MXPA97010190A - Composition of dyeing by oxidation of keratinic fibers and dyeing procedure using this composition - Google Patents

Abstract

The subject of the present invention is a ready-to-use composition for oxidation dyeing of keratin fibers, in particular human keratin fibers such as hair, comprising at least one oxidation base selected from paraphenylenediamines and bisphenilene diamines. phenylalkylenediamines, in association with at least one copulator selected from meta-phenylenediamines, at least one direct cationic dye and at least one oxidizing agent, and the dyeing process using this composition

Description

COMPOSITION OF DYEING BY OXIDATION DK THE QOERATINIC FIBERS 7 DYING PROCEDURE USING THIS COMPOSITION.

The subject of the present invention is a ready-to-use composition for oxidative dyeing of keratin fibers, in particular human keratin fibers such as hair, comprising, in a medium suitable for dyeing, at least one base oxidation selected from paraphenylenediamines and bis-phenylalkylenediamines, in association with at least one copulator selected from meta-phenylenediamines, at least one direct cationic dye and at least one oxidizing agent, as well as the dyeing process using this composition. The invention also relates to a coloring kit for the preparation of a composition of this kind ready for use. 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, generally called oxidation bases. Dye precursors by oxidation, or oxidation bases, are colorless compounds REF .: 26443 or weakly colored that, 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 meta-diamines, meta-aminophenols, meta-diphenols and some heterocyclic compounds. The variety of molecules used at the level of oxidation bases and copulators allows obtaining a rich range of colors. It is also known that in order to modify also the shades obtained and to give them reflections, it is possible to use, in association with the oxidation dye precursors and the couplers, direct dyes, that is to say colored substances that provide a coloration in the absence of oxidizing agent. The coloration called "permanent" obtained thanks to these dyes by oxidation, must on the other hand meet a certain number of demands. Thus, it must be able to obtain shades with the desired intensity and present a good behavior against external agents (light, weather, washing, permanent waving, perspiration, friction). The direct dyes belong largely to the family of the nitro compounds of the benzene series and have the drawback, when incorporated into the dyeing compositions, to lead to dyes having an insufficient toughness, in particular with respect to the shampoos. 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 reach reflections rich in color having good tenacity properties, in particular. Thus, the applicant firm ends up discovering that it is possible to obtain new dyes that are both luminous and tenacious by associating: - at least one oxidation base selected from para-phenylenediamines, bis-phenylalkylenediamines, and their addition salts with an acid, - at least one copulator selected from meta-phenylenediamines, and their addition salts with an acid, - at least one direct cationic dye of formula (I) given below, and - at least one oxidizing agent.

