MXPA99004751A - Composition of dyeing by oxidation of keratinic fibers and dyeing procedure using this composition - Google Patents

Abstract

The present invention relates to a composition for the oxidation dyeing of keratin fibers, and in particular of human keratin fibers such as hair comprising, in a medium suitable for dyeing, at least one oxidation base, and less a particular cationic dye as a direct dye, as well as the dyeing process using this composition

Description

COMPOSITION OF DYEING BY OXIDATION OF FIBERS KERATINICS AND DYEING PROCEDURE USING THIS COMPOSITION FIELD OF THE INVENTION The subject of the invention is a composition for the oxidation dyeing of keratin fibers, and in particular of human keratin fibers such as hair comprising, in a medium suitable for dyeing, at least one oxidation base, and at least a particular cationic dye as a direct dye, as well as the dyeing process using this composition.

BACKGROUND OF THE INVENTION It is known to dye keratin fibers and in particular human hair with dyeing compositions containing dye precursors by oxidation, in particular ortho or para-phenylenediamines, ortho or para-aminophenols, heterocyclic bases, generally called oxidation bases. Dye precursors by oxidation, or oxidation bases, are colorless or weakly ref. 030207 - -coloured which, associated with oxidizing products, can give rise, through a process of oxidative condensation, to colored compounds and dyes. It is also known that the shades obtained with these oxidation bases can be modified by associating them with copulators or color modifiers, the latter being chosen in particular from aromatic etadiamines, meta-aminophenols, meta-diphenols and some heterocyclic compounds. The variety of molecules used at the level of the oxidation bases and copulators allows obtaining a rich range of colors. It is also known that in order to vary the shades obtained and to give them reflections, direct dyes, that is to say colored substances which give a coloration in the absence of an oxidizing agent, can be used in association with oxidation dye precursors and copulators. These direct dyes belong mostly to the family of nitro compounds of the benzene series and have the drawback, when incorporated into dyeing compositions, of leading to discolourations that have insufficient toughness, in particular in relation to shampooing. .

The coloration called "permanent" obtained thanks to these dyes by oxidation, must on the other hand meet a certain number of demands. Thus, it should allow obtaining tonalities in the desired intensity and present a good behavior in front of external agents (light, bad weather, washing, permanent wave, perspiration, friction). The dyes should also allow the white hair to be covered, and finally be as non-selective as possible, that is to say allow to obtain as slight color differences as possible throughout the same keratin fiber, which may be distinctly sensitized (ie spoiled) between its tip and its root. The present invention seeks to propose new compositions for the oxidation coloring of keratin fibers and in particular of human keratin fibers such as hair that allow to lead to reflections rich in color having good tenacity properties. Thus, the applicant firm ends up, in fact, discovering that it is possible to obtain new dyes at once rich in reflections and tenacious by associating: - at least one oxidation base, - at least one direct cationic dye of the formula - - (I) defined below. This discovery forms the basis of the present invention.

