WO1999033436A1

WO1999033436A1 - Use of a polycyclic direct colouring agent for direct or oxidation dyeing of keratinous fibres, dyeing compositions containing same and dyeing methods

Info

Publication number: WO1999033436A1
Application number: PCT/FR1998/002356
Authority: WO
Inventors: Mireille Maubru
Original assignee: L'oreal
Priority date: 1997-12-23
Filing date: 1998-11-04
Publication date: 1999-07-08
Also published as: AU1491099A

Abstract

The invention concerns the use of a polycyclic direct colouring agent for direct or oxidation dyeing of keratinous fibres. The invention also concerns dyeing compositions containing said compound and dyeing methods using said compositions.

Description

USE OF A POLYCYCLIC DIRECT DYE

FOR DIRECT DYEING OR OXIDATION OF FIBERS

KERATINICS, TINCTORIAL COMPOSITIONS CONTAINING THE SAME AND

DYEING PROCESSES

The invention relates to the use of a polycyclic direct dye for the direct dyeing or oxidation of keratin fibers.

The subject of the invention is also the dye compositions containing this compound as well as the dyeing processes using these compositions.

There are mainly two main types of hair coloring. The first is semi-permanent coloring or direct coloring which uses dyes capable of bringing to the natural coloring of the hair, a more or less marked modification resistant to several shampoos. These dyes are called direct dyes and are used without an oxidizing agent. The second is permanent coloring or oxidation coloring. This is carried out with precursors of so-called "oxidation" dyes which are colorless or weakly colored compounds which, when mixed with oxidizing products, at the time of use, can give rise to a process of oxidative condensation. to colored and coloring compounds.

It is often necessary to combine red direct dyes or combinations of oxidation bases and couplers leading to red shades, one or more green or yellow green direct dyes so as to neutralize or reduce the red shades to shades. more brown.

Among the direct dyes available, the benzene nitro direct dyes are not sufficiently powerful, and the indoamines as well as the trinoyal dyes have a low affinity for keratin fibers and therefore lead to dyes which are not sufficiently resistant towards different treatments that the fibers can undergo, and in particular with respect to shampoos. The Applicant has therefore sought a direct dye having a good affinity for keratin fibers, which can dye the fibers in a green shade and also making it possible to reduce shades that are too red.

It is as a result of this research that the Applicant has surprisingly discovered that the use of the polycyclic direct dye of formula (I) defined below made it possible to achieve this objective.

The present invention therefore has as a first object a composition for the direct dyeing or the oxidation dyeing of keratin fibers and in particular human keratin fibers such as the hair, characterized in that it contains, in a medium suitable for the dye, at least one polycyclic direct dye of formula (I) below:

+ in which R and R ₂ , identical or different, represent a hydrogen atom, an alkyl radical in CC ₄ , monohydroxyalkyl in C _r C ₄ or polyhydroxyalkyl in C ₂ -C ₄ .

According to a preferred embodiment of the invention, the dye composition according to the invention contains at least one direct dye of formula (I) in which R ₁ and R ₂ simultaneously represent a hydrogen atom. The direct dye (s) of formula (I) preferably represent from 0.0005 to 12% by weight approximately of the total weight of the dye composition, and even more preferably from 0.005 to 6% by weight approximately of this weight.

The medium suitable for dyeing (or support) generally consists of water or of a mixture of water and at least one organic solvent to dissolve the compounds which are not sufficiently soluble in water. As organic solvent, mention may, for example, be made of lower CC ₄ alkanols, such as ethanol and isopropanol; glycerol; glycols and glycol ethers such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, monoethyl ether and diethylene glycol monomethyl ether, as well as aromatic alcohols such as benzyl alcohol or phenoxyethanol, analogous 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 dye composition according to the invention is generally between 3 and 12 approximately, and preferably between 5 and 11 approximately. It can be adjusted to the desired value by means of acidifying or basifying agents usually used in dyeing keratin fibers.