The invention therefore has as its first object a ready-to-use 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 the treatment of hair. dyeing: - at least one oxidation base selected from paraphenylenediamines, bis-phenylalkylenediamines, and their addition salts with an acid, - at least one copulator selected from meta-phenylenedianes and their addition salts with an acid: - at least one cationic direct dye selected from the following compounds of formula (I): O) in which: "Ri represents a hydrogen atom or a C 1 -C 4 alkyl radical, R 2 represents a hydrogen atom, an alkyl radical which can be substituted by a -CN radical or by an amino group, a radical 4 '-aminophenyl or form with Rx or with a carbon atom of the benzene nucleus that supports the radicals R3 and R4, an optionally oxygenated and / or nitrogenated heterocycle which can be substituted by an alkyl radical of C? -C4 R3 and R? identical or different, represent a hydrogen atom, a halogen atom such as bromine, chlorine, iodine or fluorine, a C1-C4 alkyl radical or C1-C4 alkoxy, a radical -CN, X "represents an anion of preference selected from chloride, methyl sulfate and acetate, B represents a group selected by the following structures Bl to Bll: B1 B2 B3 B4 B5 B6 B9 B10 B11 in which R5 represents a C 1 -C 4 alkyl radical, R 6 and R 7 / identical or different represent a hydrogen atom or a C 1 -C 4 alkyl radical; when Ri and R2 form a nitrogenous heterocycle, or when R3 and R4 represent a C1-C4 alkyl radical or a C1-C4 alkoxy radical, or when R2 represents a 4"-aminophenyl radical, then B may also represent a group of Structure B12 following: in which Rs has the same meaning as that indicated above for structures Bl to Bll; and - at least one oxidizing agent. The ready-to-use dye compositions according to the invention make it possible to arrive at shades in natural or ash-colored shades which have a good resistance to the different treatments that the hair may undergo and in particular with respect to the shampoos. The subject of the invention is also a process for dyeing oxidation of keratin fibers using this ready-to-use dye composition. The para-phenylenediamines which can be used as oxidation base in the ready-to-use dye compositions according to the invention are preferably selected from the following compounds of formula (II) and their addition salts with an acid: wherein: R8 represents a hydrogen atom, a C 1 -C 4 alkyl radical, C 1 -C 4 monohydroxyalkyl, C 2 -C 4 polyhydroxyalkyl, phenyl, 4'-aminophenyl or C 1 -C 4 alkoxy C 1 alkyl- C, R9 represents a hydrogen atom, a C1-C4 alkyl radical, C1-C4 monohydroxyalkyl or C2-C4 polyhydroxyalkyl, Rio represents a hydrogen atom, a halogen atom such as a chlorine, bromine atom, of iodine or of fluorine, an alkyl radical of C1-C4, monohydroxyalkyl of C1-C4, hydroxyalkoxy of C1-C4, mesylaminoalkoxy of C1-C4, carbamoylanoalkoxy of C1-C4 or acetylaminoalkoxy of Ci- R n represents a hydrogen atom or a C 1 -C 4 alkyl radical. Among the para-phenylenediamines of formula (II) mentioned above, paraphenylenediamine, para-tolylenediamine, 2-chloropraparalenylene diamine, 2,3-dimethyl paraphenylenediamine, 2,6-dimethyl paraphenylenediamine and 2,6-diethyl paraphenylenediamine can be more particularly mentioned. , 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-amino N, N-bis (β-hydroxyethyl) 3-methyl aniline, 4-amino 3-chloro N, N-bis- (β-hydroxyethyl) aniline 2 -β-hydroxyethyl paraphenylenediamine, 2-fluorparaphenylenediamine, 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 para-phenylenediamine, 2-β-hydroxyethyl-oxy-para-phenylenediamine, 2-β-acetylamino-ethyloxy-para-phenylenediamine, and their addition salts with an acid. Among the para-phenylenediamines of formula (II) indicated above, para-phenylenediamine, para-tolylenediamine, 2-isopropyl para-phenylenediamine, 2-β-hydroxyethyl paraphenylenediamine, 2-β-hydroxyethyloxy paraphenylenediamine, 2,6-dimethyl paraphenylenediamine are particularly preferred. , the 2,6-diethyl paraphenylenediamine, 2,3-dimethyl paraphenylenediamine, N, N-bis- (β-hydroxyethyl) paraphenylenediamine, 2-chloro paraphenylenediamine, and its addition salts with an acid.

