CZ20014324A3 - Preparation for oxidative dyeing of keratin fibers and method for using the same for dyeing - Google Patents

Abstract

The invention concerns an oxidation dyeing composition for keratinous fibres, and in particular human keratinous fibres such as hair comprising, in a suitable dyeing medium, at least a first oxidation base selected among certain substituted paraphenylenediamine derivatives and their addition salts with an acid, and at least a second selected oxidation base, and the dyeing method using said composition.

Description

The invention relates to novel compositions for the oxidative dyeing of keratin fibers, in particular human keratin fibers such as hair, comprising, in a dyeing environment, at least a first oxidation base selected from certain substituted para-phenylenediamine derivatives and their acid addition salts and at least a second selected oxidation base and dyeing method using the composition.

BACKGROUND OF THE INVENTION

It is known to dye keratin fibers, and in particular human hair, with dye compositions which contain oxidative dye precursors, in particular ortho-phenylenediamines or para-phenylenediamines, ortho-aminophenols or para-aminophenols or heterocyclic bases, generally known as oxidation bases. Oxidative dye precursors or oxidation bases are colorless or weakly colored compounds which, in combination with oxidizing agents, can cause oxidative condensation leading to colored compounds and dyes.

It is also known that the shades obtained with these oxidation bases can be varied by combining them with coupling agents or coloring modifiers, the latter being selected in particular from aromatic meta-diamines, metaaminophenols, meta-diphenols and certain heterocyclic compounds.

The variety of molecules used as oxidizing bases and coupling reagents makes it possible to obtain a rich color palette.

Tzv. In addition, the 'permanent' dyeing obtained by the action of these oxidising dyes must meet a certain number of requirements. Thus, it must be able to obtain shades of the desired intensity and have resistance to external agents (light, bad weather, washing, permanent waving, sweating or friction).

The dyes must also make it possible to conceal gray hair and, as far as possible, be non-selective, that is to say, to achieve as little variation as possible in the same keratin fiber which may be differently sensitive (ie damaged) between its end and root.

Compositions for oxidative dyeing of keratin fibers comprising certain substituted paraphenylenediamine derivatives as oxidative dye precursors have been described in particular in patent applications JP-11158046, JP-11158047 and JP-11158048.

However, dyes obtained using these compositions do not always have sufficient intensity, colored or resistant to the various influences to which the hair is exposed.

The inventor has just discovered that it is possible to obtain new dyes leading to colors of different shades which are colored, intense, aesthetic, not very selective and which show good resistance to the effects to which the hair may be exposed by combining at least a first oxidation base selected from certain para-phenylenediamine derivatives of the general formula I defined below and their acid addition salts and at least a second, suitably selected oxidation base.

These discoveries form the basis of the present invention.

A first object of the present invention is a composition for the oxidative dyeing of keratin fibers, in particular human keratin fibers, such as hair, characterized in that it comprises, in a suitable dyeing environment:

- at least a first oxidation base selected from substituted para-phenylenediamine derivatives and their acid addition salts:

wherein - fy and R ₂ have one of the following values i) to v):

i) R! and R ₂ together represent - (CH _{2) 2} OH 2CHOHCH; or ii) R 1 is -CH 2 (CHOH) 4 CH ₂ OH and R ₂ is hydrogen, alkyl or aryl or heterocycle; or iii) R 1 is an alkyl or aryl group or a heterocycle and R ₂ is an alkylene group - (CH ₂ ) _m - wherein m is an integer of 2 or 3, wherein when the alkylene group forms a ring together with a nitrogen atom, a benzene ring carbon atom Bearing a nitrogen atom and one of the two carbon atoms of the benzene ring adjacent thereto, it should be understood that when R 1 is an alkyl or aryl group, either R 1 or said alkylene group is substituted with a group containing at least one atom nitrogen, oxygen or sulfur;

iv) R 1 is - (CH ₂ CH ₂ O) p R ₄ , wherein p is an integer between 2 and 8 inclusive, R ₄ and R ₂ , which are the same or different, represent a hydrogen atom, an alkyl or aryl group or a heterocycle;

v) R and R ₂ form, together with the nitrogen atom to which they are attached form a 5-, 6-, or

A 7-membered saturated heterocycle, wherein said heterocycle is substituted with at least one group containing at least one carbon, nitrogen, oxygen or sulfur atom;