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

Among the basifying agents, there may be mentioned, by way of example, ammonia, alkali carbonates, alkanolamines such as mono-, di- and triethanolamines as well as their derivatives, sodium or potassium hydroxides and compounds of formula (II) below: R ₃

/ ^R 5 ⁵

N-W- N (II)

4 \

R ₄ R ₆ in which W is a propylene residue optionally substituted with a hydroxyl group or a C _r C ₆ alkyl radical; R _3, R _4, R ₅ and R _6, identical or different, represent a hydrogen atom, an alkyl radical in C _r C ₆ hydroxyalkyl CC _6.

The dye composition in accordance with the invention may, according to a preferred embodiment of the invention, and in addition to the compound or compounds of formula (I), contain one or more additional red direct dyes which can, for example, be chosen from following red benzene dyes:

- 1-hydroxy-3-nitro-4-N- (γ-hydroxypropyl) amino benzene,

- N- (β-hydroxyethyl) amino-3-nitro-4-amino benzene,

- 1-amino-3-methyl-4-N- (β-hydroxyethyl) amino-6-nitro benzene,

- 1-hydroxy-3-nitro-4-N- (β-hydroxyethyl) amino benzene, - 1, 4-diamino-2-nitrobenzene,

- 1-amino-2-nitro-4-methylamino benzene,

- N- (β-hydroxyethyl) -2-nitro-paraphenylenediamine,

- 1-amino-2-nitro-4- (β-hydroxyethyl) amino-5-chloro benzene,

- 2-nitro-4-amino-diphenylamine, and - le1-amino-3-nitro-6-hydroxybenzene.

The dye composition in accordance with the invention may also contain one or more additional orange direct dyes, among which mention may be made, for example, of the following orange benzene direct dyes: - 1- (β-aminoethyl) amino-2-nitro-4- ( β-hydroxyethyloxy) benzene,

- 1- (β, γ-dihydroxypropyl) oxy-3-nitro-4- (β-hydroxyethyl) amino benzene,

- 1-hydroxy-3-nitro-4-aminobenzene,

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

- 1-methoxy-3-nitro-4- (β-hydroxyethyl) amino benzene, - 2-nitro-4'-hydroxydiphenylamine, and - 1-amino-2-nitro-4-hydroxy-5-methylbenzene.

The dye composition in accordance with the invention may also contain, in addition to or in replacement of these red or orange benzene dyes, one or more additional direct dyes chosen from yellow, green yellow, blue or purple benzene dyes, azo dyes, anthraquinone, naphthoquinone or benzoquinone dyes, indigo dyes, or dyes derived from triarylmethane.

These additional direct dyes may in particular be basic dyes, among which there may be mentioned more particularly the dyes known under the names "Basic Brown 16", "Basic Bro n 17", "Basic Yeilow 57", "Basic Red 76", "Basic Violet 10 "," Basic Blue 26 "and" Basic Blue 99 "in the COLOR INDEX, 3rd edition or direct acid dyes among which we can more particularly mention the dyes known under the names" Acid Orange 7 "," Acid Orange 24 "," Acid Yeilow 36 ", Acid Red 33", "Acid Red 184", "Acid Black 2", "Acid Violet 43", and "Acid Blue 62" in the COLOR INDEX, 3rd edition.

