 5-acetamido-2-aminophenol, and their addition salts with an acid. 4225

  43 - (V) among the heterocyclic bases which can be used as oxidation bases in the dyeing compositions in accordance with the invention, mention may be made more particularly of pyridine derivatives, pyrimidine derivatives and pyrazole derivatives, and their addition salts with an acid.

  Among the pyridine derivatives, mention may be made more particularly of the compounds described for example in patents GB 1 026 978 and GB 1 153 196, such as 2,5-diaminopyridine, 2- (4-methoxyphenyl) amino-3- amino-pyridine, 2,3-diamino-6-methoxy-pyridine, 2 - ((3-methoxyethyl) amino-3-amino-6-methoxy pyridine, 3,4-diamino-pyridine, and their addition with an acid.

  Among the pyrimidine derivatives, mention may be made more particularly of the compounds described for example in German Patent DE 2,359,399 or Japanese JP 88-169,571 and JP 91-10659 or patent applications WO 96/15765, such as 2,4, 5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine, 2, 5,6-triaminopyrimidine, and pyrazolopyrimidine derivatives such as those mentioned in the patent application FR-A-2,750,048 and among which mention may be made of pyrazolo [1,5-a] -pyrimidine-3,7- diamine; 2,5-dimethyl-pyrazolo [1,5-a] pyrimidine-3,7-diamine; pyrazolo [1,5-a] pyrimidine-3,5-diamine; 2,7-dimethylpyrazolo [1,5-a] pyrimidine-3,5-diamine; 3-amino-pyrazolo [1,5-a] pyrimidin-7-ol; 3-amino-pyrazolo [1,5-a] pyrimidin-5-ol; 2- (3-Amino-pyrazolo [1,5-a] pyrimidin-7-ylamino) -ethanol; 2- (7-amino-pyrazolo [1,5-a] pyrimidin-3-ylamino) ethanol; 2 - [(3-Amino-pyrazolo [1,5-a] pyrimidin-7-yl) - (2-hydroxy-ethyl) amino] ethanol; 2 - [(7-amino-pyrazolo [1,5-a] pyrimidin-3-yl) - (2-hydroxyethyl) amino] ethanol; 5,6-dimethylpyrazolo [1,5-a] pyrimidine-3,7-diamine; 2,6-dimethyl-

  Pyrazolo [1,5-a] pyrimidine-3,7-diamine; 2,5-N7-N7-tetramethyl-pyrazolo [1,5-a] pyrimidine-3,7-diamine; 3-amino-5-methyl-7-imidazolylpropylamino-pyrazolo [1,5-a] pyrimidine; and their addition salts and tautomeric forms, when there is a tautomeric equilibrium and their acid addition salts.

  Among the pyrazole derivatives, mention may be made more particularly 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 such as 4,5-diamino-1-methyl-pyrazole, 3,4-diamino-pyrazole, 4,5-diamino-1- (4'-chlorobenzyl) -pyrazole, 4,5-diamino 1, 3-dimethylpyrazole, 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-1-03-hydroxyethyl-3-methyl-pyrazole, 4,5-diamino-1-β-hydroxyethyl-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-methylpyrazole, 4,5-diamino-3-hydroxymethyl-1-isopropyl-pyrazo 1, 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-methylaminopyrazole, 3,5-diamino-4-yl-hydroxyethyl) amino-1- methyl-pyrazole, and their addition salts with an acid.

  When used, the oxidation base (s) preferably represent from 0.0005 to 12% by weight approximately of the total weight of the dyeing composition, and still more preferably from 0.005 to 6% by weight approximately of this weight. .

  When it is intended for the oxidation dyeing, the dyeing composition according to the invention can also contain, in addition to cationic direct dyes (i) and (ii) as well as oxidation bases, one or more couplers of way to modify or enrich in glints the shades obtained by using the direct cationic dye (s) (i) and the oxidation base (s).

  The couplers that can be used in the dyeing composition according to the invention are those conventionally used in oxidation dyeing compositions, that is to say meta-aminophenols, meta-phenylenediamines, meta-diphenols, naphthols and heterocyclic couplers such as that, for example, indole derivatives, indoline derivatives, sesamol and its derivatives, pyridine derivatives, pyrazolotriazole derivatives, pyrazolones, indazoles, benzimidazoles, benzothiazoles, benzoxazoles, 1,3-benzodioxoles, quinolines and their addition salts with an acid.

  These couplers are more particularly chosen from 2,4-diamino-1-yl-hydroxyethyloxy-benzene, 2-methyl-5-aminophenol and 5-N- (13-hydroxyethyl) amino-2-methyl-phenol. 3-amino-phenol, 1,3-dihydroxybenzene, 1,3-dihydroxy-2-methyl-benzene, 4-chloro-1,3-dihydroxybenzene, 2-amino-4-β-hydroxyethylamino) 1-methoxy-benzene, 1,3-diamino-benzene, 1,3-bis (2,4-diaminophenoxy) -propane, sesamol,

  46 amino-2-methoxy-4,5-methylenedioxybenzene, α-naphthol, 6-hydroxyindole, 4-hydroxyindole, 4-hydroxy-N-methylindole, 6-hydroxyindoline, 2, 6-dihydroxy-4-methyl-pyridine, 1-H-3-methyl-pyrazol-5-one, 1-phenyl-3-methyl-pyrazol-5-one, 2-amino-3-hydroxypyridine, 3,6-dimethyl-pyrazolo [3,2-c] -1,2,4-triazole, 2,6-dimethyl-pyrazolo [1,5-b] -1,2,4-triazole and their addition salts with an acid.

  In general, the acid addition salts of the oxidation bases and couplers are chosen in particular from hydrochlorides, hydrobromides, sulphates and tartrates, lactates and acetates.

  When present, the coupler or couplers preferably represent from 0.0001 to 10% by weight approximately of the total weight of the dye composition and even more preferably from 0.005 to 5% by weight approximately of this weight.

  The dyeing composition according to the invention may also contain various adjuvants conventionally used in compositions for dyeing hair, such as antioxidants, penetrating agents, sequestering agents, perfumes, buffers, nonionic polymers. , anionic or amphoteric, non-silicone cationic polymers, nonionic, cationic or amphoteric surfactants, ceramides, preservatives, filtering agents, opacifying agents.

  Of course, those skilled in the art will take care to choose this or these optional additional compounds in such a way that the properties

  47 advantageous intrinsically attached to the dye composition according to the invention are not, or not substantially impaired by the addition or additions envisaged.

  The dye composition according to the invention may be in various forms, such as in the form of liquids, shampoos, creams, gels, or in any other form suitable for dyeing keratinous fibers, and in particular human hair . It can be obtained by extemporaneous mixing of a composition, optionally pulverulent, containing the cationic direct dye (s) of formula (I) with a composition containing at least one direct dye with an extranuclear quaternary ammonium group as defined previously.

  When the combination of the cationic direct dye (i) and the extranuclear quaternary ammonium direct dye (ii) according to the invention is used in a composition intended for oxidation dyeing (one or more oxidation bases are then used optionally in the presence of one or more couplers) or when it is used in a composition intended for direct lightening dyeing, then the dye composition according to the invention also contains at least one oxidizing agent, chosen for example from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulfates, and enzymes such as peroxidases, laccases and two-electron oxidoreductases. The use of hydrogen peroxide or enzymes is particularly preferred.

  Another subject of the invention is a process for dyeing keratinous fibers and in particular human keratin fibers such as

  The hair using the dye composition as defined above.

  According to a first variant of this dyeing process in accordance with the invention, at least one dye composition as defined above is applied to the fibers for a time sufficient to develop the desired coloration, after which it is rinsed and optionally washed with shampooing. , rinse again and dry.

  The time required for the development of the coloration on the keratin fibers is generally between 3 and 60 minutes and even more precisely 5 and 40 minutes.

  According to a second variant of this dyeing process according to the invention, at least one dye composition as defined above is applied to the fibers for a time sufficient to develop the desired coloration, without final rinsing.