The bis-phenylalkylenediamines which can be used as oxidation bases in the dye compositions ready for use according to the invention are preferably selected from the following compounds of formula (III), and their addition salts with an acid: wherein: Zi and Zj, identical or different, represent a hydroxyl radical or NHR? 5 in which Ri5 represents a hydrogen atom or a C1-C4 alkyl radical, R12 represents a hydrogen atom, an alkyl radical of C1-C4, C1-C4 monohydroxyalkyl, C2-C4 polyhydroxyalkyl or C1-C4 nanoalkyl whose amino moiety can be substituted, R13 and R1 identical or different, represent a hydrogen or halogen atom or a C1-6 alkyl radical C4, Y represents a radical taken from the group consisting of the following radicals: - (CH2) n; - (CH2) B-0- (CH2) a; - (CH2) a -CHOH- (CH2) m and - (CH2) m-N- (CH2) m-; CH3 in which n is an integer between 0 and 8 inclusive and m is an integer between 0 and 4 inclusive. Among the bis-phenylalkylenediamines of formula (III) indicated above, N, N'-bis- (β-hydroxyethyl) N'N-bis- (4'-aminophenyl) -1,3-diamine 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-methylaminophenyl) tetramethylenediamine, N, N'-bis- (ethyl) N, N '- bis- (4'-amino, 3'-methylphenyl) ethylenediamine, and its addition salts with an acid. Among these bis-phenylalkylenediamines of formula (III), N, N '-bis- (β-hydroxyethyl) N, N'-bis-. { 4'-aminophenyl) 1,3-diamine propanol or one of its addition salts with an acid are particularly preferred The meta-phenylenediamines which can be used as copulators in the ready-to-use dye compositions according to the invention are preferably chosen among the compounds of formula (IV) below, and their addition salts with an acid: wherein: Rie represents a hydrogen atom, an alkyl radical of C? -C monohydroxyalkyl of C1-C4, or polyhydroxyalkyl of C2-C, * R17 and RI »identical or different, represent a hydrogen atom, an alkyl radical of C1-C4, C1-C4 monohydroxyalkoxy, or C2-C4 polyhydroxyalkoxy; -R? 9 represents a hydrogen atom, a C1-C4 alkoxy radical, a C1-C4 aminoalkoxy, a C1-C4 monohydroxyalkoxy, a C2-C4 polyhydroxyalkoxy or a 2,4-dia inphenoxyalkoxy radical. Among the meta-phenylenediamines of formula (IV) indicated above, metaphenylenediamine, 3,5-diamino-1-ethyl-2-methoxybenzene, 3,5-diamino-2-methoxy-1-methyl-benzene, , 4-diamino-1-ethoxybenzene, 1,3-bis- (2,4-diaminophenoxy) propane, bis- (2,4-diaminophenoxy) methane, 1- (β-aminoethyloxy) 2,4-diamino benzene , 2-amino 1- (ß-hydroxyethyloxy) 4-methylaminobenzene, 2,4-diamino-1-ethoxy-5-methylbenzene, 2,4-diamino-5- (ß-hydroxyethyloxy) -1-methylbenzene, 2, 4-diamino l- (β, β-dihydroxypropyloxy) benzene, 2,4-diamino l- (β-hydroxyethyloxy) benzene, 2-amino 4-N- (β-hydroxyethyl) amino 1-methyloxy benzene, and their addition salts with an acid The addition salts with an acid usable in the context of the dyeing compositions of the invention are chosen in particular from hydrochlorides, hydrobromides, sulphates and tartrates The cationic direct dyes of formula (I) which can be used in the composi Dyeing preparations ready for use according to the invention are known compounds and are described, for example, in patent applications WO 95/01772, WO 95/15144 and EP-A-0 714 954. Among the direct cationic dyes of formula (I) which can be used in the ready-to-use dye compositions according to the invention, the compounds corresponding to the following structures (II) to (126) can be more particularly mentioned: CH, Cl (113) Among the particular compounds of structures (II) to (126) described above, the compound corresponding to structure (II) is very particularly preferred.

The addition salts with an acid which can be used in the framework of the dyeing compositions of the invention are chosen in particular from hydrochlorides, hydrobromides, sulfates and tartrates. The oxidizing agent present in the dyeing composition is chosen from the oxidizing agents conventionally usable in oxidation dyeing and preferably between hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulfates. Hydrogen peroxide is particularly preferred. The cationic direct dye (s) of formula (I) according to the invention preferably represent from 0.001 to 10% by weight approximately of the total weight of the ready-to-use dye composition and even more preferably from 0.05 to 2% by weight. approximately this weight.