DESCRIPTION OF THE INVENTION The invention therefore has as its first object a composition for the oxidation dyeing of keratin fibers and in particular of human keratin fibers such as hair, characterized in that it comprises, in a medium suitable for dyeing: - at least one oxidation base, - at least one direct cationic dye of the formula I) following: A-N = N-B (I) in which A represents a group selected from the following Al a A3 structures: - A1 A2 structures A1 to A3 in which: Ri denotes an alkyl radical of C-C4, a phenyl radical or a phenyl radical substituted by a C 1 -C 4 alkyl radical or by a halogen atom selected from chlorine, bromine, iodine and fluorine; R2 denotes an alkyl radical of Ci-C or a phenyl radical; - R 3 and R 4, identical or different, represent an alkyl radical of C 1 -C 4, a phenyl radical, or together form a benzene ring substituted by one or more C 1 -C 4 alkyl radicals, C 1 -C 4 alkoxy or nitro; R3 can also designate a hydrogen atom; - R5 and Rβ, identical or different, represent an alkyl radical of d-C4, a phenyl radical, or form - - together a benzene ring unsubstituted or substituted by one or more C! -C4 alkyl radicals, alkoxy C1-C4 or nitro; R5 can also designate a hydrogen atom; - R and Rg, identical or different, represent a hydrogen or halogen atom selected from chlorine, bromine, iodine and fluorine, a C 1 -C 4 alkyl radical, C 1 -C 4 alkoxy or a nitro radical; Z denotes an oxygen or sulfur atom or a group NR2 in which R2 can take the same meaning as indicated above; the vertex L represents a group -CH, -CR or -N + R9 (X ~) r; - the vertex M represents a group -CH, -CR or -N + R9 (X ~) r; r is an integer equal to 0 or 1; - R represents a C 1 -C 4 alkyl radical; R9 represents a 0"atom, a C1-C4 alkyl radical or a C1-C4 alkoxy; -X" represents an anion preferably selected from chloride, methylisulfate, ethyl sulfate, acetate and perchlorate; it being understood that: - in the groups of the formula A3, at least one of the vertices L and M represents a group -N + R9 (X ~) r; - when Re represents a C 1 -C 4 alkyl radical and when Z represents a sulfur atom, then R5 is different from an alkyl radical of C-C4; when Re represents an alkyl radical of Ci-04 and when Z represents a sulfur atom, and when one of the radicals Rio and Rp represents a hydrogen atom, then R5 is different from a hydrogen atom; when R9 designates 0", then r = 0; - when L or M designates of radical a -N + R9 (X ~) r, in which R9 represents an alkyl radical of Cj-C4 and r = 1, then at least one of the radicals R and Rg is different from a hydrogen atom: when L designates a radical -N + R9 (X ~) r then M represents a group -CH or CR; - when M designates a radical -N + R9 (X ") r, then L represents a group -CH or CR; when Z represents a group NR2 in which R2 represents a C1-C4 alkyl radical, then at least one of the radicals Ri, R5 and Re is different from an alkyl radical of Ci-C4, "- when Z represents an sulfur and when Ri represents a C1-C4 alkyl radical, and when one of the radicals Rio and R11 represents a hydrogen atom, then R5 and Re can not together form a unsubstituted benzene cycle; B represents: either (a) a group of structure Bl following structure Bl in which, Rio represents a hydrogen atom a halogen atom selected from chlorine, bromine, iodine and fluorine, a C1-C4 alkyl radical, C1-C4 alkoxy, hydroxyl, a -NHR13 group , -NR14R15 / -NHCOalkyl of C1-C4, nitro, or form with Rp a cycle of 5 or 6 links carbonized or containing one or more heteroatoms selected from nitrogen, oxygen or sulfur; - Rp represents a hydrogen atom, a halogen atom selected from chlorine, bromine, iodine and fluorine, an alkyl radical of C 1 -C 4, alkoxy of C 1 -C 4, or forms with R 12 or R 13 a cycle of 5 or 6 carbon-containing or containing one or more heteroatoms selected from nitrogen, oxygen or sulfur; R 12 represents a hydrogen atom, a hydroxyl radical, a radical -NHR 13, or a radical -NR 14 R 15; R p represents a hydrogen atom, a C 1 -C 4 alkyl radical, C 1 -C 4 monohydroxyalkyl, C 2 -C 4 polyhydroxyalkyl or phenyl; R14 and R15, identical or different, represent an alkyl radical of Ci-C4, monohydroxyalkyl of C1-C4 or polyhydroxyalkyl of C2-C4; either (b) a 5- or 6-membered nitrogenous heterocyclic group, a 5- or 6-membered nitrogen-containing heterocyclic group including one or more heteroatoms selected from oxygen and sulfur and / or one or more carbonylated groups, the indicated heterocycles being substituted by one or more C 1 -C 4 alkyl, amino or phenyl radicals. Among the indicated heterocyclic 5 or 6-membered heterocyclic groups mentioned above, the following groups of structure B2 can be mentioned in particular: - structure B2 in which R and R? 7, identical or different, represent a hydrogen atom, an alkyl radical of C! ~ C4 or a phenyl radical; - And represents a group -C = 0 -c = n is an integer equal to 0 or 1. The cationic direct dyes of the formula (I) indicated above are known compounds of the prior art and are described for example in the patent application FR-A -2,140,205 and its certificates of addition, as well as in patent application FR-A-2,189,006. The dyeing composition according to the invention leads to powerful, chromatic colorations, which exhibit low selectivity and excellent properties of resistances at the same time with respect to atmospheric agents such as light and weathering and in relation to perspiration, and to different treatments that the hair can experience. These properties are particularly remarkable in regard to chromaticity. Another object of the invention is a process for dyeing by oxidation of the fibers - -keratinics that use this dye composition. In the compounds of formula (I) indicated above, the C 1 -C 4 alkyl and alkoxy radicals are preferably chosen from the methyl, ethyl, butyl, methoxy and ethoxy radicals. The nature of the oxidation base (s) used in the dyeing composition according to the invention is not critical. They can be chosen in particular from para-phenylenediamines, double bases, para-aminophenols, ortho-aminophenols and heterocyclic oxidation bases. Among the para-phenylenediamines which can be used as a base by oxidation in the dyeing compositions according to the invention, mention may be made in particular of the following compounds of formula (II) and their addition salts with an acid: in which Ri represents a hydrogen atom, a C1-C4 alkyl radical, d-C4 monohydroxyalkyl, C2-C4 polyhydroxyalkyl, (C1-C4) alkoxy (Ci- C4) alkyl, C1-C4 alkyl substituted by a group Nitrogen, phenyl or 4'-aminophenyl; R19 represents a hydrogen atom, a C1-C4 alkyl radical, C1-C4 monohydroxyalkyl, C2-C4 polyhydroxyalkyl, (C1-C4) alkoxy (C1-C4) alkyl or C1-C4 alkyl substituted by a nitrogenous group; R20 represents a hydrogen atom, a halogen atom such as a chlorine, bromine, iodine or fluorine atom, a C1-C4 alkyl radical, C1-C4 monohydroxyalkyl, C1-C4 hydroxyalkoxy, C1 acetylaminoalkoxy -C4, C 1 -C 4 mesylaminoalkoxy or C 1 -C 4 carbamoylaminoalkoxy, R 21 represents a hydrogen atom, a halogen atom or a C 1 -C 4 alkyl radical. Among the nitrogen groups of the formula (II) indicated above, mention may be made in particular of the amino radicals, (C 1 -C 4) amino, dialkyl (C 4 -C 4) amino, trialkyl (C 1 -C 4) amino, monohydroxyalkyl (C 4 -C 4) radicals. amino, imidazolinium and ammonium. Among the para-phenylenediamines of the formula (II) indicated above, para-phenylenediamine, para-tolylenediamine, 2-chloro-para-phenylenediamine, 2,3-dimethyl paraphenylenediamine, 2,6-dimethyl paraphenylenediamine, 2,6-diethyl paraphenylenediamine, 2,5-dimethyl paraphenylenediamine, N, N-dimethyl paraphenylenediamine, N, N- diethyl paraphenylenediamine, N, N-dipropyl paraphenylenediamine, 4-amino N, N-diethyl 3-methyl aniline, N, N-bis- (β-hydroxyethyl) paraphenylenediamine, 4-N, N-bis- (β -hydroxyethyl) amino 2-methyl aniline, 4-N, N-bis- (β-hydroxyethyl) amino 2-chloroaniline, 2-β-hydroxyethyl paraphenylenediamine, 2-fluoro paraphenylenediamine, 2-isopropyl paraphenylenediamine, N- (β-hydroxypropyl) paraphenylenediamine, 2-hydroxymethyl paraphenylenediamine, N, N-dimethyl 3-methyl paraphenylenediamine, N, N- (ethyl, β-hydroxyethyl) paraphenylenediamine, N- (β, β-dihydroxypropyl) para-phenylenediamine, N- ('-aminophenyl) para-phenylenediamine, N-phenyl paraphenylenediamine, 2-β-hydroxyethyl-oxy-paraphenylenediamine, 2-β-acetylamino-ethyloxy-para-phenylenediamine, N- (β-methoxyethyl) paraphenylene diamine, and its addition salts with an acid. Among the para-phenylenediamines of formula (II) indicated above, para-phenylenediamine, para-tolylenediamine, 2-isopropyl paraphenylenediamine, 2-β-hydroxyethyl paraphenylenediamine, 2-β-hydroxyethyloxy paraphenylenediamine, 2,6-dimethyl paraphenylenediamine, 2,6-diethyl paraphenylenediamine are particularly preferred. , 2,3-dimethyl paraphenylenediamine, N, N-bis- (β-hydroxyethyl) paraphenylenediamine, 2-chloro paraphenylenediamine, 2-β-acetylaminoethyloxy paraphenylenediamine, and their addition salts with an acid. According to the invention, double bases are understood to be compounds comprising at least two aromatic nuclei on which amino and / or hydroxyl groups are carried. Among the double bases which can be used as oxidation bases in the dyeing compositions according to the invention, mention may be made in particular of the compounds which correspond to the following formula (III), and their addition salts with an acid: (III) - - in which: - Zi and Z2, identical or different, represent a hydroxyl radical or -NH2 which can be substituted by a C1-C4 alkyl radical or by a G-linking arm; the linking arm G represents an alkylene chain comprising from 1 to 14 carbon atoms, linear or branched, which 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 by one or more hydroxyl or Ci-Cβ alkoxy radicals; R 22 and R 23 represent a hydrogen or halogen atom, a C 1 -C 4 alkyl radical, a C 1 -C 4 monohydroxyalkyl, a C 2 -C 4 polyhydroxyalkyl, a C 1 -C 4 aminoalkyl or a G link arm; - R24, R25, R26, R27, R28 and R29, identical or different, represent a hydrogen atom, a G-linking arm or a C1-C4-alkyl radical; it being understood that the compounds of the formula (III) only comprise one G-link arm per molecule. Among the nitrogen groups of the formula (III) indicated above, mention may be made in particular of the amino, mono (C1-C4) amino, dialkyl (Ci- C4) amino, trialkyl (C1-C4) amino, monohydroxyalkyl (Ct-C4) amino, imidazolinium and ammonium radicals. Among the double bases of the formula (III) indicated above, N, N '-bis- (β-hydroxyethyl) N, N' -bis- (4'-aminophenyl) 1,3-diamino propanol can be more particularly mentioned. , N, N'-bis- (β-hydroxyethyl) N, N'-bis- (4'-aminophenyl) ethylenediamine, N, N'-bis- (4-aminophenyl) tetramethylenediamine, N, N'- bis- (ß-hydroxyethyl) N, N '-bis- (4-aminophenyl) tetramethylenediamine, N, N'-bis- (4- (methyl-aminophenyl) tetramethylenediamine, N, N'-bis- (ethyl) N, N'-bis- (4'-amino, 3'-methylphenyl) ethylenediamine, 1,8-bis- (2,5-diaminophenoxy) -3,5-dioxaoctane, and its addition salts with an acid. Among these double bases of formula (III), N, N'-bis- (β-hydroxyethyl) N, N '-bis- (4'-aminophenyl) 1,3-diamino propanol, 1,8-bis- (2,5-diaminophenoxy) -3,5-dioxaoctane or one of its "acid addition salts" are particularly preferred Among the para-aminophenols which can be used as oxidation bases in the dyeing compositions according to the invention n can be cited, in particular, the compounds of the following formula (IV), and their addition salts with an acid: - - wherein - R 30 represents a hydrogen or halogen atom, a C 1 -C 4 alkyl radical, C 1 -C 4 monohydroxyalkyl, (C 1 -C 4) alkoxy (C 1 -C 4) alkyl, C 1 -C 4 aminoalkyl or hydroxyalkyl ( C1-C4) C 1 -C 4 aminoalkyl, R 31 represents a hydrogen or halogen atom, a C 1 -C 4 alkyl radical, C 1 -C 4 monohydroxyalkyl, C 2 -C 4 polyhydroxyalkyl, C 1 -C 4 aminoalkyl, C 1-6 cyanoalkyl C4 or (C1-C4) alkoxy (C1-C4) alkyl, it being understood that at least one of the radicals R30 and R31 represents a hydrogen atom. Among the para-aminophenols of the formula (IV) mentioned above, para-aminophenol, 4-amino-3-methyl phenol, 4-amino-3-fluoro-phenol, 4-amino-3-hydroxymethyl-phenol, 4-amino-2-methyl-phenol, 4-amino-2-hydroxymethyl-phenol, 4-amino-2-methoxymethyl-phenol, 4-amino-2-aminomethyl-phenol, 4-amino-2- (-hydroxyethyl) aminomethyl) phenol, 4-amino-2-fluoro-phenol, and their addition salts with an acid. Among the ortho-inophenols which can be used as oxidation bases in the dyeing compositions according to the invention, mention may be made more particularly of 2-amino phenol, 2-amino-5-methyl phenol, 2-amino-6-methyl phenol, 5-acetamido 2-amino phenol, and its addition salts with an acid. Among the heterocyclic bases which can be used as oxidation bases in the dyeing compositions according to the invention, pyridine derivatives, pyrimidine derivatives, pyrazole derivatives and their addition salts with an acid can be more particularly mentioned. Among the pyridine derivatives, mention may be made more particularly of the compounds described, for example, in GB 1 026 978 and GB 1 153 196, such as 2,5-diamino pyridine, 2- (4-methoxyphenyl) amino 3-amino pyridine, 2,3-diamino-6-methoxy pyridine, 2- (β-methoxyethyl) amino 3-amino 6-methoxy pyridine, 3,4-diamino pyridine, and their addition salts with an acid. Among the pyrimidine derivatives, mention may be made more particularly of the compounds described, for example, in German Patents 2,359,399 or Japanese JP 88-169,571 and JP 91-10659 or WO Patent Application. 96/15765, such as 2, 4, 5, 6-tetra-aminopyrimidine, 4-hydroxy 2,5-, 6-triaminopyrimidine, 2-hydroxy 4,5,6-triaminopyrimidine, 2,4-dihydroxy 5, 6-diaminopyrimidine, 2, 5, 6-triaminopyrimidine, and pyrazolo-pyrimidine derivatives such as those mentioned in patent application FR-A-2,750,048 and among which pyrazolo- [1, 5 a] -pyrimidine-3,7-diamine; 2,5-dimethylpyrazolo- [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-ao-pyrazolo- [1, 5-a] -pyrimidin-3-ylamino) -ethanol, 2- [(3-amino-pyrazolo [1, 5-a] pyrimidin-7-yl) - (2-hydroxy-ethyl) -amino] -ethanol, 2 - [(7-amino-pyrazolo [1, 5-a] pyrimidin-3-yl) - (2-hydroxy-ethyl) -amino] -ethanol, 5,6-dimethyl-pyrazolo- [1,5-a] -pyrimidine-3,7-diamine , 2, 6-dimethylpyrazolo- [1,5-a] -pyrimidine-3,7-day ina, 2, 5, N7, N7-tetramethylpyrazolo- [1,5-a] -pyrimidine-3, 7 -diamine, and its addition salts and tautomeric forms, when there is a tautomeric equilibrium and its addition salts with an acid. Among the pyrazole derivatives, the compounds described in US Pat.