  According to another particular embodiment of this dyeing process, and when the dyeing composition according to the invention contains at least one oxidizing agent, the dyeing process comprises a preliminary step consisting in storing in separate form, on the one hand, a composition (A1) comprising, in a medium suitable for dyeing, at least one cationic direct dye (i) as defined above and, secondly, a composition (B1) containing, in a medium suitable for dyeing, at least one oxidizing agent, and then mixing them at the time of use before applying this mixture to the keratinous fibers, the composition (Al) or the composition (B1) containing at least one

  At least one direct dye with an extranuclear quaternary ammonium group as defined previously.

  According to another particular embodiment of this dyeing process, and when the dyeing composition according to the invention contains at least one oxidation base and at least one oxidizing agent, the dyeing process comprises a preliminary step of storing under separate form, on the one hand, a composition (A2) comprising, in a medium suitable for dyeing, at least one cationic direct dye (i) as defined above and at least one oxidation base and secondly a composition (B2) containing, in a medium suitable for dyeing, at least one oxidizing agent, then mixing them at the time of use before applying this mixture to the keratinous fibers, the composition (A2) or the composition (B2) containing at least one direct dye with extranuclear quaternary ammonium group (ii) as defined above.

  Another subject of the invention is a multi-compartment device or "kit" for dyeing or any other multi-compartment packaging system of which a first compartment contains the composition (A1) or (A2) as defined above and a second compartment contains the composition (B1) or (B2) as defined above. These devices may be equipped with means for delivering the desired mixture onto the hair, such as the devices described in patent FR-2 586 913 in the name of the applicant.

  The following examples are intended to illustrate the invention without limiting its scope.

  EXAMPLES Comp Dried Formula 1 N + 1 N N- CH 2 CH 2 OH CH 3 CH 2 CH 2 OH 2 Cl N N 1 1 N ON C I I I 187/100 OH 2 Application Examples Example 1

  The following dyeing composition (contents expressed in grams of active material) was prepared. Dye 1 according to the invention 0.2 Hydroxyethylcellulose 0.72 Decylpolyglucoside 9.00 Arianor Steel Blue (Basic Blue 99) 0.2 Benzyl alcohol 4.00 Preservatives 0 , 06 Boron buffer qs pH 9 50 demineralized water 100 The composition was applied on the one hand to locks of natural gray hair with 90% of white, on the other hand on strands of gray hair permed to 90% of white, for 30 minutes at temperature ambient (20 C).

  After the break time, the locks were rinsed, shampooed and rinsed and dried. They were dyed in a very selective low-chromatic violet-blue hue.

  Example 2 A result similar to that of Example 1 is obtained by replacing weight for weight of dye 1 with dye 2 and the Basic Blue 99 with Basic Blue 22.15.

Claims (10)