-R ₃ represents a halogen atom, an alkyl or aryl group, a heterocycle, a heterocycle bonded to the benzene ring of formula I by an ether or thio bond, cyano, nitro, hydroxyl, carboxyl, sulfo, alkoxy, aryloxy, cyanamino, amino, anilino, ureido, sulfamylamino , mono- or di-alkylsulfamylamino, alkylthio, aryithio, alkoxycarbonylamino, sulfonamido, carbamyl, mono or dialkylcarbamylsulfamyl, sulfonyl, alkoxycarbonyl, azo, acyloxy, carbamyloxy, mono- or dialkylcarbamyloxy, silyl, silyloxy, phosphoryloxy, aryloxycarbonylamino, aryloxycarbonylamino, aryloxycarbonylamino, or a mercapto group; said alkyl groups having 1 to 25 atoms and are linear, branched, or cyclic and are substituted with one or more groups selected from mono or polyhydroxyalkyl, alkoxyalkyl, aminoalkyl, optionally substituted on nitrogen, carboxyalkyl, alkylcarboxyalkyl, thioalkyl, alkylthioalkyl, cyanoalkyl, trifluoroalkyl, sulfoalkyl, phosphoalkyl or haloalkyl; said alkoxy group having 1 to 25 carbon atoms and is linear, branched or cyclic;

said aryl groups contain from 6 to 26 carbon atoms and may be substituted with one or more groups selected from the group consisting of alkyl, substituted alkyl, or alkoxy;

the heterocycle may be mono- or polycyclic and may contain one or more heteroatoms, provided that, in the case of polycyclic heterocycles, at least one ring contains at least one heteroatom such as N, O or S;

n is an integer from 0 to 4; it is to be understood that when n is greater than 1, then the groups

R ₃ may be the same or different and may form a 3-, 4-, 5- or 6-membered saturated or unsaturated ring with each other;

with the proviso that;

1) when R 1 and R 2 are as defined in (v), then the compounds of formula I contain no more than 3 hydroxyl groups;

2) when R 1 and R ₂ have the meanings defined in (v) and R 1 and R ₂ form a pyrrolidine ring substituted with a carbamoyl group on the carbon atom in the alpha position with respect to the nitrogen atom to which they are bound, then n is different from zero; or alternatively, the pyrrolidine ring carries at least two substituents;

(3) when R 1 and R ₂ have the meanings defined in (v), and R 1 and R ₂ form a pyrrolidine ring substituted with a hydroxymethyl group on a carbon atom positioned at the alpha position relative to the nitrogen atom to which they are bound, and n is 0 or 1; said ring bearing at least two additional substituents or said ring containing only a second substituent other than a hydroxyl group on a carbon atom in the β position relative to the nitrogen atom and relative to the carbon atom bearing the hydroxymethyl substituent; or alternatively, when R 1 and R ₂ have the meanings defined in (v) and R 1 and R ₂ form a pyrrolidine ring substituted with a hydroxymethyl group on the carbon atom situated at the alpha position relative to the nitrogen atom to which they are attached, and n = 1, then R 3 is different from alkyl, mono or polyhydroxyalkyl;

4) when R 1 and R ₂ are as defined in iii), the compound of Formula I must meet at least one of the following conditions:

a) irrespective of the value of n alkylene ring formed by R ₂ contains a substituent besides the substituent R ι; or

b) n is greater than 1; or

c) when n is 1, then R 3 represents an aryl group or a heterocycle; or

d) when n is zero or one, then R 1 represents an aryl group, a heterocycle or a substituted alkyl group other than a monohydroxyalkyl group;

5) when R 1 and R ₂ have the meanings defined in (v), then the groups R 1 and R ₂ form a heterocycle which is different from the piperazines and diazacycloheptanes.

and at least a second oxidation base selected from heterocyclic oxidation bases, double bases, substituted para-aminophenols, ortho-aminophenols, para.

phenylenediamine derivatives of the following formula II and their acid addition salts:

(H) where:

R 5 is hydrogen, C 1 -C 4 alkyl, C 1 -C 4 monohydroxyalkyl, C 2 -C 4 polyhydroxyalkyl, (C 1 -C 4) alkoxy (C 1 -C 4) alkyl, C 1 -C 4 alkyl substituted with a nitrogen-containing group, phenyl group or 4'-aminophenyl group ;

R ₆ represents hydrogen, C 1 -C 4 alkyl, C 1 -C 4 monohydroxyalkyl, C ₂ -C ₄ polyhydroxyalkyl, (C 1 -C 4) alkoxy (C 1 -C 4) alkyl, C 1 -C 4 alkyl substituted with a nitrogen-containing group;