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 l- (4'-chlorobenzyl) pyrazole, 4,5-diamino-1,3-dimethyl pyrazole, 4,5-diamino-3-methyl-1-phenyl pyrazole, 4,5-diamino 1-methyl-3-phenyl pyrazole, 4-amino-1,3-dimethyl-5-hydrazinopyrazole, 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- (β-hydroxyethyl) 3-methyl pyrazole, 4,5-diamino-1-ethyl-3-methyl pyrazole, 4,5-diamino-1-ethyl 3- (4'-methoxyphenyl) pyrazole, 4,5-diamino-1-ethyl-3-hydroxymethyl pyrazole, 4,5-diamino-3-hydroxymethyl-1-methyl-pyrazole, 4, 5-diamino-3-hydroxymethyl-1-isopropylpyrazole, 4,5-diamino-3-methyl-1-isopropylpyrazole, 4-amino-5- (2'-aminoethyl) amino-1,3-dimethylpyrazole, 3, 4, 5-triamino pyrazole, 1-methyl 3,4-, 5-triamino pyrazole, 3,5-diamino-1-methyl-4-methylamino pyrazole, 3,5-diamino 4- (β-hydroxyethyl) amino 1-methyl pyrazole , and its addition salts with an acid. The oxidation base (s) preferably represent from 0.0005 to 12% by weight approximately of the total weight of the dyeing composition according to the invention, and even more preferably from 0.005 to 6% by weight. approximately this weight. The cationic direct dye (s) of formula (I) according to the invention are preferably chosen from: - the 4'-dimethylamino-phenyl-2-azo-pyridine-N-oxide of the formula: 4'-dimethylamino-methyl-2'-phenyl-azo-2-pyridine-N-oxide of the formula: 2- [(1, 3-diamino-6-methyl-4-phenyl) -azo] -3-methyl-benzothiazolium iodide of the formula: - - 6'-Hydroxy-1'-benzomorpholine-2-aza-3-methylbenzothiazolium chloride of the formula: 6 '-hydroxy-7' -benzomorpholine-2-aza-4-methyl-3-phenyl thiazolium perchlorate of the formula: 6 '-hydroxy-7'-benzomorpholine-2-azo-3,4-diphenyl thiazolium perchlorate of the formula: 6 '-hydroxy-7'-benzomorpholine-2-aza-3-methyl benzothiazolium chloride of the formula: 6 '-hydroxy-7' -benzomorpholine-2-aza-4-methyl-3-phenyl thiazolium perchlorate of the formula: CIO4" 2 ', 4' -diamino-5'-methoxy-phenyl-2-azo-pyridine-N-oxide of the formula: the 2 '-acetamido 4' -hydroxy-5 '-methyl-phenyl-2-azo pyridine N-oxide of the formula: 2'-Acetamido-4'-dimethylamino-phenyl-2-azo pyridine-N-oxide of the formula: 2'-amino-4'-dimethylamino-phenyl-2-azo pyridine-N-oxide of the formula: 2 ', 4' -diamino-5 '-methyl-phenyl-2-azo-1-methoxy pyridinium perchlorate of the formula: 2 ', 5' -dimethyl-4 '-hydroxy-f-enyl-2-azo pyridine-N-oxide of the formula: the 2'-dimethylamino-4'-hydroxy-phenyl-2-azo pyridine-N-oxide of the formula: 4'-dimethylamino-2'-hydroxy-phenyl-2-azo pyridine-N-oxide of the formula: 3 ', 5' -dimethyl-4 '-hydroxy-phenyl-2-azo-pyridine-N-oxide of the formula: 4'-dimethylamino-2f-nitro-phenyl-2-azo pyridine-N-oxide of the formula: 8 '-hydroxy-quinoline-5' -azo 2 '-pyridine-N-oxide of the formula: 2 '-nitro-4'-dimethylamino-phenyl-2-azo-1-methoxy pyridinium methosulfate of the formula: 4'-dimethylamino-phenyl-2-azo-5-nitro pyridine-N-oxide of the formula: 4'-dimethylamino-phenyl-2-azo-6-methyl pyridine-N-oxide of the formula: 4'-dimethylamino-phenyl-2-azo-5-methyl pyridine-N-oxide of the formula: 4'-dimethylamino-phenyl-2-azo-3-methyl pyridine-N-oxide of the formula: 4'-diethylamino-phenyl-2-azo-3-methyl pyridine-N-oxide of the formula: 4'-dimethylamino-2'-acetylamino-phenyl-2-azo-3-methyl pyridine-N-oxide of the formula: 4'-amino-naphthalene-1'-azo: 2-methyl-6-pyridine-N-oxide of the formula: the di- (β-hydroxyethyl) amino-4 '-f-enyl-2-azo-6-methyl-pyridine-N-oxide of the formula: 4'-diethylamino-phenyl-2-azo-6-methyl pyridine-N-oxide of the formula: 2 ', 5' -dimethyl-4 '-hydroxy-phenyl-2-azo-6-methyl pyridine-N-oxide of the formula: the di- (β-hydroxyethyl) 4'-amino-phenyl-2-azo-4-methyl pyridine-N-oxide of the formula: 4'-diethylamino-phenyl-2-azo-4-methyl pyridine-N-oxide of the formula: 4'-amino-naphthalene-1'-azo: 2-methyl-4-pyridine-N-oxide of the formula: 2 ', 4' -diamino-5 '-methyl-phenyl-2-azo-4-methyl pyridine-N-oxide of the formula: 4'-dimethylamphenol-2-azo-4-methyl pyridine-N-oxide of the formula: 4'-dimethylamino-phenyl-2-azo-4,6-dimethylpyridine-N-oxide of the formula: 2 ', 5' -dimethyl-4 '-hydroxy-phenyl-2-azo-4-methyl pyridine-N-oxide of the formula: 4'-dimethylamino-phenyl-2-azo-5-chloro-pyridine-N-oxide of the formula: 4 '-di-ethylamino-2'-methyl-phenyl-2-azo-5-chloro-pyridine-N-oxide of the formula: 4'-diethylamino-phenyl-2-azo-5-chloro-pyridine-N-oxide of the formula: 6'-hydroxy-benzomorpholine-7'-azo: 2-pyridine-N-oxide of the formula: 6'-Hydroxy-benzomorpholine-7'-azo: 2-methoxy-1-pyridinium methosulfate of the formula: 2 ', 4"-diamino 5' -methyl-phenyl-2-azo-pyridine-N-oxide of the formula: 2 '-methyl-5' -oxo-4'-phenyl-dihydropyrazolyl-2-azo-l-methoxy-pyridinium methosulfate of the formula: 3 '-methyl 2', 4 ', 6' -trioxo-hexahydro-pyrimidinyl-2-azo pyridine-N-oxide of the formula: 4'-amino-phenyl-2-azo pyridine-N-oxide of the formula: (β-phenylamino) -4'-phenyl-2-azo pyridine-N-oxide of the formula: (N-phenylamino) -4'-phenyl-2-azo pyridine-N-oxide of the formula: 4 '- (N-phenylamino) -4'-phenyl-2-azo-3-methyl pyridine-N-oxide of the formula: 4 '-amino-phenyl-2-azo-l, 3-dimethyl pyridinium methosulfate of the formula: di-4 '- (β-hydroxyethyl) amino-phenyl-2-azo-1,4-dimethyl pyridinium methosulfate of the formula: 4 '-dimethylamino-phenyl-2-azo-l, 3-dimethyl pyridinium methosulfate of the formula: N-4-phenylamino-phenyl-2-azo-l, 6-dimethyl pyridinium methosulfate the formula: 4 '-dimethylamino-phenyl-2-azo-l, 5-dimethyl pyridinium methosulfate of the formula: 4 '-dimethylamino-phenyl-2-azo-l, 6-dimethyl pyridinium methosulfate of the formula: 2 ', 4', 6 '-trioxo-trioxo-hexahydro-pyrimidinyl-2-azo pyridine-N-oxide of the formula: 4 '-dimethylamino-phenyl-2-azo-l, 3-dimethylbenzimidazolium perchlorate of the formula: 2 ', 4' -diamino 3'-pyridine-2-azo pyridine-N-oxide of the formula: The cationic direct dye (s) of formula (I) used according to the invention preferably represent from 0.001 to 10% by weight approximately of the total weight of the dyeing composition and even more preferably from 0.01 to 5% by weight approximately of this weight. The dyeing composition according to the invention can also contain one or more couplers and / or one or more additional direct dyes different from the compounds of the formula (I), in particular to modify the shades or enrich with reflections.