Among the additional yellow and green yellow benzenic direct dyes, mention may, for example, be made of the compounds chosen from:

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

- 1-methylamino-2-nitro-5- (β, γ-dihydroxypropyl) oxy benzene,

- 1- (β-hydroxyethyl) amino-2-methoxy-4-nitrobenzene, - 1- (β-aminoethyl) amino-2-nitro-5-methoxy-benzene,

- 1,3-di (β-hydroxyethyl) amino-4-nitro-6-chlorobenzene,

- 1-amino-2-nitro-6-methyl-benzene,

- 1- (β-hydroxyethyl) amino-2-hydroxy-4-nitrobenzene,

- N- (β-hydroxyethyl) -2-nitro-4-trifluoromethylaniline, - 4- (β-hydroxyethyl) amino-3-nitro-benzenesulfonic acid,

- 4-ethylamino-3-nitro-benzoic acid,

- 4- (β-hydroxyethyl) amino-3-nitro-chlorobenzene, - 4- (β-hydroxyethyl) amino-3-nitro-methylbenzene,

- 4- (β, γ-dihydroxypropyl) amino-3-nitro-trifluoromethylbenzene,

- 1- (β-ureidoethyl) amino-4-nitrobenzene,

- 1, 3-diamino-4-nitrobenzene, - 1-hydroxy-2-amino-5-nitrobenzene,

- 1-amino-2- [tris (hydroxymethyl) methyl] amino-5-nitro-benzene,

- 1- (β-hydroxyethyl) amino-2-nitrobenzene, and

- 4- (β-hydroxyethyl) amino-3-nitrobenzamide.

Among the additional direct benzene blue or purple dyes, mention may, for example, be made of the compounds chosen from:

- 1- (β-hydroxyethyl) amino-4-N, N-bis- (β-hydroxyethyl) amino 2-nitrobenzene,

- 1- (γ-hydroxypropyl) amino 4-N, N-bis- (β-hydroxyethyl) amino 2-nitrobenzene,

- 1- (β-hydroxyethyl) amino 4- (N-methyl, N-β-hydroxyethyl) amino 2-nitrobenzene,

- 1- (β-hydroxyethyl) amino 4- (N-ethyl, N-β-hydroxyethyl) amino 2-nitrobenzene,

- 1- (β, γ- ^' dihydroxypropyl) amino 4- (N-ethyl, N-β-hydroxyethyl) amino 2-nitrobenzene,

- the 2-nitroparaphenylenediamines of formula (III) below:

in which :

- R7 represents a C-1-C4 alkyl radical, a β-hydroxyethyl or β-hydroxypropyl or γ-hydroxypropyl radical;

- Rβ and Rg, identical or different, represent a β-hydroxyethyl radical, - hydroxypropyl, γ-hydroxypropyl, or β, γ-dihydroxypropyl, at least one of radicals R7, Rs or Rg representing a γ-hydroxypropyl radical and R7 and RQ which cannot simultaneously denote a β-hydroxyethyl radical when R7 is a γ-hydroxypropyl radical, such as those described in patent application FR 92-07515.

When they are present, the additional direct dye (s) preferably represent from 0.0005 to 12% by weight approximately of the total weight of the dye composition, and even more preferably from 0.005 to 6% by weight approximately of this weight.

When it is intended for the oxidation dye, the dye composition according to the invention contains, in addition to the compound or compounds of formula (I), one or more oxidation bases chosen from the oxidation bases conventionally used for oxidation dyeing and among which there may be mentioned in particular para-phenylenediamines, bis-phenylalkylenediamines, para-aminophenols, ortho-aminop ^' henols and heterocyclic bases.

Among the paraphenylenediamines that may be mentioned more particularly by way of example, paraphenylenediamine, paratoluylenediamine, 2-chloro paraphenylenediamine, 2,3-dimethyl paraphenylenediamine, 2,6-dimethyl paraphenylenediamine, 2,6-diethyl paraphenylenediamine , 2,5-dimethyl paraphenylenediamine, N, N-dimethyl paraphenylenediamine, N, N-diethyl paraphenylenediamine, N, N-dipropyl paraphenylenediamine, 4-amino N, N-diethyl 3-methyl aniline, NN- bis- (β-hydroxyethyl) paraphenylenediamine, 4-N, N-bis- (β-hydroxyethyl) amino 2-methyl aniline, 4-N, N-bis- (β-hydroxyethyl) amino 2-chloro aniline, 2-β-hydroxyethyl paraphenylenediamine, 2-fluoro paraphenylenediamine, 2-isopropyl paraphenylenediamine, N- (β-hydroxypropyl) paraphenylenediamine, 2-hydroxymethyl paraphenylenediamine, N, N-dimethyl 3-methyl paraphenylenediamine, N, N, - (ethyl, β-hydroxyethyl) paraphenylenediamine, N- (β, γ-dihydroxypropyl) paraphenyl nediamine, N- (4'-aminophenyl) paraphenylenediamine, N-phenyl paraphenylenediamine, 2-β-hydroxyethyloxy paraphenylenediamine, 2-β-acetylaminoethyloxy paraphenylenediamine, N- (β-methoxyethyl) paraphenylenediamine, and their addition salts with an acid.