The oxidation base or bases according to the invention, that is to say the paraphenylenediamines of formula (II) and / or the bis-phenylalkylenediamines of formula (III), preferably represent from 0.0001 to 10% by weight approximately of the total weight of the dye composition ready for use and even more preferably from 0.001 to 5% by weight of about this weight. The meta-phenylenediamines of formula (IV) according to the invention preferably represent from 0.0001 to 5% by weight approximately of the total weight of the ready-to-use dye composition and even more preferably from 0.005 to 3% in weight approximately of this weight. The pH of the dyeing composition as defined above is generally 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, carboxylic acids such as tartaric acid, citric acid, lactic acid, 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 tetranolamines as well as their derivatives, sodium or potassium hydroxides and compounds of formula (V) following: wherein R is a propylene moiety optionally substituted by a hydroxyl group or a C1-C4 alkyl radical; R20 R21 »R22 and 3 3 identical or different, represent a hydrogen atom, a C1-C4 alkyl radical or a C1-C4 hydroxyalkyl radical. The dyeing composition according to the invention can also contain, in addition to the dyes defined above, other coupling agents and / or other direct dyes, in particular for modifying the shades or enriching them with reflections. The suitable medium for dyeing (or support) of the ready-to-use dye composition according to the invention is generally constituted by water or by a mixture of water and by at least one organic solvent to solubilize the compounds that were not sufficiently soluble in water As the organic solvent, there may be mentioned, for example, the lower C1-C4 alkanols, such as ethanol and isopropanol; giicerol; glycols and ethers of glycols such as 2-butoxyethanol, propylene glycol, propylene glycol monomethylether, monoethylether and diethylene glycol monomethylether, as well as aromatic alcohols such as benzyl alcohol or phenoxyethanol, similar products and mixtures thereof. The solvents can be present in proportions preferably 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 ready-to-use dye compositions according to the invention can also include various adjuvants conventionally used in dyeing compositions for hair, such as anionic, cationic, non-ionic, amphoteric surfactants or mixtures thereof, anionic, cationic polymers, ionic, amphoteric, or their mixtures, mineral or organic thickeners, antioxidants, penetration agents, sequestering agents, perfumes, buffers, dispersing agents, conditioning agents, smoke agents, preserving agents, opacifying agents.

Of course, the person skilled in the art will take care to choose the one or any additional compounds mentioned above in such a way that the advantageous properties intrinsically related to the ready-to-use dye composition according to the invention are not, or substantially, altered by the the additions considered. The ready-to-use dye compositions according to the invention can be present in various forms, such as in the form of liquids, creams, gels, or in any other form suitable for dyeing the keratin fibers, and in particular the hair humans. The subject of the invention is also a process for dyeing keratin fibers and in particular human keratin fibers, such as hair using the ready-to-use dye composition as defined above.

According to this process, the ready-to-use dye composition as defined above is applied to the fibers and allowed to stand for about 3 to 40 minutes, preferably about 5 to 30 minutes, after which it is clarified, it is eventually washed with shampoo, rinsed again and dried. According to a first preferred embodiment, the method comprises a preliminary step consisting of storing separately, on the one hand, a composition (A) comprising, in a medium suitable for dyeing, at least one oxidation base selected from among the para-phenylenediamines, bis-phenylalkylenediamines, and their addition salts with an acid, at least one copulator selected from meta-phenylenediamines, and their addition salts with an acid and at least one cationic direct dye selected from the compounds of formula (I) ) as defined above, and on the other hand, a composition (B) that includes, in a medium suitable for dyeing, at least one oxidizing agent as defined above, and in proceeding to its mixing at the time of the use before applying this mixture on the keratin fibers. According to a second preferred embodiment, the method includes a preliminary step consisting of storing separately, for a part, a composition (A) comprising, in a medium suitable for dyeing, at least one oxidation base selected from paraphenylenediamines, bis-phenylalkylenediamines, and their addition salts with an acid, at least one copulator selected from meta-phenylenediamines and their addition salts with an acid; on the other hand a composition (A * ") comprising, in a medium suitable for dyeing, at least one direct cationic dye selected from the compounds of formula (I) as defined above, and finally, a composition (B ) which includes, in a medium suitable for dyeing, at least one oxidizing agent as defined above, and in proceeding to its mixing at the time of use before applying this mixture to the keratin fibers. ') used according to this second variant of the process according to the invention, can optionally be present in the form of a powder, the cationic direct dye (s) of formula (I) according to the invention then constituting the entire composition by itself indicated (A ') or optionally dispersed in an organic and / or mineral pulverulent excipient When present in the composition A', the organic excipient may be of synthetic origin. or vegetable and is chosen particularly between cross-linked and non-crosslinked synthetic polymers, polysaccharides such as celluloses and modified or non-modified starches as well as the natural products that include them such as wood sawdust and vegetable gums (guar, carob, xanthan, etc ..) When present in the composition (A '), the mineral excipient may be constituted by metal oxides such as titanium oxides, the aluminum oxides, the kaolin, the talc, the silicates, the mica and the silicas. An advantageously preferred excipient according to the invention is wood sawdust. The powder composition (A ') may also include binders or coating products in an amount not exceeding preferably about 3% by weight of the total of said composition (A'). These binders are preferably chosen from oils and liquid fatty substances of mineral, synthetic, animal or vegetable origin. The composition (A ') may optionally also contain other adjuvants, in powder form, in particular surfactants of any nature, hair conditioning agents such as cationic polymers, etc. Another object of the invention is a multi-device. dyeing compartments or "kit" or any other multi-compartment conditioning system of which a first compartment includes the composition (A) as defined above, a second eventual compartment includes the composition (A ') as defined above when the same is present and a third compartment includes the oxidizing composition (B) as defined above. These devices can be equipped with a means for providing the hair with the desired mixture, such as the devices described in patent FR-A-2,586,913 in the name of the applicant. The following examples are intended to illustrate the invention without thereby limiting the scope thereof.