Among the copulators that may be present in the dye composition according to the invention, mention may be made in particular of meta-phenylenediamines, meta-aminophenols, meta-diphenols, heterocyclic couplers and their addition salts with an acid. When present, these couplers preferably represent from 0.0001 to 10% by weight approximately of the total weight of the dyeing composition and even more preferably from 0.005 to 5% by weight approximately of this weight. In a general manner, the addition salts with an acid which can be used within the framework of the dyeing compositions of the invention (oxidation bases and couplers) are particularly chosen from hydrochlorides, hydrobromides, sulfates and tartrates, lactates and acetates. The suitable medium for dyeing (or support) of the dyeing composition according to the invention is generally constituted by water or by a mixture of water and at least one organic solvent to solubilize the compounds that were not sufficiently soluble in water. As the organic solvent, for example, the Ci-C4 alkanols, such as ethanol and isopropanol, can be mentioned. The solvents may be present in preferably proportions comprised between 1 and 40% by weight approximately relative to the total weight of the dyeing 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 about 3 and about 12, and preferably between about 5 and about 12. It can be adjusted to the desired value by means of acidifying or alkalizing agents usually used in the dyeing of keratin fibers. Among the acidulating 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, acid lactic, sulfonic acids. Among the alkalizing agents, mention may be made, by way of example, of ammonia, alkali metal carbonates, alkanolamines such as mono-, di- and triethanolamines, 2-methyl-2-aminopropanol and its derivatives, sodium hydroxides. or of potassium and the compounds of formula (IX) below: wherein W is a propylene moiety optionally substituted by a hydroxyl group or a C1-C4 alkyl radical; R32, R33, R34 and R35, which are identical or different, represent a hydrogen atom, a C 1 -C 4 alkyl radical or a C 1 -C 4 hydroxyalkyl compound. The dye composition according to the invention can also include various adjuvants conventionally used in the compositions for the dyeing of the hair. Of course, the person skilled in the art will take care to choose this or these possible complementary compounds in such a way that the advantageous properties intrinsically related to the dyeing composition according to the invention are not substantially altered by the addition (s) considered. The dyeing composition according to the invention can be present in various forms, such as in the form of liquids, creams, gels, optionally pressurized, or in any other form suitable for dyeing the keratin fibers, and in particular human hair. .