Among the paraphenylenediamines mentioned above, very particularly preferred are paraphenylenediamine, paratoluylenediamine, 2-isopropyl paraphenylenediamine, 2-β-hydroxyethyl paraphenylenediamine, 2-β-hydroxyethyloxy paraphenylenediamine, 2,6-dimethyl paraphenylened , 6-diethyl paraphenylenediamine, 2,3-dimethyl paraphenylenediamine, N, N-bis- (β-hydroxyethyl) paraphenylenediamine, 2-chloro paraphenylenediamine, 2-β-acetylaminoethyloxy paraphenylenediamine, and their addition salts with a acid.

Mention may more particularly be made, among bis-phenylalkylenediamines, by way of example, of 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'-brs- (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 their addition salts with an acid.

Among the para-aminophenols, mention may more particularly be made, by way of example, of para-aminophenol, 4-amino 3-methyl phenol, 4-amino 3-fluoro phenol, 4-amino 3-hydroxymethyl phenol, 4-amino 2-methyl phenol, 4-amino 2-hydroxymethyl phenol, 4-amino 2-methoxymethyl phenol, 4-amino 2-aminomethyl phenol, 4-amino 2- (β-hydroxyethyl aminomethyl) phenol, 4-amino 2-fluoro phenol, and their addition salts with an acid.

Among the ortho-aminophenols, there may be mentioned more particularly by way of example, 2-amino phenol, 2-amino 5-methyl phenol, 2-amino 6-methyl phenol, 5-acetamido 2-amino phenol, and their addition salts with an acid. there

Among the heterocyclic bases that may be mentioned more particularly by way of example, pyridine derivatives, pyrimidine derivatives and pyrazole derivatives.

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

When it is intended for oxidation dyeing, the dye composition in accordance with the invention may also contain, in addition to the compounds of formula (I) and oxidation bases, one or more couplers so as to modify or enriching the shades obtained by reflecting the compounds of formula (I) and the oxidation base (s).

The couplers which can be used in the dye composition in accordance with the invention can be chosen from the couplers conventionally used in oxidation dyeing and among which mention may be made of metaphenylenediamines, meta-aminophenols, metadiphenols and heterocyclic couplers.

These couplers are more particularly chosen from 2-methyl 5-amino phenol, 5-N- (β-hydroxyethyl) amino 2-methyl phenol, 3-amino phenol, 1, 3-dihydroxy benzene, 1, 3 -dihydroxy 2-methyl benzene, 4-chloro 1, 3-dihydroxy benzene, 2,4-diamino l- (β-hydroxyethyloxy) benzene, 2-amino 4- (β-hydroxyethylamino) 1-methoxy benzene, 1, 3-diamino benzene, 1,3-bis- (2,4-diaminophenoxy) propane, sesamol, α-naphthol, 6-hydroxy indole, 4-hydroxy indole, 4-hydroxy N- methyl indole, 6-hydroxy indoline, 2,6-dihydroxy 4-methyl pyridine, 1-H 3-methyl pyrazole 5-one, 1-phenyl 3-methyl pyrazole 5-one, 2,6-dimethyl pyrazolo [1, 5-b] -1, 2,4-triazole, 2,6-dimethyl [3,2-c] -1, 2,4-triazole, 6-methyl pyrazolo [1, 5-a ] -benzimidazole, and their addition salts with an acid. When they are 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.