  1.Composition for dyeing keratinous fibers, in particular human keratinous fibers and more particularly hair comprising, in a medium suitable for dyeing (i) at least one tetraazapentamethine compound of formula (I) and (ii) at least one direct dye having at least one extranuclear quaternary ammonium group. In which - Wi represents a cationic heteroaromatic radical of formula (II) or (III): (II) (III) - W2 represents a heteroaromatic radical of formula (IV) or (V): R3 X-R8 (V) in which: - Zo represents a radical CR2, a nitrogen atom or a radical NR21, - Z1 represents an oxygen atom, sulfur or a radical NR9, - Z2 represents a nitrogen atom or a CR10 radical, -Z3 represents a nitrogen atom or a CR11 radical, - Z4 represents a nitrogen atom or a CR12 radical, - Z5 represents a nitrogen atom or a CR13 radical, Z6 represents a nitrogen atom or a CR14 radical; Z7 represents an oxygen atom, sulfur atom or an NR15 radical; Z8 represents a nitrogen atom or a CR16 radical; Z9 represents a nitrogen atom; or a radical CR17, - Z10 represents a nitrogen atom or a radical CR18, - Z11 represents a nitrogen atom or a radical CR19, - Z12 represents a nitrogen atom or a radical CR20, - Z13 represents a CR6 radical, a nitrogen atom or an NR22 radical, - it being understood that each of the rings of formulas (II), (III), (IV) and (V) contain not more than three nitrogen atoms, and that two of the three nitrogen atoms may be contiguous, the link a of the cationic heteroaromatic 5-membered radical of the formula (II) being connected to the nitrogen atom N1 of the formula (I), the bond b of the 6-membered cationic heteroaromatic radical of the formula (III) being connected to the nitrogen atom N1 of the formula (I). the double bond to the 5-membered heteroaromatic radical of the formula (IV) being connected to the nitrogen atom N 2 of the formula (I), the double bond b 'of the heteroaromatic 6-membered radical of the formula (V) being connected to the nitrogen atom N2 of the formula (I), the bond b connecting the cationic heteroaromatic radical of the formula III to the nitrogen atom N1 of the formula (I) being located in the ortho or para position of the nitrogen atom carrying the radical R4 when Z5 represents a radical CR13; the bond b being located in the ortho position of the nitrogen atom carrying the radical R4 when Z5 represents a nitrogen atom, - the bond b ', connecting the heteroaromatic radical of the formula V to the nitrogen atom N2 of the formula (I) being located ortho or para position of the nitrogen atom carrying the radical R7 when Z11 represents a CR19 radical; the bond b 'being located in the ortho position of the nitrogen atom bearing the radical R7 when Z11 represents a nitrogen atom, - R2, R6, Rio and R16 represent, independently of one another, an atom hydrogen; a linear or branched C1-C4 alkyl radical, unsubstituted or substituted with one to three radicals chosen from hydroxyl, C1-C2 alkoxy, (poly) -hydroxyalkoxy C2-C4, amino, (di) alkylamino C1 radicals; -C2, carboxy or sulfonic; a phenyl radical which is unsubstituted or substituted by one to three radicals chosen from hydroxyl, C 1 -C 2 alkoxy, (C 2 -C 4) (poly) hydroxyalkoxy, amino, C 1 -C 2 (di) alkylamino radicals; a carboxy radical; a sulfonylamino radical, -R1, R4, R5, R7, R9, R15, R21, and R22 represent, independently of one another, a linear or branched C1-C8 alkyl radical, unsubstituted or substituted with a three radicals selected from hydroxy, C1-C2 alkoxy, (C2-C4) poly (poly) hydroxyalkoxy, amino, C1-C2, di (C1-C2alkyl), carboxy or sulfonic; - Ro, R3, R8, R11, R12, R13, R14, R17, R18, R19, and R20 represent, independently of one another, a hydrogen atom, a linear or branched C1-C16 hydrocarbon chain this chain may be saturated or unsaturated by one to three unsaturations, this chain being unsubstituted or substituted by one to three radicals chosen from hydroxyl, C 1 -C 2 alkoxy, (C 2 -C 4) (poly) hydroxyalkoxy, amino, (di) C1-C2 alkylcarbino, carboxy, sulfonic, sulfonylamino, (poly) -hydroxyalkylamino C2-C4 or a halogen atom such as chlorine, fluorine or bromine; a phenyl radical which is unsubstituted or substituted with one to three radicals chosen from hydroxyl, C 1 -C 2 alkoxy, C 2 -C 4 (poly) hydroxyalkoxy, amino, C 1 -C 2 (di) alkylamino, carboxy, sulphonic and sulphonylamino radicals; (C 2 -C 4) (poly) -hydroxyalkylamino or a halogen atom such as chlorine, fluorine or bromine; a heteroaryl radical chosen from pyrazolyl, pyrrolyl, imidazolyl, thiazolyl, oxazolyl, triazolyl, pyridinyl, pyrimidinyl, triazinyl, pyrazinyl and pyridazinyl radicals, in addition this hydrocarbon-based chain may be interrupted by one or two oxygen and nitrogen atoms, of sulfur or by a radical SO2, - being understood that Ro, R3, R8, R11, R12, R13, R14, R17, R18, R19, and R20 do not comprise a peroxide bond, or diazo or nitroso radicals, - R2 with Rlo, R11 with R12, R6 with R16, and R17 with R18 being able to form independently of each other a 5- or 6-membered aromatic carbon ring unsubstituted or substituted by one or two hydroxy, amino, (di) alkyl radicals. C2 amino, C1-C2 alkoxy, (poly) hydroxyalkyl C2-C4 amino, X is an organic or inorganic anion.   2.Composition according to claim 1 characterized in that in the formula I, ZI represents an oxygen atom or a radical NR9 and Z7 represents an oxygen atom or a radical NR15   3.Composition according to claims 1 and 2 wherein Ro represents a hydrogen atom; a linear or branched C 1 -C 6 alkyl radical, unsubstituted or substituted with one to three radicals selected from hydroxy, C 1 -C 2 alkoxy, (C 2 -C 4) (poly) hydroxyalkoxy, amino, (C 1 -C) alkylamino radicals; C2, (poly) hydroxyalkylamino C2-C4, carboxy or sulfonic; a phenyl radical, unsubstituted or substituted with one to three radicals chosen from hydroxyl, C 1 -C 2 alkoxy, (C 2 -C 4) (poly) hydroxyalkoxy, amino, C 1 -C 2 (di) alkylamino, carboxyl, sulfonic or a halogen atom such as chlorine, fluorine or bromine; an optionally cationic heteroaryl radical chosen from pyrazolyl, pyrrolyl, imidazolyl, thiazolyl, oxazolyl, triazolyl, pyridinyl, pyrimidinyl, triazinyl, pyrazinyl and pyridazinyl radicals.   4.Composition according to any one of the preceding claims wherein Ro represents a hydrogen atom; a methyl, ethyl, 2-methoxyethyl radical; a phenyl radical which is unsubstituted or substituted by an amino, (di) methylamino, (di) (2-hydroxyethyl) amino radical, an optionally cationic heteroaryl radical chosen from pyrazolyl, pyrrolyl, imidazolyl and pyridinyl radicals.   5.Composition according to any one of the preceding claims wherein R2, R6, Rio and R16 represent a hydrogen atom, a C1-C4 alkyl radical unsubstituted or substituted with one to two radicals chosen from hydroxyl and amino radicals. (di) C1-C2 alkylamino, carboxy, phenyl radical.   6.Composition according to any one of the preceding claims wherein R2, R6, Rio and R16 preferably represent a hydrogen atom, a methyl radical, phenyl, 2-hydroxymethyl, a carboxy.   