The subject of the invention is also a process for dyeing keratin fibers, and in particular human keratin fibers such as hair using the dyeing composition as defined above. According to this process, the dyeing composition as defined above is applied to the fibers, the color revealed being at an acidic, neutral or alkaline pH with the aid of an oxidizing agent that is added just at the time of use in the composition. dye or that is present in an oxidizing composition applied simultaneously or sequentially separately. According to a particularly preferred embodiment of the dyeing process according to the invention, the dyeing composition described above is mixed, at the time of use, with an oxidizing composition containing, in a medium suitable for dyeing, at least one oxidizing agent present in an amount sufficient to develop a coloration. The mixture obtained is then applied to the keratin fibers and allowed to sit for about 3 to 50 minutes, preferably about 5 to 30 minutes, after which it is rinsed, washed with shampoo, rinsed again and dried.

The oxidizing agent present in the oxidizing composition as defined above can be chosen from the oxidizing agents conventionally used for dyeing by oxidation of the keratin fibers, and among which may be mentioned hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulfates, peracids, enzymes such as 2-electron oxido-reductases, peroxidases and laccases. Hydrogen peroxide is particularly preferred. The pH of the oxidizing composition including the oxidizing agent as defined above is such that after mixing with the dyeing composition, the pH of the resulting composition applied to the keratin fibers preferably ranges from about 3 to about 12 and still more preferably between 5 and 11. It is adjusted to the desired value by means of acidifying or alkalizing agents usually used in the dyeing of keratin fibers and as defined above. The oxidizing composition as defined above may also include various adjuvants conventionally used in the dyeing compositions of the hair.

The composition that is finally applied on the keratin fibers may be presented in various forms, such as in the form of liquids, creams, gels, or in any other form suitable for dyeing the keratin fibers, and particularly the human hair. . Another object of the invention is a multi-compartment device or dyeing kit or any other conditioning system of several compartments of which a first compartment includes the dyeing composition as defined above and a second compartment including the oxidizing composition. as defined above. These devices can be equipped with a means that allows to provide the desired mixture on the hair, such as the devices described in patent FR-2,586,913 in the name of the applicant firm. The following examples are intended to illustrate the invention without thereby limiting the scope.

EXAMPLES EXAMPLES OF DYE 1 to 4 The following dye compositions according to the invention (contained in grams) were prepared: (*): Common dye support: - Polyglycerolated oleic alcohol in 2 moles of glycerol 4.0 g Polyglycerolated oleic alcohol in 4 moles of glycerol "to 78% of active materials (M.A.) 5.69 g M.A.

- Oleic acid 3.0 g - Oleic amines in 2 moles of ethylene oxide sold under the trade name ETHOMEEN 012® by the AKZO Society 7.0 g - Diethylaminopropyl laurylamino succinamate, 55% sodium salt of M.A. 3.0 g M.A.

- Oleic alcohol 5.0 g - Dietanola ida of oleic acid 12.0 g - Propylene glycol 3.5 g - Ethyl alcohol 16.5 g - Sodium metabisulfite in 35% aqueous solution of M.A. 0.455 g M.A. Ammonium acetate 0.8 g - Antioxidant, sequestrant C.S. Perfume, preservative C.S. - Ammonia at 20% NH3 10.0 g At the time of use, each of the dyeing compositions described above was mixed with an equivalent weight amount of hydrogen peroxide in 20 volumes (6% by weight) having a pH of about 3. Each resulting mixture had a pH of approximately 10 ± 0.2 and was applied for 30 minutes on strands of gray hair at 90% of permanent targets. The hair was then rinsed with water, washed with a conventional shampoo, rinsed again and then dried.