In general, the addition salts with an acid which can be used in the context of the dye compositions of the invention (oxidation bases and couplers) are in particular chosen from hydrochlorides, hydrobromides, sulphates, citrates, succinates, tartrates, tosylates, benzenesulfonates, lactates and acetates.

The dye composition in accordance with the invention may also contain various adjuvants conventionally used in compositions for dyeing the hair, such as anionic, cationic, nonionic, amphoteric, zwitterionic surfactants or mixtures thereof, anionic polymers, cationic, nonionic, amphoteric, zwitterionic or mixtures thereof, mineral or organic thickening agents, antioxidant agents, penetration agents, sequestering agents, perfumes, buffers, dispersing agents, conditioning agents such as by example of volatile or non-volatile silicones, modified or unmodified, film-forming agents, ceramides, preserving 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 advantageous properties intrinsically attached to the dye composition according to the invention are not, or not substantially, altered by the planned additions.

The dye composition according to the invention can be in various forms, such as in the form of liquids, shampoos, creams, gels, or in any other form suitable for dyeing keratin fibers, and in particular human hair. . The presentation in the form of shampoo is particularly preferred. When one or more oxidation bases are used, optionally in the presence of one or more couplers, then the dye composition in accordance with the invention may also contain 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 and two-electron oxidoreductases. The use of hydrogen peroxide or enzymes is particularly preferred.

A subject of the invention is also the use of the compounds of formula (I) as defined above for the direct dyeing or the oxidation dyeing of keratin fibers, and in particular human keratin fibers such as the hair.

Another subject of the invention is a process for dyeing keratin 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 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, after which it is rinsed, optionally washed with shampoo , rinse again and dry.

The time necessary 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 a particular embodiment of this dyeing process, and when the dye composition according to the invention contains at least one oxidation base and at least one oxidizing agent, the dyeing process comprises a preliminary step consisting in storing in the form separate, on the one hand, a composition (A) comprising, in a medium suitable for dyeing, at least one compound of formula (I) as defined above and at least one oxidation base and, on the other hand, a composition (B) 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 keratin fibers.

Another object of the invention is a device with several compartments or "kit" for dyeing or any other packaging system with several compartments of which a first compartment contains the composition (A) as defined above and a second compartment contains the composition (B) as defined above. devices can be equipped with a means enabling the desired mixture to be delivered to the hair, such as the devices described in patent FR-2,586,913 in the name of the applicant.

The examples which follow are intended to illustrate the invention without however limiting its scope.

EXAMPLES

COMPARATIVE EXAMPLES 1 AND 2

The following dye compositions were prepared (contents in grams)

( ^* ) Composition not part of the invention

( ^** ) Common dye support

- Propylene glycol monomethyl ether 10 g

- Hydroxyethylcellulose 0.7 g

- Alkylpolyglucoside in aqueous solution at 60% of active ingredient (M.A.) 15 g

Locks of natural gray hair containing 90% white hairs were immersed in each of the dye compositions described above for 20 minutes. The hair was then rinsed and dried.

The color of the locks was evaluated before and after dyeing, in the Munsell system, using a CM 2002 MINOLTA® spectrophotometer. According to the Munsell notation, a color is defined by the formula:

HV / C in which the three parameters respectively designate the "Hue" or hue (H), the "Value" or intensity (V) and the "Chroma" or saturation (C), the slash being simply a convention and not designating not a ratio.

The increase in color ΔE can be calculated by applying the Nickerson equation:

ΔE ≈ 0.4C ₀ dH + 6dV + 3dC

as described for example in "Color, Industry and Technology"; pages 14-17; flight. # 5; 1978.