7.Composition according to any one of the preceding claims wherein R1, R4, R5, R7, R9, R15, R21 and R22 preferably represent a C1-C4 alkyl radical, unsubstituted or substituted by one to two radicals selected from the radicals. hydroxy, C 1 -C 2 alkoxy, amino, (di) C 1 -C 2 alkyl, carboxy, sulfonic.   8.Composition according to any one of the preceding claims wherein R1, R4, R5, R7, R9, R15, R21 and R22 represent a methyl, ethyl, 2-hydroxyethyl, 1-carboxymethyl, 2-carboxyethyl, 2- radical. sulfonyléthyle.   9.Composition according to any one of the preceding claims wherein R3, R8, R11, R12, R13, R14, R17, R18, R19, and R20 represent independently of each other, a hydrogen atom; a linear or branched C1-C4 alkyl radical, unsubstituted or substituted with one to two radicals chosen from hydroxyl, C1-C2 alkoxy, (C2-C4) poly (-hydroxyalkoxy), amino, (di) C1-C4 alkylamino radicals; C2, carboxy or sulfonic; a phenyl radical, unsubstituted or substituted by one to two radicals chosen from hydroxyl, C 1 -C 2 alkoxy, (C 2 -C 4) (poly) -hydroxyalkoxy, amino, (C 1 -C 2) alkyl, di (C 1 -C 2) alkyl, carboxy or sulfonic radicals; a halogen atom such as chlorine, fluorine or bromine; a sulfonylamino radical; a C2-C4 (poly) -hydroxyalkylamino radical. 1O.Composition according to any one of the preceding claims wherein R3, R8, R11, R12, R13, R14, R17, R18, R19, andR20 represent independently of one another a hydrogen atom, a methyl radical , 2-hydroxymethyl, carboxy, methoxy, ethoxy, 2-hydroxyethyloxy, amino, methylamino, dimethylamino, 2-hydroxyethylamino. 11.Composition according to any one of the preceding claims wherein W1 is a 2-pyridinium radical and W2 is a 2-pyridine radical. 12.Composition according to claim 11 wherein the compound of formula (I) is selected from the following compounds: - 2- [5- (N-methyl-2-pyridinylidene) -1-formazano] -N-methylpyridinium chloride. 2- [5- (N-methyl-2-pyridinylidene) -3-methyl-1-formazano] -N-methylpyridinium chloride. 2- [5- (N-methyl-2-pyridinylidene) -3-ethyl-1-formazano] -N-methylpyridinium chloride. 2- [5- (N-methyl-2-pyridinylidene) -3-isopropyl-1-formazano] -N-methylpyridinium chloride. 2- [5- (N-methyl-2-pyridinylidene) -3-phenyl-1-formazano] -N-methylpyridinium chloride. 2- [5- (N-methyl-2-pyridinylidene) -3- (4'-methoxyphenyl) -1-formazano] -N-methylpyridinium chloride. 2- [5- (N-methyl-2-pyridinylidene) -3- (4'-hydroxyphenyl) -1-formazano] -N-methylpyridinium chloride. 2- [5- (N-methyl-2-pyridinylidene) -3- (4'-N, N-dimethylaminophenyl) -1-formazano] -N-methylpyridinium chloride. 2- [5- (4-Pyrrolidino-N-methyl-2-pyridinylidene) -1-formazano] -4-pyrrolidino-N-methylpyridinium chloride. 2- [5- (4-Pyrrolidino-N-methyl-2-pyridinylidene) 3-methyl-1-formazano] -4-pyrrolidino-N-methylpyridinium chloride. 2- [5- (4-Pyrrolidino-N-methyl-2-pyridinylidene) 3-ethyl-1-formazano] -4-pyrrolidino-N-methylpyridinium chloride. 2- [5- (4-Pyrrolidino-N-methyl-2-pyridinylidene) -3-isopropyl-1-formazano] -4-pyrrolidino-N-methylpyridinium chloride. 2- [5- (4-Pyrrolidino-N-methyl-2-pyridinylidene) 3-phenyl-1-formazano] -4-pyrrolidino-N-methylpyridinium chloride. 2- [5- (4-Pyrrolidino-N-methyl-2-pyridinylidene) -3- (4'-methoxyphenyl) -1-formazano] -4-pyrrolidino-N-methylpyridinium chloride. 2- [5- (4-Pyrrolidino-N-methyl-2-pyridinylidene) -3- (4'-hydroxyphenyl) -1-formazano] -4-pyrrolidino-N-methylpyridinium chloride. 2- [5- (4-Pyrrolidino-N-methyl-2-pyridinylidene) -3- (4'-N, N-dimethylaminophenyl) -1-formazano] -4-pyrrolidino-N-methylpyridinium chloride. 2- [5- (N-hydroxyethyl-2-pyridinylidene) -1-formazano] -N-hydroxyethylpyridinium chloride. 2- [5- (N-hydroxyethyl-2-pyridinylidene) -3-methyl-1-formazano] -N-hydroxyethylpyridinium chloride. 2- [5- (N-hydroxyethyl-2-pyridinylidene) -3-ethyl-1-formazano] -N-hydroxyethyl-pyridinium chloride. 2- [5- (N-hydroxyethyl-2-pyridinylidene) -3-phenyl-1-formazano] -N-hydroxyethyl-pyridinium chloride. 2- [5- (N-hydroxyethyl -2-pyridinylidene) -3-isopropyl-1-formazano] -N-hydroxyethylpyridinium chloride. 2- [5- (N-Hydroxyethyl-2-pyridinylidene) -3- (4'-methoxyphenyl) 1-formazano] -N-hydroxyethylpyridinium chloride. 2- [5- (N-hydroxyethyl-2-pyridinylidene) -3- (4'-hydroxyphenyl) -1-formazano] -N-hydroxyethylpyridinium chloride. 2- [5- (N-hydroxyethyl-2-pyridinylidene) -3- (4'-N, N-dimethylaminophenyl) -1-formazano] -N-hydroxyethyl-pyridinium chloride. 2- [5- (N-carboxyethyl-2-pyridinylidene) -1-formazano] -N-carboxyethylpyridinium chloride. 2- [5- (N-carboxyethyl-2-pyridinylidene) -3-methyl-1-formazano] -N-carboxyethylpyridinium chloride. 2- [5- (N-carboxyethyl-2-pyridinylidene) -3-ethyl-1-formazano] -N-carboxyethylpyridinium chloride. 2- [5- (N-carboxyethyl-2-pyridinylidene) -3-phenyl-1-formazano] -N-carboxyethylpyridinium chloride. 2- [5- (N-carboxyethyl-2-pyridinylidene) -3-isopropyl-1-formazano] -N-carboxyethylpyridinium chloride. 2- [5- (N-carboxyethyl-2-pyridinylidene) -3- (4'-methoxyphenyl) -1-formazano] -N-carboxyethylpyridinium chloride. 2- [5- (N-carboxyethyl-2-pyridinylidene) -3- (4-hydroxyphenyl) -1-formazano] -N-carboxyethylpyridinium chloride. 2- [5- (N-carboxyethyl-2-pyridinylidene) -3- (4'-N, N-dimethylaminophenyl) -1-formazano] -N-carboxymethylpyridinium chloride. 13.Composition according to any one of claims 1 to 10 wherein Wi is a 4-pyridinium radical and W2 is a 4-pyridine radical. 14.Composition according to claim 13 wherein the compound of formula (I) is selected from the following compounds: - 4- [5- (N-methyl-4-pyridinylidene) -1-formazano] N-methylpyridinium chloride. 4- [5- (N-methyl-4-pyridinylidene) -3-methyl-1-formazano] -N-methylpyridinium chloride. 4- [5- (N-methyl-4-pyridinylidene) -3-ethyl-1-formazano] -N-methylpyridinium chloride. 4- [5- (N-methyl-4-pyridinylidene) -3-isopropyl-1-formazano] -N-methylpyridinium chloride. 4- [5- (N-methyl-4-pyridinylidene) -3-phenyl-1-formazano] -N-methylpyridinium chloride. 4- [5- (N-methyl-4-pyridinylidene) -3- (4'-methoxyphenyl) -1-formazano] -N-methylpyridinium chloride. 4- [5- (N-methyl-4-pyridinylidene) -3- (4'-hydroxyphenyl) -1-formazano] -N-methylpyridinium chloride. 4- [5- (N-methyl-4-pyridinylidene) -3- (4'-N, N-dimethylaminophenyl) -1-formazano] -N-methylpyridinium chloride. 4- [5- (N-hydroxyethyl-4-pyridinylidene) -1-formazano] -N-hydroxyethylpyridinium chloride. 4- [5- (N-hydroxyethyl-4-pyridinylidene) -3-methyl-1-formazano] -N-hydroxyethylpyridinium chloride. 4- [5- (N-hydroxyethyl-4-pyridinylidene) -3-ethyl-1-formazano] -N-hydroxyethyl-pyridinium chloride. 4- [5- (N-hydroxyethyl-4-pyridinylidene) -3-phenyl-1-formazano] -N-hydroxyethyl-pyridinium chloride. 4- [5- (N-hydroxyethyl-4-pyridinylidene) -3-isopropyl-1-formazano] -N-hydroxyethylpyridinium chloride. 4- [5- (N-Hydroxyethyl-4-pyridinylidene) -3- (4'-methoxyphenyl) 1-formazano] -N-hydroxyethylpyridinium chloride. 4- [5- (N-hydroxyethyl-4-pyridinylidene) -3- (4'-hydroxyphenyl) -1-formazano] -N-hydroxyethylpyridinium chloride. 4- [5- (N-hydroxyethyl-4-pyridinylidene) -3- (4'-N, N-dimethylaminophenyl) -1-formazano] -N-hydroxyethyl pyridinium chloride. 