R 7 represents a hydrogen atom, a halogen atom such as chlorine, bromine, iodine or fluorine, C 1 -C 4 alkyl, C 1 -C 4 monohydroxyalkyl, C 1 -C 4 hydroxyalkoxy, C 1 -C 4 acetylaminoalkoxy, C 1 -C 4 mesylaminoalkoxy or C 1 -C 4 carbamoylaminoalkoxy;

R ₈ represents a hydrogen atom, a halogen atom or a C 1 -C 4 alkyl group; provided that when R 5, R 6 and R ₈ simultaneously represent a hydrogen atom, then R 7 is not a hydrogen atom, a chlorine atom or a methyl group.

The dye composition of the invention results in dyes of different shades that are colored, intense, aesthetic, not very selective, and which exhibit good resistance to atmospheric influences such as light, bad weather and various influences to which the hair may be exposed.

According to a further preferred embodiment, the oxidation base is selected from substituted para-phennylenediamine derivatives of the following general formula (I) and its acid addition salts:

- (R _{3) n} (!)

9 · 99 9 »··· 9 9 9 9 9 9 9 9 where:

- R 1 and R 2 have one of the following meanings (i) to (v):

i) R 1 and R ₂ together represent - (CH _{2) 2} OH 2CHOHCH; or ii) R 1 is -CH ₂ (CHOH) 4 CH ₂ OH and R ₂ is hydrogen, alkyl; or iv) R 1 is - (CH ₂ CH ₂ O) _P R 4, wherein p is an integer between 2 and 8 inclusive, R ₄ and R ₂ , which are the same or different, are hydrogen, alkyl;

v) R 1 and R ₂ form, together with the nitrogen atom to which they are attached form a 5-, 6- or 7-membered saturated heterocycle, wherein said heterocycle is substituted with at least one group containing at least one atom of carbon, nitrogen, oxygen or sulfur, which is not in the meta-position with respect to the nitrogen atom of the heterocycle;

R 3 represents a halogen atom, an alkyl or aryl group or a heterocycle;

n is an integer of 0, 1 or 2.

In one embodiment of the invention, R 1 and R 2 form a heterocycle containing one nitrogen heteroatom, for example a pyrrolidine heterocycle.

Substituted para-phenylenediamine derivatives of formula I above include, in particular, 1-N, N-bis (3 ', 4'-dihydroxybutyl) -paraphenylenediamine, 1-N, N-bis (3', 4'-dihydroxybutyl) - 3-methyl-para-phenylenediamine), 1-N, N-bis (3 ', 4'-dihydroxybutyl) -3-ethylpara-phenylenediamine,

-N, N-bis (3 ', 4'-dihydroxybutyl) -3-propyl-para-phenylenediamine, 1 -N, N-bis (3', 4'-dihydroxybutyl) -3-methoxy-para-phenylenediamine, 1 -N, N-bis (3 ', 4'-dihydroxybutyl) -3-ethoxy-para-phenylenediamine, 1-N, N-bis (3', 4'-dihydroxybutyl) -3-propyloxy-para-phenylenediamine, 1 -N, N-bis (3 ', 4'-dihydroxybutyl) -3-hexyloxy-para-phenylenediamine, 1 -N, N-bis (3', 4'-dihydroxybutyl) -3- (1 >> -N- 3 ', 5'-dimethylpyrazole) -para-phenylenediamine, 1N, N-bis (3', 4'-dihydroxybutyl) -3-ureido-para-phenylenediamine, 1-N, N-bis (3 ', 4'- dihydroxybutyl) -3-trimethyl-1, 3 ', 3'-urido-para-phenylenediamine, 1-N, N-bis (3', 4'-dihydroxybutyl) -3-dimethylamino-para-phenylenediamine, 1- N, N-bis (3 ', 4'-dihydroxybutyl) -3-methylthio-para-phenylenediamine, 1-N, N-bis (3', 4'-dihydroxybutyl) -3-ethylhio-para-phenylenediamine, 1-N, N-bis (3 ', 4'-dihydroxybutyl) -3-mercapto-para-phenylenediamine, 1-N, Nbis (3', 4'-dihydroxybutyl) -3-n-butylthio-para-phenylenediamine, 1-N, N-bis (3 ', 4'-dihydro7) 4-dihydro-4-dihydro-4-dihydro Xybutyl) -3-n-octylthio-para-phenylenediamine, 1-N, N-bis (3 ', 4'-dihydroxybutyl) -3-mercaptoethyl-para-phenylenediamine,