In this equation, ΔE represents the difference in color between the locks before and after dyeing, (ie in this case the increase in coloring), dH, dV, and dC represents the variation in absolute value of the three parameters H, V , and C, C ₀ representing the saturation of the wick with respect to which we want to evaluate the color difference.

The greater the value of ΔE, the greater the difference in color between the two locks, and in this case, the greater the increase in coloration.

The results are shown in the table below

(*) example not part of the invention These results show that the dye composition of Example 1 in accordance with the invention since it contains a direct dye corresponding to formula (I) leads to a coloration that is much more powerful than the composition of Example 2 which is not part of the because the invention contains a direct dye not corresponding to formula (I).

On the previously dyed locks, a resistance test to the action of three shampoos was carried out (Ahiba-Texomat® machine).

To do this, the locks of hair were placed in a basket which was immersed in a solution of a standard shampoo at 37 ° C. The basket was subjected to a vertical reciprocating movement of variable frequency as well as to a rotational movement which reproduce the action of manual friction, which generates the formation of foam.

After 3 minutes of testing, the locks were removed, rinsed and then dried.

The tinted locks were subjected to 3 consecutive shampoo tests.

The color of the locks was then evaluated again in the MUNSELL system using a CM 2002 MINOLTA colorimeter.

The difference between the color of the lock before shampooing and the color of the lock after shampooing was calculated by applying the NICKERSON formula as previously described.

ΔE here represents the difference between the color of the lock before and after shampooing.

The higher the value of ΔE, the less satisfactory the resistance to the action of shampoos. The results are given in the table below.

(*) example not part of the invention

These results show that the dye composition of example 1 in accordance with the invention because containing a direct dye corresponding to formula (I) leads to a coloration which is better resistant to the action of shampoos than the composition of example 2 not forming part of the invention since it contains a direct dye not corresponding to formula (I).

Claims

1. Composition for the direct dyeing or the oxidation dyeing of keratin fibers and in particular human keratin fibers such as the hair, characterized in that it contains, in a medium suitable for dyeing, at least one direct dye polycyclic of formula (I) below:

+ in which R and R ₂ , which are identical or different, represent a hydrogen atom, a C ₁ -C ₄ alkyl radical, CC ₄ monohydroxyalkyl or C ₂ -C ₄ polyhydroxyalkyl.

2. Composition according to claim 1, characterized in that it contains at least one direct dye of formula (I) in which R, and R ₂ simultaneously represent a hydrogen atom.

3. Composition according to claim 1 or 2, characterized in that the direct dye (s) of formula (I) represent from 0.0005 to 12% by weight of the total weight of the dye composition.

4. Composition according to claim 3, characterized in that the direct dye (s) of formula (I) represent from 0.005 to 6% by weight of the total weight of the dye composition.

5. Composition according to any one of the preceding claims, characterized in that the medium suitable for dyeing (or support) consists of water or of a mixture of water and at least one organic solvent.

6. Composition according to any one of the preceding claims, characterized in that it has a pH of between 3 and 12, and preferably between 5 and 11.

7. Composition according to any one of the preceding claims, characterized in that it contains one or more additional direct red dyes.

8. Composition according to Claim 7, characterized in that the additional direct red dyes are chosen from the following red benzenic dyes:

- 1-hydroxy-3-nitro-4-N- (γ-hydroxypropyl) amino benzene,

- N- (β-hydroxyethyl) amino-3-nitro-4-amino benzene,

- 1-amino-3-methyl-4-N- (β-hydroxyethyl) amino-6-nitro benzene, - 1-hydroxy-3-nitro-4-N- (β-hydroxyethyl) amino benzene,

- 1, 4-diamino-2-nitrobenzene,

- 1-amino-2-nitro-4-methylamino benzene,

- N- (β-hydroxyethyl) -2-nitro-paraphenylenediamine,

- 1-amino-2-nitro-4- (β-hydroxyethyl) amino-5-chloro benzene, - 2-nitro-4-amino-diphenylamine, and

- 1-amino-3-nitro-6-hydroxybenzene.