The hair was dyed in the shades listed in the table given below: It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention. Having de crit or the invention as above, is claimed as property contained in the following:

Claims (24)

1. Composition for dyeing by oxidation of keratin fibers and in particular of human keratin fibers such as hair, characterized in that it comprises, in a medium suitable for dyeing: - at least one oxidation base, - at least one direct cationic dye of formula (I) below: AN = NB (I) in which: A represents a group selected from the following Al a A3 structures: A1 A2 Al A3 structures in which: Ri denotes an alkyl radical of d-C4, a phenyl radical or a phenyl radical substituted by a C 1 -C 4 alkyl radical or by a halogen atom selected from chlorine, bromine, iodine and fluorine; R 2 denotes a C 1 -C 4 alkyl radical or a phenyl radical; - R3 and R4, identical or different, represent a C1-C4 alkyl radical, a phenyl radical, or together form a benzene ring substituted by one or more C1-C4 alkyl radicals, C1-C4 alkoxy or nitro; R3 can also designate a hydrogen atom; - and Rβ, identical or different, represent a C1-C4 alkyl radical, a phenyl radical, or together form a benzene ring unsubstituted or substituted by one or more C1-C4 alkyl radicals, C1-C4 alkoxy or nitro; R5 can also designate a hydrogen atom; - R7 and R8, identical or different, represent a hydrogen or halogen atom selected from chlorine, bromine, iodine and fluorine, a C1-C4 alkyl radical, C1-C4 alkoxy or a nitro radical; Z designates an oxygen or sulfur atom or a group NR2 in which R2 can take the same meaning as indicated above; - the vertex L represents a group -CH, -CR or -N + R9 (X ~) r; - the vertex M represents a group -CH, -CR or -N + R9 (X ~) r; - r is an integer equal to 0 or 1; R represents a C 1 -C 4 alkyl radical; R9 represents a 0"atom, a C1-C4 alkyl or C1-C4 alkoxy radical; -X" represents an anion; it being understood that: - in the groups of the formula A3, at least one of the vertices L and M represents a group -N + R9 (X ~) r; - when R6 represents a C 1 -C 4 alkyl radical and when Z represents a sulfur atom, then R 5 is different from a C 1 -C 4 alkyl radical; when Re represents a C 1 -C 4 alkyl radical and when Z represents a sulfur atom, and when one of the radicals Rio and Rp represents a hydrogen atom, then R 5 is different from a hydrogen atom; when R9 designates 0", then r = 0; when L or M designates as radical a -N + R9 (X ") r, in which R represents a C1-C4 alkyl radical and r = 1, then at least one of the radicals R7 and Rg is different from a carbon atom. hydrogen, when L designates a radical -N + R9 (X ~) r, then M represents a group -CH or CR, when M designates a radical -N + R9 (X ~) r, then L represents a group -CH or CR: when Z represents a group NR2 in which R2 represents a C 1 -C 4 alkyl radical, then at least one of the radicals Ri, R 5 and R β is different from a C 1 -C 4 alkyl radical; - when Z represents an atom of sulfur and when Ri represents a C 1 -C 4 alkyl radical, and when one of the radicals Rio and Rp represents a hydrogen atom, then R 5 and R 2 can not together form an unsubstituted benzene ring; B represents: either ) a group of structure Bl following: B1 structure Bl in which RIO represents a hydrogen atom a halogen atom selected from chlorine, bromine, iodine and fluorine, a C1-C4 alkyl radical, C1-C4 alkoxy, hydroxyl, a -NHR13 group , -NR14R15, -NHCOalkyl of C1-C4, nitro, or form with Rp a cycle of 5 or 6 links carbonized or containing one or more heteroatoms selected from nitrogen, oxygen or sulfur; - R n represents a hydrogen atom, a halogen atom selected from chlorine, bromine, iodine and fluorine, a C 1 -C 4 alkyl radical, C 1 -C 4 alkoxy, or a R 5 or R 13 form or 6 carbon-containing or containing one or more heteroatoms selected from nitrogen, oxygen or sulfur; R 12 represents a hydrogen atom, a hydroxyl radical, a radical -NHR 13, or a radical -NR 14 R 15; - R 13 represents a hydrogen atom, a C 1 -C 4 alkyl radical, C 1 -C 4 monohydroxyalkyl, C 2 -C 4 polyhydroxyalkyl or phenyl; R 14 and R 15, identical or different, represent a C 1 -C 4 alkyl, C 1 -C 4 monohydroxyalkyl or C 2 -C 4 polyhydroxyalkyl radical; either (b) a 5- or 6-membered nitrogenous heterocyclic group, a 5- or 6-membered heterocyclic nitrogen group including one or more heteroatoms selected from oxygen and sulfur and / or one or more carbonylated groups, the indicated heterocycles being substituted by one or more C 1 -C 4 alkyl, amino or phenyl radicals.

2. Composition according to claim 1, characterized in that the anion X "is chosen from chloride, methylisulfate, ethyl sulfate, acetate and perchlorate.

3. Composition according to claim 1 or 2, characterized in that the 5 or 6-membered nitrogenous heterocyclic groups are chosen from the groups of structure B2 below: structure B2 in which Ri6 and Ri7 identical or different, represent an atom of hydrogen, a C1-C4 alkyl radical or a phenyl radical; Y represents a group CH, I 3 -C = 0 -C =; Y n is an integer equal to 0 or 1.

4. Composition according to any of the preceding claims, characterized in that the oxidation base (s) are chosen from paraphenylenediamines, double bases, para-aminophenols, ortho-aminophenols and heterocyclic oxidation bases.

5. Composition according to claim 4, characterized in that the para-phenylenediamines are chosen from the following compounds of formula (II) and their addition salts with an acid: - in which R18 represents a hydrogen atom, an alkyl radical of Ct-C4, monohydroxyalkyl of C1-C4, polyhydroxyalkyl of C2-C4, alkoxy (C1-C4) alkyl (Ci- C4), alkyl of C1-C4 substituted by a nitrogen, phenyl or 4'-a-phenyl group; Ri9 represents a hydrogen atom, a radical of C1-C4 alkyl, monohydroxyalkyl of d-C4, polyhydroxyalkyl of C2-C4, alkoxy (C1-C4) alkyl (C1-C4) or C1-C4 alkyl substituted by a nitrogen group; R20 represents a hydrogen atom, a halogen atom such as a chlorine, bromine, iodine or fluorine atom, a C1-C4 alkyl radical, C1-C4 monohydroxyalkyl, C1-C4 hydroxyalkoxy, C1 acetylaminoalkoxy -C4, C1-C4 mesylaminoalkoxy or C1-C4 carbamoylaminoalkoxy, -R21 represents a hydrogen atom, a halogen atom or a C1-C4 alkyl radical.