4- [5- (N-carboxyethyl-4-pyridinylidene) -1-formazano] -N-carboxyethylpyridinium chloride. 4- [5- (N-carboxyethyl-4-pyridinylidene) -3-methyl-1-formazano] -N-carboxyethyl-pyridinium chloride. 4- [5- (Ncarboxyethyl-4-pyridinylidene) -3-ethyl-1-formazano] -N-carboxyethylpyridinium chloride. 4- [5- (N-carboxyethyl-4-pyridinylidene) -3-phenyl-1-formazano] -N-carboxyethylpyridinium chloride. 4- [5- (N-carboxyethyl-4-pyridinylidene) -3-isopropyl-1-formazano] -N-carboxyethylpyridinium chloride. 4- [5- (N-carboxyethyl-4-pyridinylidene) -3- (4'-methoxyphenyl) 1-formazano] -N-carboxyethylpyridinium chloride. 4- [5- (Ncarboxyethyl-4-pyridinylidene) -3- (4'-hydroxyphenyl) -1-formazano] -N-carboxymethylpyridinium chloride. 4- [5- (N-carboxyethyl-4-pyridinylidene) -3- (4'-N, N-dimethylaminophenyl) -1-formazano] -N-carboxyethyl-pyridinium chloride. 15.Composition according to any one of claims 1 to 10 wherein Wi is a 2-imidazolium radical and W2 is a 2-imidazole radical. 16.Composition according to claim 15 wherein the compound of formula (I) is chosen from the following compounds: - 2- [5- (1,3-dimethyl-2-imidazolidene) -1-formazano] -1 chloride, 3-dimethyl-imidazolium. 2- [5- (1,3-Dimethyl-2-imidazolidene) -3-methyl-1-formazano] -1,3-dimethylimidazolium chloride. 2- [5- (1,3-Dimethyl-2-imidazolidene) -3-ethyl-1-formazano] -1,3-dimethylimidazolium chloride. 2- [5- (1,3-Dimethyl-2-imidazolidene) -3-isopropyl-1-formazano] -1,3-dimethylimidazolium chloride. 2- [5- (1,3-Dimethyl-2-imidazolidene) -3-phenyl-1-formazano] -1,3-dimethylimidazolium chloride. 2- [5- (1,3-Dimethyl-2-imidazolidene) -3- (4'-methoxyphenyl) -1-formazano] -1,3-dimethylimidazolium chloride. 2- [5- (1,3-Dimethyl-2-imidazolidene) -3- (4'-hydroxyphenyl) -1-formazano] -1,3-dimethylimidazolium chloride. 2- [5- (1,3-Dimethyl-2-imidazolidene) -3- (4'-N, N-dimethylaminophenyl) -1-formazano] -1,3-dimethylimidazolium chloride. 2- [5- (1,3-dihydroxyethyl-2-imidazolidene) -1-formazano] -1,3-dihydroxyethylimidazolium chloride. 2- [5- (1,3-dihydroxyethyl-2-imidazolidene) -3-methyl-1-formazano] -1,3-dihydroxyethylimidazolium chloride. 2- [5- (1,3-dihydroxyethyl-2-imidazolidene) -3-ethyl-1-formazano] -1,3-dihydroxyethylimidazolium chloride. 2- [5- (1,3-dihydroxyethyl-2-imidazolidene) -3-phenyl-1-formazano] -1,3-dihydroxyethylimidazolium chloride. 2- [5- (1,3-dihydroxyethyl-2-imidazolidene) -3-isopropyl-1-formazano] -1,3-dihydroxyethylimidazolium chloride. 2- [5- (1,3-Dihydroxyethyl-2-imidazolidene) -3- (4'-methoxyphenyl) -1-formazano] -1,3-dihydroxyethylimidazolium chloride. 2- [5- (1,3-dihydroxyethyl-2-imidazolidene) -3 (4'-hydroxyphenyl) -1-formazano] -1,3-dihydroxyethylimidazolium chloride. 2- [5- (1,3-Dihydroxyethyl-2-imidazolidene) -3- (4'-N, N-dimethylaminophenyl) -1-formazano] -1,3-dihydroxyethylimidazolium chloride. 2- [5- (1,3-dicarboxyethyl-2-imidazolidene) -1-formazano] -1,3-dicarboxyethylimidazolium chloride. 2- [5- (1,3-dicarboxyethyl-2-imidazolidene) -3-methyl-1-formazano] -1,3-dicarboxyethylimidazolium chloride. 2- [5- (1,3-Dimethyl) -2- dicarboxyethyl-2-imidazolidene) -3-ethyl-1-formazano] -1,3-dicarboxyethylimidazolium. 2- [5- (1,3-Dicarboxyethyl-2-imidazolidene) -3-phenyl-1-formazano] -1,3-dicarboxyethylimidazolium chloride. 2- [5- (1,3-Dicarboxyethyl-2-imidazolidene) -3-isopropyl-1-formazano] -1,3-dicarboxyethylimidazolium chloride. 2- [5- (1,3-Dicarboxyethyl-2-imidazolidene) -3- (4'-methoxyphenyl) -1-formazano] -1,3-dicarboxyethylimidazolium chloride. 2- [5- (1,3-Dicarboxyethyl-2-imidazolidene) -3- (4'-hydroxyphenyl) -1-formazano] -1,3-dicarboxyethylimidazolium chloride. 2- [5- (1,3-Dicarboxyethyl-2-imidazolidene) -3- (4'-N, N-dimethylaminophenyl) -1-formazano] -1,3-dicarboxyethylimidazolium chloride. 17.Composition according to any one of claims 1 to 10 wherein Wi is a 5-pyrazolium radical and W2 is a 5-pyrazole radical. 18.Composition according to claim 17 wherein the compound of formula (I) is selected from the following compounds: - 5- [5- (1,2-dimethyl-5-pyrazolidene) -1-formazano] -1 chloride, dimethyl-2-pyrazolinium. 5- [5- (1,2-Dimethyl-5-pyrazolidene) -3-methyl-1-formazano] -1,2-dimethyl-pyrazolinium chloride. 5- [5- (1,2-Dimethyl-5-pyrazolidene) -3-ethyl-1-formazano] -1,2-dimethyl-pyrazolinium chloride. 5- [5- (1,2-Dimethyl-5-pyrazolidene) -3-isopropyl-1-formazano] -1,2-dimethyl-pyrazolinium chloride. 5- [5- (1,2-Dimethyl-5-pyrazolidene) -3-phenyl-1-formazano] -1,2-dimethyl-pyrazolinium chloride. 5- [5- (1,2-Dimethyl-5-pyrazolidene) -3- (4'-methoxyphenyl) -1-formazano] -1,2-dimethyl-pyrazolinium chloride. 5- [5- (1,2-Dimethyl-5-pyrazolidene) -3- (4'-hydroxyphenyl) -1-formazano] -1,2-dimethyl-pyrazolinium Chloride. (1,2-Dimethyl-5-pyrazolidene) -3- (4'-N, N-dimethylaminophenyl) -1-formazano] -1,2-dimethyl-pyrazolinium. 5- [5- (1,2-dihydroxyethyl-5-pyrazolidene) -1-formazano] -1,2-dihydroxyethylpyrazolinium chloride. 5- [5- (1,2-dihydroxyethyl-5-pyrazolidene) -3-methyl-1-formazano] -1,2-dihydroxyethylpyrazolinium chloride. 5- [5- (1,2-dihydroxyethyl-5-pyrazolidene) -3-ethyl-1-formazano] -1,2-dihydroxyethyl-pyrazolinium chloride. 5- [5- (1,2-Dihydroxyethyl-5-pyrazolidene) -3-phenyl-1-formazano] -1,2-dihydroxyethyl-pyrazolinium chloride. 5- [5- (1,2-dihydroxyethyl-5-pyrazolidene) -3-isopropyl-1-formazano] -1,2-dihydroxyethyl-pyrazolinium chloride. 5- [5- (1,2-dihydroxyethyl-5-pyrazolidene) -3- (4'-methoxyphenyl) -1-formazano] -1,2-dihydroxyethyl-pyrazolinium chloride. 5- [5- (1,2-dihydroxyethyl-5-pyrazolidene) -3- (4'-hydroxyphenyl) -1-formazano] -1,2-dihydroxyethyl-pyrazolinium chloride. 5- [5- (1,2-dihydroxyethyl-5-pyrazolidene) -3- (4'-N, N-dimethylaminophenyl) -1-formazano] -1,2-dihydroxyethyl pyrazolinium chloride. 5- [5- (1,2-dicarboxyethyl-5-pyrazolidene) -1-formazano] -1,2-dicarboxyethyl-pyrazolinium chloride. 5- [5- (1,2-dicarboxyethyl-5-pyrazolidene) -3-methyl-1-formazano] -1,2-dicarboxyethyl-pyrazolinium chloride. 5- [5- (1,2-dicarboxyethyl-5-pyrazolidene) -3-ethyl-1-formazano] -1,2-dicarboxyethyl-pyrazolinium chloride. 5- [5- (1,2-Dicarboxyethyl-5-pyrazolidene) -3-phenyl-1-formazano] -1,2-dicarboxyethyl-pyrazolinium chloride. 5- [5- (1,2-dicarboxyethyl-5-pyrazolidene) -3-isopropyl-1-formazano] -1,2-dicarboxyethyl-pyrazolinium chloride. 5- [5- (1,2-dicarboxyethyl-5-pyrazolidene) -3- (4'-methoxyphenyl) -1-formazano] -1,2-dicarboxyethyl-pyrazolinium chloride. 5- [5- (1,2-dicarboxyethyl-5-pyrazolidene) -3- (4'-hydroxyphenyl) -1-formazano] -1,2-dicarboxyethyl-pyrazolinium chloride. 5- [5- (1,2-dicarboxyethyl-5-pyrazolidene) -3- (4'-N, N-dimethylaminophenyl) -1-formazano] -1,2-dicarboxyethyl pyrazolinium chloride. 19. Composition according to any one of claims 1 to 10 wherein Wi is a 2-benzimidazolium radical and W2 is a 2-pyridine radical. 20.Composition according to claim 19 wherein the compound of formula (I) is selected from the following compounds: - 2- [5- (N-methyl-2-pyridinylidene) -1-formazano] -1,3-chloride; dimethyl-benzimidazolium. 2- [5- (N-methyl-2-pyridinylidene) -3-methyl-1-formazano] -1,3-dimethylbenzimidazolium chloride. 