EXAMPLES EXAMPLE 1 Composition 1 (A), according to the invention, was prepared as follows (contents in grams): (*) Common dye support: - Polyglycerolated oleic alcohol in 2 moles of glycerol 4.0 g - Polyglycerolated oleic alcohol in 4 moles of glycerol, 78% of active substances (M.A.) 5.69 g M.A. - Oleic acid - Oleic amine in 2 moles of ethylene oxide sold under the name ETHOMEEN 012 by the AKZO Society 7.0 g - Diethylaminopropyl laurylamino succinamate, sodium salt, 55% of M.A. 3.0 g M.A.

- Oleic alcohol 5.0 g - Oleanic acid diethanolamide 12.0 g - Propylene glycol 3.5 g - Ethyl alcohol 7.0 g - Dipropylene glycol 0.5 g - Propylene glycol monomethyl ether 9.0 g - Sodium metabisulphite in aqueous solution ai 3b% of M.A. 0.4bb g M.A. - 0.8 g ammonium acetate - Antioxidant, sequestrant 'c.s. - Perfume, preservative c. s. - Ammonia at 20% NH3 10.0 g At the time of use, each of these compositions 1 (A) to 4 (A) was mixed with an equal amount of a composition (B) constituted by a solution of hydrogen peroxide in 20 volumes (6% by weight) . Each resulting composition (composition ready for use according to the invention) was applied for 30 minutes on wicks of natural gray hair at 90% white. The hair strands were then rinsed, washed with standard shampoo and then dried. The hair was stained in a luminous ash-brown shade that resists well to the subsequent shampoos. According to the variant of the invention, the direct cationic dye of structure (II) can be incorporated into composition 1 (A) at the time of use.

Example 2 The following composition 2 (A) was prepared: - Paratoluylenediamine sulphate 1.25 g - 2-amino 4-N- (ß-hydroxyethyl) -amino-1-methoxybenzene dichloride. 0.35 g - Common dye support as described above for example 1 (*) - Demineralized water c.s.p. 100 g The following composition 2 (A '') was prepared: - Cationic dye of structure (II) 4 g - Quaternary polyammon sold under the trade name CELQUAT SC-240 by the National Starch Society 10 g - Wood sawdust c.s. 100 g At the time of use, one part by weight of the composition 2 (A) indicated above was mixed with 0.1 part by weight of the composition 2 (A ') and with one part by weight of a composition (B) constituted by a solution of hydrogen peroxide in 20 volumes (6% by weight).

The resulting composition was applied for 30 minutes on wicks of natural gray hair at 90% white. The hair was then rinsed, washed with standard shampoo and then dried. The hair was stained in an ashen brown color that resists well to the subsequent shampoos.

Claims (21)

1. A ready-to-use composition for 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 selected from para-phenylenediamines, bis-phenylalkylenediamines, and their addition salts with an acid, - at least one copulator selected from meta-phenylenediamines and their addition salts with an acid: - at least one cationic direct dye selected from the following compounds of formula (I): wherein: Ri represents a hydrogen atom or an alkyl radical of C? -C4 R2 represents a hydrogen atom, an alkyl radical that can be substituted by a -CN radical or by an amino group, a 4'-aminophenyl radical or form with Ri or with a carbon atom of the benzene nucleus which supports the radicals R3 and R4, an optionally oxygenated and / or nitrogenated heterocycle which can be substituted by an alkyl radical of C1-C4, R3 and R4, identical or different, they represent a hydrogen atom, a halogen atom such as bromine, chlorine, iodine or fluorine, a C 1 -C 4 alkyl radical or C 1 -C 4 alkoxy a -CN radical, X "represents an anion preferably selected from chloride, methyl sulfate and acetate, B represents a group selected by the following structures Bl to Bll: B1 B2 B3 B4 B5 B6 B9 B10 B11 in which R5 represents an alkyl radical of C1-C4, R6 and R7r identical or different represent a hydrogen atom or an alkyl radical of C? -C4; when Rx and R2 form a nitrogen heterocycle, or when R3 and R4 represent a C1-C4 alkyl radical or a C1-C4 alkoxy radical. or when R2 represents a 4'-aminophenyl radical, then B may also represent a group of structure B12 below: wherein R5 has the same meaning as that indicated above for structures Bl to Bll; and - at least one oxidizing agent.