6. Composition according to claim 5, characterized in that the para-phenylenediamines of the formula (II) are chosen from para-phenylenediamine, para-tolylene-diamine, 2-chloro-para-phenylenediamine, 2,3-dimethyl paraphenylenediamine, 2,6-dimethyl paraphenylenediamine, 2,6-diethyl paraphenylenediamine, 2,5-dimethyl paraphenylenediamine, N, N-dimethyl paraphenylenediamine, N, N-diethyl paraphenylenediamine, N , N-dipropyl paraphenylenediamine, 4-amino N, N-diethyl 3-methyl aniline, N, N-bis- (β-hydroxyethyl) -paraphenylenediamine, 4-N, N-bis- (β-hydroxyethyl) amino 2- ethyl aniline, 4-N, N-bis- (β-hydroxyethyl) amino 2-chloroaniline, 2-β-hydroxyethyl paraphenylenediamine, 2-fluoro paraphenylenediamine, 2-isopropyl paraphenylenediamine, N- (β -hydroxypropyl) paraphenylenediamine, 2-hydroxymethyl paraphenylenediamine, N, N-dimethyl 3-methyl paraphenylenediamine, N, N- (ethyl, β-hydroxyethyl) paraphenylenediamine, N- (β, β-dihydroxypropyl) paraphenylenediamine, N - (4'-aminophenyl) paraphenylenediamine, N-phenyl paraphenylenediamine, 2-β-hydroxyethyl-oxy-paraphenylenediamine, 2-β-acetylamino-ethyloxy paraphenylenediamine, N- (β-methoxyethyl) paraphenylenediamine, and their salts tion with an acid.

7. Composition according to claim 4, characterized in that the double bases are chosen from the following compounds of formula (III), and their addition salts with an acid: wherein: Z and Z, identical or different, represent a hydroxyl radical or -NH2 which can be substituted by a C1-C alkyl radical or by a G-linking arm; - the linking arm G represents an alkylene chain comprising from 1 to 14 carbon atoms, linear or branched, which may be interrupted or terminated by one or more nitrogen groups and / or by one or more heteroatoms such as oxygen atoms, sulfur or nitrogen, and optionally substituted by one or more hydroxyl or Ci-Cβ alkoxy radicals; - R22 and R23 represent a hydrogen or halogen atom, a C1-C4 alkyl radical, a C1-C4 monohydroxyalkyl, a C2-C4 polyhydroxyalkyl, a C1-C4 aminoalkyl or a G-linking arm; - R24, R25, 26, R27, 28 and 29, identical or different, represent a hydrogen atom, a linking arm G or a C 1 -C 4 alkyl radical; it being understood that the compounds of the formula (III) only comprise one G-link arm per molecule.

8. Composition according to claim 7, characterized in that the double bases of formula (III) are chosen from N, N '-bis- (β-hydroxyethyl) N, N'-bis- (4'-aminophenyl) 1,3-diamino propanol, N, N'-bis- (β-hydroxyethyl) N, N'-bis- (4'-aminophenyl) ethylenediamine, N, N'-bis- (4-aminophenyl) tetramethylenediamine, N, N'-bis- (β-hydroxyethyl) N, N'-bis- (4-aminophenyl) tetramethylenediamine, N, N'-bis- ( 4- (methyl-aminophenyl) -tetramethylenediamine, N, N'-bis- (ethyl) N, N'-bis- (4'-amino, 3'-methylphenyl) ethylenediamine, 1,8-bis- (2, 5-diaminophenoxy) -3,5-dioxaoctane, and its addition salts with an acid.

9. Composition according to claim 4, characterized in that the para-aminophenols are chosen from the following compounds of formula (IV), and their addition salts with an acid: (IV) wherein: R30 represents a hydrogen or halogen atom, a C1-C4 alkyl radical, a C1-C4 monohydroxyalkyl, a (C1-C4) alkoxy (C1-C4) alkyl, a C1-C4 aminoalkyl or a hydroxyalkyl (C1 -C4) C 1 -C 4 aminoalkyl, R 31 represents a hydrogen or halogen atom, a C 1 -C 4 alkyl radical, d-C 4 monohydroxyalkyl, C 2 -C 4 polyhydroxyalkyl, C 1 -C 4 aminoalkyl, C 1 -C 4 cyanoalkyl or (C 1 -C 4) alkoxy (C 1 -C 4) alkyl, it being understood that at least one of the radicals R 30 and R31 represents a hydrogen atom.

10. Composition according to claim 9, characterized in that the para-aminophenols of formula (IV) are chosen from para-aminophenol, 4-amino 3-methyl phenol, 4-amino-3-fluoro-phenol, 4-amino-3-hydroxymethyl-phenol, 4-amino-2-methyl-phenol, 4-amino 2-hydroxymethyl phenol, 4-amino-2-methoxymethyl phenol, 4-amino-2-aminomethyl phenol, 4-amino 2- (β-hydroxyethyl aminomethyl) phenol, 4-amino-2-fluoro-phenol, and its salts addition with an acid.

11. Composition according to claim 4, characterized in that the ortho-aminophenols are chosen from 2-amino phenol, 2-amino-5-methyl phenol, 2-amino-6-methyl phenol, 5-acetamido-2-amino phenol, and their salts. addition with an acid.

12. Composition according to claim 4, characterized in that the heterocyclic oxidation bases are chosen from the pyridine derivatives, the pyrimidine derivatives, the pyrazole derivatives, and their addition salts with an acid.

13. Composition according to any of the preceding claims, characterized in that the oxidation base (s) represent from 0.0005 to 12% by weight of the total weight of the dyeing composition.

14. Composition according to claim 13, characterized in that the oxidation base (s) represent from 0.005 to 6% by weight of the total weight of the dyeing composition.