1-N, N-bis (3 ', 4'-dihydroxybutyl) -3-mercaptoethylthio-para-phenylenediamine, 1-N, N-bis (3', 4'-dihydroxybutyl) -3-hydroxyethylthio-para-phenylenediamine, 1-N- (2 ', 3', 4 ', 5', 6'-pentahydroxyhexyl) para-phenylenediamine, 1-N- (2 ', 3', 4 ', 5', 6'-pentahydroxyhexyl) 3-methyl para-phenylenediamine, 1-N- (2 ', 3', 4 ', 5', 6'-pentahydroxyhexyl) -3-isopropyl-para-phenylenediamine,

1-N- (2 ', 3', 4 ', 5', 6'-pentahydroxyhexyl) -3-methoxy-para-phenylenediamine, 1-N (2', 3 ', 4', 5 ', 6'-pentahydroxyhexyl) 1-N- (4 ', N' -methylpiperidyl) -3-ethoxy-para-phenylenediamine, 1-N- (2 ', 3', 4 ', 5', 6'-pentahydroxyhexyl) -3- isopropyloxy-para-phenylenediamine, 1-N- (2 ', 3', 4 ', 5', 6'-pentahydroxyhexyl) -3-dimethylamino-para-phenylenediamine, 1-N- (2 ', 3', 4 ', 5 ', 6'-pentahydroxyhexyl) -3-methylthio-para-phenylenediamine, 1-N (2', 3 ', 4', 5 ', 6'-pentahydroxyhexyl) -3-mercapto-para-phenylenediamine, 1-N - (hexyl) -1-N (2 ', 3', 4 ', 5', 6'-pentahydroxyhexyl) -3-isopropyl-para-phenylenediamine, 1-N- (methyl) -1-N (2345 '), 6'-pentahydroxyhexyl) -3-isooctyloxy-para-phenylenediamine, 1 -N- (methyl) -1 N- (2 ', 3', 4 ', 5', 6'-pentahydroxyhexyl) -3-isopropyloxy-para- phenylenediamine, 1-N- (methyl) -1-N- (2 ', 3', 4 ', 5', 6'-pentahydroxyhexyl) -3-methyl-para-phenylenediamine, 1-N- (methyl) -1 -N- (2 ', 3', 4 ', 5', 6'-pentahydroxyhexyl) -3-ethyl-para-phenylenediamine, 1-N- (methyl) -1-N- (2 ', 3', 4 1 ', 5', 6'-pentahydroxyhexyl) -3-hydroxyethyloxy-para-phenylenediamine ₁₁ 1 -N- (methyl) -1 -N- (2 ', 3', 4 ', 5', 6 ' -pentahydroxyhexyl) -3-mercaptoethyloxy-para-phenylenediamine, 1 N- (methyl) -1-N- (2 ', 3', 4 ', 5', 6'-pentahydroxyhexyl) -paraphenylenediamine, 1-N- ( phenyl) -1-N- (2 ', 3', 4 ', 5', 6'-pentahydroxyhexyl) -3-ethyloxy-para-phenylenediamine, 1-N- (4'-N-methylpiperidyl) -1-N - (2 ', 3', 4 ', 5', 6'-pentahydroxyhexyl) -3-ethyloxy-para-phenylenediamine, 4-N- (methyl) -4-N- (2 ', 3', 4 ', 5 ', 6'-pentahydroxyhexyl) amino-7-amino-1-methylindole, 1 -N- (hydroxyethyloxyethyl) -1 -N- (2', 3 ', 4', 5 ', 6'-pentahydroxyhexyl) -3-ethyl -Para-phenylenediamine and their acid addition salts.