2- [5- (N-methyl-2-pyridinylidene) -3-ethyl-1-formazano] -1,3-dimethylbenzimidazolium chloride. 2- [5- (N-methyl-2-pyridinylidene) -3-isopropyl-1-formazano] -1,3-dimethylbenzimidazolium chloride. 2- [5- (N-methyl-2-pyridinylidene) -3-phenyl-1-formazano] -1,3-dimethylbenzimidazolium chloride. 2- [5- (N-methyl-2-pyridinylidene) -3- (4'-methoxyphenyl) -1-formazano] -1,3-dimethylbenzimidazolium chloride. 2- [5- (N-methyl-2-pyridinylidene) -3- (4'-hydroxyphenyl) -1-formazano] -1,3-dimethylbenzimidazolium chloride. 2- [5- (N-methyl-2-pyridinylidene) -3- (4'-N, N-dimethylaminophenyl) -1-formazano] -1,3-dimethylbenzimidazolium chloride. 2- [5- (N-hydroxyethyl-2-pyridinylidene) -1-formazano] -1,3-dihydroxyethylbenzimidazolium chloride. 2- [5- (N-hydroxyethyl-2-pyridinylidene) -3-methyl-1-formazano] -1,3-dihydroxyethylbenzimidazolium chloride. 2- [5- (N-hydroxyethyl-2-pyridinylidene) -3-ethyl-1-formazano] -1,3-dihydroxyethyl-benzimidazolium chloride. 2- [5- (N-hydroxyethyl-2-pyridinylidene) -3-phenyl-1-formazano] -1,3-dihydroxyethyl-benzimidazolium chloride. 2- [5- (N-hydroxyethyl-2-pyridinylidene) -3-isopropyl-1-formazano] -1,3-dihydroxyethyl-benzimidazolium chloride. 2- [5- (N-hydroxyethyl-2-pyridinylidene) -3- (4'-methoxyphenyl) -1-formazano] -1,3-dihydroxyethyl-benzimidazolium chloride. 2- [5- (N-hydroxyethyl-2-pyridinylidene) -3- (4'-hydroxyphenyl) -1-formazano] -1,3-dihydroxyethyl-benzimidazolium chloride. 2- [5- (N-hydroxyethyl-2-pyridinylidene) -3- (4'-N, N-dimethylaminophenyl) -1-formazano] -1,3-dihydroxyethylbenzimidazolium chloride. 2- [5- (N-carboxyethyl-2-pyridinylidene) -1-formazano] -1,3-dicarboxyethylbenzimidazolium chloride. 2- [5- (N-carboxyethyl-2-pyridinylidene) -3-methyl-1-formazano] -1,3-dicarboxyethylbenzimidazolium chloride. 2- [5- (N-carboxyethyl-2-pyridinylidene) -3-ethyl-1-formazano] -1,3-dicarboxyethylbenzimidazolium chloride. 2- [5- (N-carboxyethyl-2-pyridinylidene) -3-phenyl-1-formazano] -1,3-dicarboxyethylbenzimidazolium chloride. 2- [5- (N-carboxyethyl-2-pyridinylidene) -3-isopropyl-1-formazano] -1,3-dicarboxyethylbenzimidazolium chloride. 2- [5- (N-carboxyethyl-2-pyridinylidene) -3- (4'-methoxyphenyl) -1-formazano] -1,3-dicarboxyethylbenzimidazolium chloride. 2- [5- (N-carboxyethyl-2-pyridinylidene) -3- (4'-hydroxyphenyl) -1-formazano] -1,3-dicarboxyethylbenzimidazolium chloride. 2- [5- (N-carboxyethyl-2-pyridinylidene) -3- (4'-N, N-dimethylaminophenyl) -1-formazano] -1,3-dicarboxyethylbenzimidazolium chloride. 21.Composition according to any one of claims 1 to 10 wherein Wi is a 2-benzimidazolium radical and W2 is a 4-pyridine radical. 22.Composition according to claim 21 wherein the compound of formula (I) is selected from the following compounds: - 2- [5- (N-methyl-4-pyridinylidene) -1-formazano] -1,3-chloride dimethylbenzimidazolium. 2- [5- (N-methyl-4-pyridinylidene) -3-methyl-1-formazano] -1,3-dimethylbenzimidazolium chloride. 2- [5- (N-methyl-4-pyridinylidene) -3-ethyl-1-formazano] -1,3-dimethylbenzimidazolium chloride. 2- [5- (N-methyl-4-pyridinylidene) -3-isopropyl-1-formazano] -1,3-dimethylbenzimidazolium chloride. 2- [5- (N-methyl-4-pyridinylidene) -3-phenyl-1-formazano] -1,3-dimethylbenzimidazolium chloride. 2- [5- (N-methyl-4-pyridinylidene) -3- (4'-methoxyphenyl) -1-formazano] -1,3-dimethylbenzimidazolium chloride. 2- [5- (N-methyl-4-pyridinylidene) -3- (4'-hydroxyphenyl) -1-formazano] -1,3-dimethylbenzimidazolium chloride. 2- [5- (N-methyl-4-pyridinylidene) -3- (4'-N, N-dimethylaminophenyl) -1-formazano] -1,3-dimethylbenzimidazolium chloride. 2- [5- (N-hydroxyethyl-4-pyridinylidene) -1-formazano] -1,3-dihydroxyethylbenzimidazolium chloride. 2- [5- (N-hydroxyethyl-4-pyridinylidene) -3-methyl-1-formazano] -1,3-dihydroxyethylbenzimidazolium chloride. 2- [5- (N-hydroxyethyl-4-pyridinylidene) -3-ethyl-1-formazano] -1,3-dihydroxyethyl-benzimidazolium chloride. 2- [5- (N-hydroxyethyl-4-pyridinylidene) -3-phenyl-1-formazano] -1,3-dihydroxyethyl-benzimidazolium chloride. 2- [5- (N-hydroxyethyl-4-pyridinylidene) -3-isopropyl-1-formazano] -1,3-dihydroxyethyl-benzimidazolium chloride. 2- [5- (N-hydroxyethyl-4-pyridinylidene) -3- (4'-methoxyphenyl) -1-formazano] -1,3-dihydroxyethyl-benzimidazolium chloride. 2- [5- (N-Hydroxyethyl-4-pyridinylidene) -3- (4'-hydroxyphenyl) -1-formazano] -1,3-dihydroxyethyl-benzimidazolium chloride. 2- [5- (N-Hydroxyethyl-4-pyridinylidene) -3- (4'-N, N-dimethylaminophenyl) -1-formazano] -1,3-dihydroxyethyl-benzimidazolium chloride. 2- [5- (N-carboxyethyl-4-pyridinylidene) -1-formazano] -1,3-dicarboxyethylbenzimidazolium chloride. 2- [5- (N-carboxyethyl-4-pyridinylidene) -3-methyl-1-formazano] -1,3-dicarboxyethylbenzimidazolium chloride. 2- [5- (N-carboxyethyl-4-pyridinylidene) -3-ethyl-1-formazano] -1,3-dicarboxyethylbenzimidazolium chloride. 2- [5- (N-carboxyethyl-4-pyridinylidene) -3-phenyl-1-formazano] -1,3-dicarboxyethylbenzimidazolium chloride. 2- [5- (N-carboxyethyl-4-pyridinylidene) -3-isopropyl-1-formazano] -1,3-dicarboxyethylbenzimidazolium chloride. 2- [5- (N-carboxyethyl-4-pyridinylidene) -3- (4'-methoxyphenyl) -1-formazano] -1,3-dicarboxyethylbenzimidazolium chloride. 2- [5- (N-carboxyethyl-4-pyridinylidene) -3- (4'-hydroxyphenyl) -1-formazano] -1,3-dicarboxyethylbenzimidazolium chloride. 2- [5- (N-carboxyethyl-4-pyridinylidene) -3- (4'-N, N-dimethylaminophenyl) -1-formazano] -1,3-dicarboxyethyl benzimidazolium chloride. 23.Composition according to any one of claims 1 to 10 wherein Wi is a 2-imidazolium radical and W2 is a 2-pyridine radical. 24. Composition according to claim 23, in which the compound of formula (I) is chosen from the following compounds: - 2- [5- (N-methyl-2-pyridinylidene) -1-formazano] -1,3-dimethyl chloride -imidazolium. 2- [5- (N-methyl-2-pyridinylidene) -3-methyl-1-formazano] -1,3-dimethylimidazolium chloride. 2- [5- (N-methyl-2-pyridinylidene) -3-ethyl-1-formazano] -1,3-dimethylimidazolium chloride. 2- [5- (N-methyl-2-pyridinylidene) -3-isopropyl-1-formazano] -1,3-dimethylimidazolium chloride. 2- [5- (N-methyl-2-pyridinylidene) -3-phenyl-1-formazano] -1,3-dimethylimidazolium chloride. 2- [5- (N-methyl-2-pyridinylidene) -3- (4'-methoxyphenyl) -1-formazano] -1,3-dimethylimidazolium chloride. 2- [5- (N-methyl-2-pyridinylidene) -3- (4'-hydroxyphenyl) -1-formazano] -1,3-dimethylimidazolium chloride. 2- [5- (N-methyl-2-pyridinylidene) -3- (4'-N, N-dimethylaminophenyl) -1-formazano] -1,3-dimethylimidazolium chloride. 2- [5- (N-hydroxyethyl-2-pyridinylidene) -1-formazano] -1,3-dihydroxyethylimidazolium chloride. 2- [5- (N-hydroxyethyl-2-pyridinylidene) -3-methyl-1-formazano] -1,3-dihydroxyethylimidazolium chloride. 2- [5- (N-hydroxyethyl-2-pyridinylidene) -3-ethyl-1-formazano] -1,3-dihydroxyethylimidazolium chloride. 2- [5- (N-hydroxyethyl-2-pyridinylidene) -3-phenyl-1-formazano] -1,3-dihydroxyethylimidazolium chloride. 2- [5- (N-hydroxyethyl-2-pyridinylidene) -3-isopropyl-1-formazano] -1,3-dihydroxyethylimidazolium chloride. 