9. Composition according to any one of the preceding claims, characterized in that it contains one or more additional direct orange dyes.

10. Composition according to claim 9, characterized in that the additional orange direct dyes are chosen from the following orange benzene direct dyes:

- 1- (β-aminoethyl) amino-2-nitro-4- (β-hydroxyethyloxy) benzene, - 1- (β, γ-dihydroxypropyl) oxy-3-nitro-4- (β-hydroxyethyl) amino benzene ,

- 1-hydroxy-3-nitro-4-aminobenzene,

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

- 1-methoxy-3-nitro-4- (β-hydroxyethyl) amino benzene,

- 2-nitro-4'-hydroxydiphenylamine, and - 1-amino-2-nitro-4-hydroxy-5-methylbenzene.

11. Composition according to any one of the preceding claims, characterized in that it contains, one or more additional direct dyes chosen from yellow, yellow green, blue or purple benzene dyes, azo dyes, anthraquinone dyes, naphthoquinone dyes or benzoquinonic, indigo dyes, or dyes derived from triarylmethane.

12. Composition according to any one of claims 7 to 11, characterized in that the additional direct dye (s) represent from 0.0005 to

12% by weight of the total weight of the dye composition.

13. Composition according to claim 12, characterized in that the additional direct dye (s) represent from 0.005 to 6% by weight of the total weight of the dye composition.

14. Composition according to any one of the preceding claims, characterized in that it is intended for oxidation dyeing and that it contains one or more oxidation bases chosen from paraphenylenediamines, bis-phenylalkylenediamines, para-aminophenols, ortho-aminophenols and heterocyclic bases.

15. Composition according to Claim 14, characterized in that the oxidation base or bases represent 0.0005 to 12% by weight of the total weight of the dye composition.

16. Composition according to Claim 15, characterized in that the oxidation base or bases represent 0.005 to 6% by weight of the total weight of the dye composition.

17. Composition according to any one of claims 14 to 16, characterized in that it contains one or more couplers chosen from metaphenylenediamines, meta-aminophenols, metadiphenols and heterocyclic couplers.

18. Composition according to Claim 17, characterized in that the coupler (s) represent from 0.0001 to 10% by weight of the total weight of the dye composition.

19. Composition according to Claim 18, characterized in that the coupler (s) represent from 0.005 to 5% by weight of the total weight of the dye composition.

20. Composition according to any one of claims 14 to 19, characterized in that it contains at least one oxidizing agent.

21. Use of the compounds of formula (I) as defined in claim 1 or 2 for the direct dyeing or the oxidation dyeing of keratin fibers, and in particular human keratin fibers such as the hair.

22. Process for dyeing keratin fibers and in particular human keratin fibers such as the hair, characterized in that at least one dye composition as defined in any one of claims 1 to 20 is applied to the fibers , for a time sufficient to develop the desired coloring, after which it is rinsed, washed optionally with shampoo, rinsed again and dried.

23. A process for dyeing keratin fibers and in particular human keratin fibers such as the hair, characterized in that at least one dye composition as defined in any one of claims 1 to 20 is applied to the fibers. , for a time sufficient to develop the desired coloration, without final rinsing.

24. A process for dyeing keratin fibers and in particular human keratin 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 (A) comprising, in a medium suitable for dyeing, at least one compound of formula (I) as defined in claim 1 or 2 and at least one oxidation base and, on the other hand, a composition (B) containing, in a medium suitable for dyeing. minus an oxidizing agent, then mix them at the time of use before applying this mixture to the keratin fibers.

25. Multi-compartment device or "kit" for multi-compartment dyeing, characterized in that a first compartment contains the composition (A) as defined in claim 24 and a second compartment contains the composition (B) as defined in claim 24.