Preferably, the oxidation bases are selected from the group consisting of 1-N, N-bis (3 ', 4'-dihydroxybutyl) para-phenylenediamine, 1-N, N-bis (3', 4'-dihydroxybutyl) -3- methylparaphenylenediamine), 1-N, N-bis (3 ', 4'-dihydroxybutyl) -3-ethyl-para-phenylenediamine, 1-N, N-bis (3', 4'-dihydroxybutyl) -3-propyl -Para-phenylenediamine, 1-N- (2 ', 3', 4 ', 5', 6'-pentahydroxyhexyl) -Para-phenylenediamine, 1-N- (2 ', 3', 4 ', 5', 6 '-pentahydroxyhexyl) -3-methylpara-phenylenediamine, 1-N- (2', 3 ', 4', 5 ', 6'-pentahydroxyhexyl) -3-isopropyl-paraphenylenediamine, 1-N- (hexyl) -1- N- (2 ', 3', 4 ', 5', 6'-pentahydroxyhexyl) -3-isopropyl-paraphenylenediamine, 1 -N- (methyl) -1 -N- (2 ', 3', 4 ', 5 1 ', 6'-pentahydroxyhexyl) -3-methyl-para-phenylenediamine, 1'- (methyl) -1-N- (2', 3 ', 4', 5 ', 6'-pentahydroxyhexyl) -3-ethyl- para-phenylenediamine, 1-N- (methyl) -1-N- (2 ', 3', 4 ', 5', 6'-pentahydroxyhexyl) para-phenylenediamine, 1-N- (hydroxyethyloxyethyl) -1N- ( 2 ', 3', 4 ', 5', 6'-pentahydroxyhexyl) -3-ethyl-para-phenylenediamine and their acid addition salts.

In particular, I-N- (3 ', 4'-dihydroxybutyl) -5-aminoindoline, 1- (2'-hydroxyethyl) -2-methyl-5-aminoindoline, 1-methyl-2-hydroxymethyl-5-aminoindoline can be mentioned in particular. , 6-methyl-2-hydroxyethyl-5-aminoindoline, 2-hydroxyethyloxyethyl-5-aminoindoline, 2-hydroxyethyloxyethyloxyethyloxyethyl-5-aminoindoline, 2-hydroxyethyloxyethyloxyethyloxyethyloxyethyloxyethyloxyethyl-6-isopropyl-5-aminoindoline, 2-hydroxyethyl-3-methyl-5 -aminoindoline, 2-hydroxyethyloxyethyloxyethyl-5-aminoindoline, 1 carboxymethyl-2,3,3-trimethyl-5-aminoindoline, 1-methylsulfonamidoethyl-3-methyl-5-aminoindoline, 1-ureidoethyl-6-methoxy-5-aminoindoline, 1- (2 ', 3', 4 ', 5', 6'-pentahydroxyhexyl) -5-aminoindoline, 1-N- (2'-mercaptoethyl) -5-aminoindoline, 6-amino-1-methyl-1,2 dimethyl ester 3,4-tetrahydrofuro [2,3, h] quinoline 4-methylphosphoric ester, 6-amino-1,2,2-trimethyl-4-trimethylsilanyloxy-1,2,3,4-tetrahydroquinoline, 6-amino -1-hexyl-2,2,7-trimethyl-4-mercaptomethyl-1,2,3,4-tetrahydroquinoline, 6-amino-1- (3 ', 4'-dihydroxybutyl) -2,2,3- trimethyl-1,2,3,4-tetrahydroquinoline, 6-amino-1- (ethoxyethoxyethoxyethoxy-3 ', 4'-dihydroxybutyl) -2,2,3,7-tetramethyl-1,2,3,4-tetrahydroquinoline, 6-amino-1- (hydroxyethyloxyethyloxyethyloxyethyl) -2,2,3-trimethyl-1,2,3,4-tetrahydroquinoline, 6-amino-1- (hydroxyethyloxyethyl) -2,2,3-trimethyl-1,2,3, 4-Tetrahydroquinoline, 6-amino-1- (ethylbis (hydroxyethyloxyethyloxyethyloxyethyl)) 2,2,3,7-tetramethyl-1,2,3,4-tetrahydroquinoline, 1- (carboxymethyl) -2,2,3,7-tetramethyl1, 2,3,4-tetrahydroquinoline, 1- (hydroxypropyl) -2,2,3-trimethyl-7-methoxy-1,2,3,4-tetrahydroquinoline, 6-amino-1- (hydroxyethyloxyethyloxyethyl) -2,2, 3-trimethyl-7-isopropyl-1,2,3,4-tetrahydroquinoline, 6-amino-1- (hydroxyethyloxyethyloxyethyloxyethyloxyethyloxyethyloxyethyloxyethyl) -2,2,3-trimethyl-7-isopropyl-1,2,3,4-tetrahydroquinoline, 6- amino-1- (hydroxyethyloxyethyloxyethyloxyethyloxyethyloxyethyloxyethyloxyethyl) 2,2,3-trimethyl 1-1,2,3,4-tetrahydroquinoline, 6-amino-1- (mercaptoethyl) -1,2,3,4-tetrahydroquinoline, 6-amino- 1- (3 ', 4'-dihydroxyb butyl) -2,2,3-trimethyl-7-isopropyl-1,2,3,4-tetrahydroquinoline, 6-amino-1- (3 ', 4'-dihydroxybutyl) -2,2,7-trimethyl-4-hydroxymethyl 2,3,4-tetrahydroquinoline, 6-amino-1- (3 ', 4'-dihydroxybutyl) -2,2-dimethyl-4-hydroxymethyl-7-isopropyl-1,2,3,4-tetrahydroquinoline; -amino-1- (3-hydroxypropyl) -2,2-dimethyl-4-hydroxymethyl-7-isopropyl-1,2,3,4-tetrahydroquinoline, 6-amino-1- (hydroxyethyloxyethyloxyethyloxyethyloxyethyloxyethyloxyethyloxyethyl) -2,2-dimethyl -4-hy • • · ϊ, ϊ. . .. droxymethyl-7-isopropyl-1,2,3,4-tetrahydroquinoline, 6-amino-1 .. .. · · · · · · · «rox rox rox rox rox - (hydroxyethyloxyethyloxyethyloxyethyl) -2,2-dimethyl-4-hydroxymethyl-7-isopropyl-1,2,3,4-tetrahydroquinoline, 6-amino-1- (hydroxyethyloxyethyloxyethyloxyethyloxyethyl) -2,2-dimethyl-7-isopropyl-1 2,3,4-tetrahydroquinoline, 6-amino-1- (hydroxyethyloxyethyloxyethyloxyethyloxyethyloxyethyl) -2,2-dimethyl-7-isopropyl-1,2,3,4-tetrahydroquinoline, 6 amino-1- (hydroxyethyloxyethyl) -2, 2-dimethyl-1,2,3,4-tetrahydroquinoline, 6-amino-1,2,2,4.7-pentamethyl-3-hydroxy-1,2,3,4-tetrahydroquinoline, 6-amino-1- (3'-hydroxypropyl) -4- (hydroxyethyloxyethyloxyethyloxyethyl) -2,2-dimethyl-7-isopropyl-1,2,3,4-tetrahydroquinoline, 6-amino-1- (hydroxyethyloxyethyloxyethyloxyethyl) -4,4-dimethyl-1,2,3,4-tetrahydroquinoline, 6 -amino-1- (3 ', 4'-dihydroxybutyl) -2,2-dimethyl-7-isopropyl