2. Composition according to claim 1, characterized in that the para-phenylenediamines are chosen from the following compounds of formula (II), and their addition salts with an acid: wherein: R8 represents a hydrogen atom, a C1-C4 alkyl monohydroxyalkyl radical of C1-C4, polyhydroxyalkyl of C2-C, phenyl, 4'-aminophenyl or (C1-C4) alkoxy C1-C4 alkyl, Rg represents a hydrogen atom, a C1-C4 monohydroxyalkyl C1-C4 alkyl or a C2-C4 polyhydroxyalkyl radical, Rio represents a hydrogen atom, a halogen atom such as a chlorine, bromine, iodine or fluorine, an alkyl radical of C? -Cr monohydroxyalkyl of C1-C4, hydroxyalkoxy of C1-C4, mesylaminoalkoxy of C1-C4, carbamoylaminoalkoxy of C1-C4 or acetylaminoalkoxy of C? ~ C4, Rn represents a hydrogen atom or a radical C1-C4 alkyl.

3. Composition according to claim 2, characterized in that the para-phenylenediamines of formula (II) are chosen from para-phenylenediamine, para-tolylenediamine, 2-chloro-araphenylenediamine, 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-amino N, N-bis (β-hydroxyethyl) 3-methyl aniline, 4-amino 3-chloro N, N-bis- (ß-hydroxyethyl) aniline, 2-ß-hydroxyethyl paraphenylenediamine, 2-fluorparaphenylenediamine, 2-isopropyl paraphenylenediamine, N- (ß-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) raphenylenediamine, N-phenyl paraphenylenediamine, 2-β-hydroxyethyloxy paraphenylenediamine, 2-β-acetylaminoethyloxy paraphenylenediamine, and their addition salts with an acid.

4. Composition according to claim 1, characterized in that the bis-phenylenediamines are chosen from the following compounds of formula (III), and their addition salts with an acid: wherein: Zi and ^ 2, identical or different, represent a hydroxyl radical or NHR15 in which R15 represents a hydrogen atom or a C1-C4 alkyl radical, R12 represents a hydrogen atom, a C1-6 alkyl radical C4, C1-C4 monohydroxyalkyl, C2-C4 polyhydroxyalkyl or C1-C4 aminoalkyl whose amino moiety can be substituted, R13 and R14, identical or different, represent a hydrogen or halogen atom or a C1-C4 alkyl radical , Y represents a radical taken from the group consisting of the following radicals: - (CH2) n; - (CH2) «- 0- (CH2) B; - (CH2) m-CHOH- (CH2) m and CH3 in which n is an integer between 0 and 8 inclusive and m is an integer between 0 and 4 inclusive.

5. Composition according to claim 4, characterized in that the bis-phenylalkylenediamines 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- (ß-hydroxyethyl) N, N'-bis- (4-aminophenyl) tetramethylenediamine, N,' -bis- (4-methylaminophenyl) tetramethylenediamine, N, N'-bis- (ethyl) N, N'-bis- (4'-amino, 3-methylphenyl) ethylenediamine, and their addition salts with an acid.

6. Composition according to any one of the preceding claims, characterized in that the meta-diphenylenediamines are chosen from the following compounds of formula (IV) and their salts of addition salts with an acid: wherein: Rie represents a hydrogen atom, a C 1 -C 4 alkyl radical, C 1 -C 4 monohydroxyalkyl, or C 2 -C 4 polyhydroxyalkyl; R17 and Rißf identical or different, represent a hydrogen atom, a C1-C4 alkyl radical, C1-C4 monohydroxyalkoxy, or C2-C polyhydroxyalkoxy, * -Rig represents a hydrogen atom, an alkoxy radical of C? C4, C1-C4 aminoalkoxy, C1-C4 monohydroxyalkoxy, C2-C4 polyhydroxyalkoxy or a 2,4-diaminophenoxyalkoxy radical.