2- [5- (N-hydroxyethyl-2-pyridinylidene) -3- (4'-methoxyphenyl) -1-formazano] -1,3-dihydroxyethylimidazolium chloride. 2- [5- (N-hydroxyethyl-2-pyridinylidene) -3- (4'-hydroxyphenyl) -1-formazano] -1,3-dihydroxyethylimidazolium chloride. 2- [5- (N-hydroxyethyl-2-pyridinylidene) -3- (4'-N, N-dimethylaminophenyl) -1-formazano] -1,3-dihydroxyethylimidazolium chloride. 2- [5- (N-carboxyethyl-2-pyridinylidene) -1-formazano] -1,3-dicarboxyethylimidazolium chloride. 2- [5- (N-carboxyethyl-2-pyridinylidene) -3-methyl-1-formazano] -1,3-dicarboxyethylimidazolium chloride. 2- [5- (N-carboxyethyl-2-pyridinylidene) -3-ethyl-1-formazano] -1,3-dicarboxyethylimidazolium chloride. 2- [5- (N-carboxyethyl-2-pyridinylidene) -3-phenyl-1-formazano] -1,3-dicarboxyethylimidazolium chloride. 2- [5- (N-carboxyethyl-2-pyridinylidene) -3-isopropyl-1-formazano] -1,3-dicarboxyethylimidazolium chloride. 2- [5- (N-carboxyethyl-2-pyridinylidene) -3- (4'-methoxyphenyl) -1-formazano] -1,3-dicarboxyethylimidazolium chloride. 2- [5- (N-carboxyethyl-2-pyridinylidene) -3- (4'-hydroxyphenyl) -1-formazano] -1,3-dicarboxyethylimidazolium chloride. 2- [5- (N) -chloride -carboxyethyl-2-pyridinylidene) -3- (4'-N, N-dimethylaminophenyl) -1-formazano] -1,3-dicarboxyethyl imidazolium. 25.Composition according to any one of claims 1 to 10 wherein Wi is a 2-imidazolium radical and W2 is a 4-pyridine radical. 26.Composition according to claim 25 wherein the compound of formula (I) is selected from the following compounds: - 2- [5- (N-methyl-4-pyridinylidene) -1-formazano] chloride -1,3- dimethyl-imidazolium. 2- [5- (N-methyl-4-pyridinylidene) -3-methyl-1-formazano] -1,3-dimethylimidazolium chloride. 2- [5- (N-methyl-4-pyridinylidene) -3-ethyl-1-formazano] -1,3-dimethylimidazolium chloride. 2- [5- (N-methyl-4-pyridinylidene) -3-isopropyl-1-formazano] -1,3-dimethylimidazolium chloride. 2- [5- (N-methyl-4-pyridinylidene) -3-phenyl-1-formazano] -1,3-dimethylimidazolium chloride. 2- [5- (N-methyl-4-pyridinylidene) -3- (4'-methoxyphenyl) -1-formazano] -1,3-dimethylimidazolium chloride. 2- [5- (N-methyl-4-pyridinylidene) -3- (4-hydroxyphenyl) -1-formazano] -1,3-dimethylimidazolium chloride. 2- [5- (N-methyl-4-pyridinylidene) -3- (4'-N, N-dimethylaminophenyl) -1-formazano] -1,3-dimethylimidazolium chloride. 2- [5- (N-hydroxyethyl-4-pyridinylidene) -1-formazano] -1,3-dihydroxyethylimidazolium chloride. 2- [5- (N-hydroxyethyl-4-pyridinylidene) -3-methyl-1-formazano] -1,3-dihydroxyethylimidazolium chloride. 2- [5- (N-hydroxyethyl-4-pyridinylidene) -3-ethyl-1-formazano] -1,3-dihydroxyethylimidazolium chloride. 2- [5- (N-hydroxyethyl-4-pyridinylidene) -3-phenyl-1-formazano] -1,3-dihydroxyethylimidazolium chloride. 2- [5- (N-hydroxyethyl) -4-hydroxychloride pyridinylidene) -3-isopropyl-1-formazano] -1,3-dihydroxyethylimidazolium. 2- [5- (N-hydroxyethyl-4-pyridinylidene) -3- (4'-methoxyphenyl) -1-formazano] -1,3-dihydroxyethylimidazolium chloride. 2- [5- (N-hydroxyethyl-4-pyridinylidene) -3- (4'-hydroxyphenyl) -1-formazano] -1,3-dihydroxyethylimidazolium chloride. 2- [5- (N-hydroxyethyl-4-pyridinylidene) -3- (4'-N, N-dimethylaminophenyl) -1-formazano] -1,3-dihydroxyethyl imidazolium chloride. 2- [5- (N-carboxyethyl-4-pyridinylidene) -1-formazano] -1,3-dicarboxyethylimidazolium chloride. 2- [5- (N-carboxyethyl-4-pyridinylidene) -3-methyl-1-formazano] -1,3-dicarboxyethylimidazolium chloride. 2- [5- (N-carboxyethyl-4-pyridinylidene) -3-ethyl-1-formazano] -1,3-dicarboxyethylimidazolium chloride. 2- [5- (N-carboxyethyl-4-pyridinylidene) -3-phenyl-1-formazano] -1,3-dicarboxyethylimidazolium chloride. 2- [5- (N-carboxyethyl-4-pyridinylidene) -3-isopropyl-1-formazano] -1,3-dicarboxyethylimidazolium chloride. 2- [5- (N-carboxyethyl-4-pyridinylidene) -3- (4'-methoxyphenyl) -1-formazano] -1,3-dicarboxyethylimidazolium chloride. 2- [5- (N-carboxyethyl-4-pyridinylidene) -3- (4'-hydroxyphenyl) -1-formazano] -1,3-dicarboxyethylimidazolium chloride. 2- [5- (N-carboxyethyl-4-pyridinylidene) -3- (4'-N, N-dimethylaminophenyl) -1-formazano] -1,3-dicarboxyethylimidazolium chloride. 27.Composition according to any one of claims 1 to 10 wherein Wi is a 2-benzimidazolium radical and W2 is a 2-benzimidazole radical. 28.Composition according to claim 27 wherein the compound of formula (I) is selected from the following compounds: 2- [5- (1,3-Dimethyl-2-benzimidazolidene) -1-formazano] chloride 3-dimethylbenzimidazolium. 2- [5- (1,3-Dimethyl-2-benzimidazolidene) -3-methyl-1-formazano] -1,3-dimethylbenzimidazolium chloride. 2- [5- (1,3-Dimethyl-2-benzimidazolidene) -3-ethyl-1-formazano] -1,3-dimethylbenzimidazolium chloride. 2- [5- (1,3-Dimethyl-2-benzimidazolidene) -3-isopropyl-1-formazano] -1,3-dimethylbenzimidazolium chloride. 2- [5- (1,3-Dimethyl-2-benzimidazolidene) -3-phenyl-1-formazano] -1,3-dimethylbenzimidazolium chloride. 2- [5- (1,3-Dimethyl-2-benzimidazolidene) -3- (4'-methoxyphenyl) -1-formazano] -1,3-dimethylbenzimidazolium chloride. 2- [5- (1,3-Dimethyl-2-benzimidazolidene) -3- (4'-hydroxyphenyl) -1-formazano] -1,3-dimethylbenzimidazolium chloride. 2- [5- (1,3-Dimethyl-2-benzimidazolidene) -3- (4'-N, N-dimethylaminophenyl) -1-formazano] -1,3-dimethylbenzimidazolium chloride. 2- [5- (1,3-dihydroxyethyl-2-benzimidazolidene) -1-formazano] -1,3-dihydroxyethylbenzimidazolium chloride. 2- [5- (1,3-dihydroxyethyl-2-benzimidazolidene) -3-20 methyl-1-formazano] -1,3-dihydroxyethylbenzimidazolium chloride. 2- [5- (1,3-dihydroxyethyl-2-benzimidazolidene) -3-ethyl-1-formazano] -1,3-dihydroxyethyl-benzimidazolium chloride. 2- [5- (1,3-dihydroxyethyl-2-benzimidazolidene) -3-phenyl-1-formazano] -1,3-dihydroxyethyl-benzimidazolium chloride. 2- [5- (1,3-Dihydroxyethyl-2-benzimidazolidene) -3-isopropyl-1-formazano] -1,3-dihydroxyethyl-benzimidazolium chloride. 2- [5- (1,3-dihydroxyethyl-2-benzimidazolidene) -3- (4'-methoxyphenyl) -1-formazano] -1,3-dihydroxyethyl-benzimidazolium chloride. 2- [5- (1,3-Dihydroxyethyl-2-benzimidazolidene) -3- (4'-hydroxyphenyl) -1-formazano] -1,3-dihydroxyethyl-benzimidazolium chloride. 2- [5-Chloride (1,3-dihydroxyethyl-2-benzimidazolidene) -3- (4'-N, N-dimethylaminophenyl) -1-formazano] -1,3-dihydroxyethylbenzimidazolium. 2- [5- (1,3-Dicarboxyethyl-2-benzimidazolidene) -1-formazano] -1,3-dicarboxyethylbenzimidazolium chloride. 2- [5- (1,3-Dicarboxyethyl-2-benzimidazolidene) -3-methyl-1-formazano] -1,3-dicarboxyethyl-benzimidazolium chloride. 2- [5- (1,3-Dicarboxyethyl-2-benzimidazolidene) -3-ethyl-1-formazano] -1,3-dicarboxyethyl-benzimidazolium chloride. 2- [5- (1,3-Dicarboxyethyl-2-benzimidazolidene) -3-phenyl-1-formazano] -1,3-dicarboxyethyl-benzimidazolium chloride. 2- [5- (1,3-Dicarboxyethyl-2-benzimidazolidene) -3-isopropyl-1-formazano] -1,3-dicarboxyethyl-benzimidazolium chloride. 2- [5- (1,3-Dicarboxyethyl-2-benzimidazolidene) -3- (4'-methoxyphenyl) -1-formazano] -1,3-dicarboxyethyl-benzimidazolium chloride. 2- [5- (1,3-Dicarboxyethyl-2-benzimidazolidene) -3- (4'-hydroxyphenyl) -1-formazano] -1,3-dicarboxyethyl-benzimidazolium chloride. 