15. Composition according to any of the preceding claims, characterized in that the cationic direct dye (s) of formula (I) are chosen from: the 4'-dimethylamino-phenyl-2-azo-pyridine-N-oxide of the formula: 4'-dimethylamino-methyl-2'-phenyl-azo-2-pyridine-N-oxide of the formula: 2- [(1, 3-diamino-6-methyl-4-phenyl) -azo] -3-methyl-benzothiazolium iodide of the formula: 6 '-hydroxy-7'-benzomorpholine-2-aza-3-ethyl-benzothiazolium chloride of the formula: 6 '-hydroxy-7' -benzomorpholine-2-aza-4-methyl-3-phenyl thiazolium perchlorate of the formula: 6 '-hydroxy-7'-benzomorpholine-2-azo-3,4-diphenyl thiazolium perchlorate of the formula: CIO? 6 '-hydroxy-7'-benzomorpholine-2-aza-3-methyl benzothiazolium chloride of the formula: 6 '-hydroxy-7' -benzomorpholine-2-aza-4-methyl-3-phenyl thiazolium perchlorate of the formula: 2 ', 4' -diamino-5'-methoxy-phenyl-2-azo-pyridine-N-oxide of the formula: the 2 '-acetamido 4' -hydroxy-5 '-methyl-f-enyl-2-azo pyridine N-oxide of the formula: 2'-Acetamido-4'-dimethylamino-phenyl-2-azo pyridine-N-oxide of the formula: 2'-amino-4'-dimethylamino-phenyl-2-azo pyridine-N-oxide of the formula: 2 ', 4' -diamino-5 '-methyl-phenyl-2-azo perchlorate 1-methoxy pyridinium of the formula: 2 ', 5' -dimethyl-4 '-hydroxy-phenyl-2-azo pyridine-N-oxide of the formula: the 2'-dimethylamino-4'-hydroxy-phenyl-2-azo pyridine-N-oxide of the formula: 4'-dimethylamino-2'-hydroxy-phenyl-2-azo pyridine-N-oxide of the formula: 3 ', 5' -dimethyl-4 '-hydroxy-phenyl-2-azo-pyridine-N-oxide of the formula: 4'-dimethylamino-2-nitro-phenyl-2-azo pyridine-N-oxide of the formula: 8 '-hydroxy-quinoline-5' -azo 2 '-pyridine-N-oxide of the formula: 2 '-nitro-4'-dimethylamino-phenyl-2-azo-1-methoxy pyridinium methosulfate of the formula: 4'-dimethylamino-f-enyl-2-azo-5-nitro pyridine-N-oxide of the formula: 4'-dimethylamino-phenyl-2-azo-6-methyl pyridine-N- oxide of the formula: 4'-dimethylamino-phenyl-2-azo-5-methyl pyridine-N-oxide of the formula: 4'-dimethylamino-phenyl-2-azo-3-methyl pyridine-N-oxide of the formula: 4'-diethylamino-f-enyl-2-azo-3-methyl pyridine-N-oxide of the formula: 4'-dimethylamino-2'-acetylamino-phenyl-2-azo-3-methyl pyridine-N-oxide of the formula: 4'-amino-naphthalene-1'-azo: 2-methyl-6-pyridine-N-oxide of the formula: the di- (β-hydroxyethyl) amino-4'-phenyl-2-azo-6-methyl-pyridine-N-oxide of the formula: 4'-diethylamino-phenyl-2-azo-6-methyl pyridine-N-oxide of the formula: 2 ', 5' -dimeti1-4 '-hydroxy-pheny1-2-azo-6-methy1 pyridine-N-oxide of the formula: the di- (β-hydroxyethyl) 4'-amino-phenyl-2-azo-4-methyl pyridine-N-oxide of the formula: 4'-diethylamino-phenyl-2-azo-4-methyl pyridine-N-oxide of the formula: 4'-amino-naphthalene-1'-azo: 2-methyl-4-pyridine-N-oxide of the formula: 2 ', 4' -diamino-5 '-methyl-phenyl-2-azo-4-methyl pyridine-N-oxide of the formula: 4'-dimethylamino-phenyl-2-azo-4-methyl pyridine-N-oxide of the formula: 4'-dimethylamino-phenyl-2-azo-4,6-dimethylpyridine-N-oxide of the formula: 2 ', 5' -dimethyl-4 '-hydroxy-phenyl-2-azo-4-methyl pyridine-N-oxide of the formula: 4'-dimethylamino-phenyl-2-azo-5-chloro-pyridine-N-oxide of the formula: 4'-dimethylamino-2'-methyl-phenyl-2-azo-5-chloro-pyridine-N-oxide of the formula: 4'-diethylamino-phenyl-2-azo-5-chloro-pyridine-N-oxide of the formula: 6'-hydroxy-benzomorpholine-7'-azo: 2-pyridine-N-oxide of the formula: 6 '-hydroxy-benzomorpholine-7'-azo 2-methoxy-1-pyridinium methosulfate of the formula: 2 ', 4' -diamino 5 '-methyl-phenyl-2-azo-pyridine-N-oxide of the formula: 2 '-methyl-5' -oxo-4'-phenyl-dihydropyrazolyl-2-azo-l-methoxy-pyridinium methosulfate of the formula: 3 '-methyl 2', 4 ', 6' -trioxo-hexahydro-pyrimidinyl-2-azo pyridine-N-oxide of the formula: 4'-amino-phenyl-2-azo pyridine-N-oxide of the formula: (β-phenylamino) -4'-phenyl-2-azo pyridine-N-oxide of the formula: (N-phenylamino) -4'-phenyl-2-azo pyridine-N-oxide of the formula: 4 '- (N-phenylamino) -4'-phenyl-2-azo-3-methyl pyridine-N-oxide of the formula: 4 '-amino-phenyl-2-azo-l, 3-dimethyl pyridinium methosulfate of the formula: di-4 '- (β-hydroxyethyl) amino-f-enyl-2-azo-1,4-dimethyl pyridinium methosulfate of the formula: 4 '-dimethylamino-phenyl-2-azo-l, 3-dimethyl pyridinium methosulfate of the formula: N-4-phenylamino-phenyl-2-azo-l, 6-dimethyl pyridinium methosulfate the formula: 4 '-dimethylamino-phenyl-2-azo-l, 5-dimethyl pyridinium methosulfate of the formula: 4 '-dimethylamino-phenyl-2-azo-l, 6-dimethyl pyridinium methosulfate of the formula: 2 ', 4', 6 '-trioxo-trioxo-hexahydro-pyrimidinyl-2-azo pyridine-N-oxide of the formula: 4 '-dimethylamino-phenyl-2-azo-l, 3-dimethylbenzimidazolium perchlorate of the formula: 2 ', 4' -diamino 3'-pyridine-2-azo pyridine-N-oxide of the formula:

16. Composition according to any of the preceding claims, characterized in that the cationic direct dye (s) of formula (I) represent from 0.001 to 10% by weight of the total weight of the dyeing composition.

17. Composition according to claim 16, characterized in that the cationic direct dye (s) of formula (I) represent from 0.01 to 5% by weight of the total weight of the dyeing composition.

18. Composition according to any one of the preceding claims, characterized in that it contains one or more couplers and / or one or more additional direct dyes different from the cationic direct dyes of formula (I) as defined in claim 1.

19. Composition according to claim 18, characterized in that the coupler or couplers are chosen from meta-phenylenediamines, meta-aminophenols, meta-diphenols, heterocyclic couplers, and their addition salts with an acid.

20. Composition according to claim 18 or 19, characterized in that the coupler (s) represent from 0.0001 to 10% by weight of the total weight of the dyeing composition.

21. Composition according to claim 20, characterized in that the coupler (s) represent from 0.005 to 5% by weight of the total weight of the dyeing composition.

22. Composition according to any one of the preceding claims, characterized in that the addition salts with an acid are chosen from hydrochlorides, hydrobromides, sulfates and tartrates, lactates and acetates.

23 Procedure for dyeing keratin fibers and in particular human keratin fibers such as hair, characterized in that applies to said fibers at least one dyeing composition as defined in any of claims 1 to 22, and because the color is revealed at an acidic, neutral or alkaline pH with the aid of an oxidizing agent that is added just at the time of use to the dye composition or that is present in a simultaneous applied oxidant composition * or sequentially.

24. Process according to claim 23, characterized in that the oxidizing agent present in the oxidizing composition is chosen from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates, percarbonates and persulphates, perishes, and the enzymes. 25p. Multi-compartment device, or multi-compartment dye kit, of which a first, compartment includes a dye composition as defined in any of claims 1 to 22 and a second compartment includes an oxidizing composition.