7. Composition according to claim 6, characterized in that the methylenediamines of formula (IV) are chosen from metaphenylenediamines, 3,5-diamino-1-ethyl-2-methoxybenzene, 3,5-diamino-2-methoxy-1-methyl benzene, 2,4-diamino-1-ethoxybenzene, 1,3-bis- (2,4-diaminophenoxy) propane, bis- (2,4-diaminophenoxy) methane, 1- (β-aminoethyloxy) 2, 4-diamino benzene, 2-amino 1- (ß-hydroxyethyloxy) 4-methylaminobenzene, 2,4-diamino-1-ethoxy-5-methylbenzene, 2,4-diamino-5- (ß-hydroxyethyloxy) -1-methylbenzene , 2,4-diamino l- (β, β-dihydroxypropyloxy) benzene, 2,4-diamino l- (β-hydroxyethyloxy) benzene, 2-amino 4-N- (β-hydroxyethyl) amino 1-methyloxy benzene, and its addition salts with an acid.

8. Composition according to any one of the preceding claims, characterized in that the cationic direct dyes of formula (I) are chosen from the compounds that respond to the following structures (II) to (126): CH, / N

9. 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.

10. Composition according to any one of the preceding claims, characterized in that the oxidizing agent is chosen from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulfates.

11. Composition according to any one 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 dye composition ready for use.

12. Composition according to any one of the preceding claims, characterized in that the paraphenylenediamines of formula (II) and / or the bis-phenylalkylenediamines of formula (III) represent from 0.0001 to 10% by weight of the weight total of the dye composition ready for employment.

13. Composition according to any one of the preceding claims, characterized in that the meta-phenylenediamines of formula (IV) represent from 0.0001 to 5% by weight of the total weight of the dye composition ready for use.

14. Composition according to any one of the preceding claims, characterized in that it has a pH comprised between 5 and 12.

15. Composition according to any one of the preceding claims, characterized in that the medium suitable for the dye is constituted by water or by a mixture of water and by at least one organic solvent.

16. Dyeing process of keratin fibers and in particular of human keratin fibers such as hair, characterized in that at least one dyeing composition as defined in any one of claims 1 to 15 is applied to these fibers.

17. Process according to claim 16, characterized in that it comprises a preliminary step consisting of storing separately, on the one hand, a composition (A) that includes, in a medium suitable for dyeing, at least one oxidation base selected between the para-phenylenediamines, the bis-phenylalkyne diamines, and their addition salts with an acid, at least one copulator selected from the meta-phenylenediamines, and their addition salts with an acid and at least one cationic direct dye selected from the compounds of the formula (I) as defined in claim 1, and on the other hand, a composition (B) which includes, in a medium suitable for dyeing, at least one oxidizing agent as defined above, and in proceeding to its mixing at the time of use before applying this mixture on the keratin fibers.

18. Dyeing process according to claim 16, characterized in that it includes a preliminary step consisting of storing separately, on the one hand a composition (A) comprising, in a medium suitable for dyeing at least one oxidation base selected from para-phenylenediamines, bis-phenylalkylenediamines, and their addition salts with an acid, at least one copulator selected from meta-phenylenediamines and their addition salts with an acid; on the other hand a composition (A ') comprising, in a medium suitable for dyeing, at least one direct cationic dye selected from the compounds of formula (I) as defined above, and finally, a composition (B) which includes, in a medium suitable for dyeing, at least one oxidizing agent as defined above, and in proceeding to its mixing at the time of use before applying this mixture to the keratin fibers.

19. Process according to claim 18, characterized in that the composition (A ') is in powder form.

20. Multi-compartment device or dyeing kit, characterized in that a first compartment includes a composition (A) as defined in claim 17 and a second compartment includes an oxidizing composition (B).

21. Multi-compartment device or "kit" for dyeing, characterized in that a first compartment includes a composition (A) as defined in claim 18, a second compartment includes a composition (A ') as defined in Claim 18 or 19 and a third compartment includes an oxidizing composition (B)