2- [5- (1,3-Dicarboxyethyl-2-benzimidazolidene) -3- (4'-N, N-dimethylaminophenyl) -1-formazano] -1,3-dicarboxyethylbenzimidazolium chloride. 29.Composition according to any one of the preceding claims, characterized in that the compound (s) of formula I are present in 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. 30.Composition according to any one of the preceding claims, characterized in that the direct dye with extranuclear quaternary ammonium group has in its structure at least one group (N) (+) R1R2R3, R1, R2, R3 independently designating the the other is an optionally substituted C1-C30 alkyl radical or an optionally substituted phenyl radical. 31.Composition according to the preceding claim, characterized in that R1, R2, R3 all denote a C1C4 alkyl group. 32.Composition according to the preceding claim, characterized in that R1, R2, R3 denote a methyl group. 33. Composition according to any one of the preceding claims, characterized in that the extranuclear ammonium group is attached to an aliphatic chain and in particular to an alkyl chain. 34. Composition according to any one of claims 1 to 32, characterized in that the extranuclear ammonium group is attached to an aromatic carbon ring and in particular to a phenyl or naphthyl ring. 35. Composition according to any one of the preceding claims, characterized in that the cationic direct dye with extranuclear quaternary ammonium group is the Basic Blue 22 anthraquinone dye or a benzene nitro dye. 36.Composition according to any one of the preceding claims, characterized in that the direct dye with extranuclear quaternary ammonium group is chosen from those of formulas (VI), (VII) and (VIII): OH R4 O HNùR5 NH OH (VIII) formulas (VI) to (VIII) in which: R1 represents a hydrogen atom or an amino radical; R2 represents a hydrogen atom or a nitro group; R3 represents a hydrogen atom, a nitro group or a C1-C4 alkoxy radical; R4 represents a C1-C4 alkyl radical; R4 X 75 X 76 R5 represents a hydrogen atom or a paratrialkylCI-C4 ammoniophenyl group; R6 represents a bromine atom or a C1-C4 NH-paratrialkyl ammoniophenyl group; Xrepresente an anion preferably selected from chloride, methyl sulfate and acetate. 37.Composition according to the preceding claim, characterized in that the direct dye with extranuclear quaternary ammonium group is chosen from the salts of the following compounds: 8 - [(4-aminophenyl) azo] -7-hydroxy-2-trimethylammonio-naphthalene, 8 - [(2-methoxyphenyl) azo] -7-hydroxy-2-trimethylammonio-naphthalene, 8 - [(4- amino-3-nitrophenyl) azo] -7-hydroxy-2-trimethylammonionaphthalene, 8 - [(4-amino-2-nitrophenyl) azo] -7-hydroxy-2-trimethylammonionaphthalene, 3 - [(3-methyl) -2- 5-hydroxyl-phenyl-1H-pyrazol-4-yl) azo] -trimethylammonio-benzene, .3 - [(4-amino-6-bromo-5,8-dihydro-1-hydroxy-8-imino-5- 2-oxo-naphthalenyl) -amino] -trimethylammonio-benzene, 3 - [(3,7-dibromo-5,8-dihydro-4-hydroxy-5-imino-8-oxo-1-naphthalenyl) -amino] -trimethylammonio -benzene. 38.Composition according to the preceding claim, characterized in that the salt is a chloride. 39. Composition according to any one of the preceding claims, characterized in that the direct dye (s) with extranuclear quaternary ammonium group used according to the invention preferably represent from 0.001 to 10% by weight, based on the total weight of the composition. dyeing and even more preferably from 0.005 to 5% by weight approximately of this weight. 40.Composition according to any one of the preceding claims, characterized in that it comprises at least one additional direct dye different from the direct dyes of the invention. 41.Composition according to claim 40 characterized in that the additional direct dyes are present at a concentration ranging from 0.001 to 20% by weight relative to the total weight of the composition. 42.Composition according to any one of the preceding claims, characterized in that it further comprises an oxidizing agent. 43. Composition according to any one of the preceding claims, characterized in that it comprises at least one oxidation base chosen from the group formed by para-phenylenediamines, bis-phenylalkylenediamines, para-aminophenols and ortho-aminophenols. heterocyclic bases and their addition salts. 44.Composition according to claim 43, characterized in that the oxidation base (s) are present at a concentration ranging from 0.001 to 10% by weight relative to the total weight of the composition. 45.Composition according to one of claims 43 and 44, characterized in that it comprises at least one coupler selected from the group consisting of meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalenic couplers, heterocyclic couplers and their salts. addition. 46.Composition according to claim 45, characterized in that the coupler or couplers are present at a concentration ranging from 0.001 to 10% by weight relative to the total weight of the composition. 47.Dyeing process for keratinous 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 41 is applied to the fibers. for a time sufficient to obtain the desired coloration, after which it is rinsed, washed optionally with shampoo, rinsed again and dried. 48.Dyeing process for keratinous 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 41 is applied to the fibers. for a time sufficient to obtain the desired coloration, without final rinsing. 49.Dyeing process for keratinous fibers and in particular human keratinous fibers such as the hair, characterized in that it comprises a preliminary step consisting in storing, in separate form, on the one hand, a composition (Al) comprising: in a medium suitable for dyeing, at least one cationic direct dye (i) as defined in claims 1 to 28 and, secondly, a composition (B1) containing, in a medium suitable for dyeing, at least an oxidizing agent, then to be mixed at the time of use before applying this mixture to the keratin fibers, the composition (Al) or the composition (B1) containing at least one direct dye having at least one extranuclear quaternary ammonium group as defined in claims 1 and 30 to 38. 50.Dyeing process of keratinous fibers and in particular human keratinous fibers such as hair, characteristics in that it comprises a preliminary step of separately storing, on the one hand, a composition (A2) comprising, in a medium suitable for dyeing, at least one cationic direct dye (i) as defined in claims 1 to 28 and at least one oxidation base and, secondly, a composition (B2) containing, in a medium suitable for dyeing, at least one oxidizing agent, and then mixing them at the moment of use before applying this mixture to the keratin fibers, the composition (A2) or the composition (B2) containing at least one direct dye having at least one extranuclear quaternary ammonium group as defined in claims 1 and 30 38. 51.Multi compartment device or dye kit with several compartments, characterized in that a first compartment contains the composition (A1) or (A2) as defined in claim 49 or 50 and a This compartment contains the composition (B1) or (B2) as defined in claim 49 or 50.25.