1,2.3.4-tetrahydroquinoline, 6-amino-1- (hydroxyethyloxyethyloxyethyloxyethyl) -4- (hydroxyethyloxyethyloxyethyloxyethyl) -2,2,7-trimethyl-1,2,3,4-tetrahydroquinoline, 6-amino-1- (hydroxyethyloxyethyloxyethyloxyethyl) -2,2-dimethyl-7-isopropyl-1,2,3,4-tetrahydroquinoline, 6-amino-1- (2 ', 3', 4 ', 5', 6'-pentahydroxyhexyl) -2,2, 4-trimethyl-7-isopropyl-1,2,3,4-tetrahydroquinoline, 6-amino-1- (mercaptoethyl) -2,2,4-trimethyl-7- (2 ', 3'-dihydroxypropyloxy) -1,2 , 3,4-tetrahydroquinoline, 6-amino-1- (3 ', 4'-dihydroxybutyl) 2,2,7-trimethyl-3-mercaptomethyl-1,2,3,4-tetrahydroquinoline, 6-amino-1- (ureidoethyl) )

6-amino-2,2-dimethyl-7-chloro-1,2,3,4-tetrahydroquinoline-1-propylsulfonic acid, 6-amino- 1- (4'-Pyridinyl) -2,2,7-trimethyl-1,2,3,4-tetrahydroquinoline, 6-amino-1- (3 ', 4'-dihydroxybutyl) -2,2,4,7-tetramethyl1,2 , 3,4-tetrahydroquinoline, 6-amino-1,7-diisopropyl-2,2-dimethyl-4-trimethylsilanyloxy ·

1,2,3,4-tetrahydroquinoline, 6-amino-1,2,2,4-teramethyl-3-hydroxy-1,2,3,4-tetrahydroquinoline, 6-amino-1-bromo-2,2, -dimethyl-4-mercapto-7-isopropyloxy-1,2,3,4-tetrahydroquinoline and their salts.

Also particularly mentioned may be 1- (4'-amino-3'-isopropyloxyphenyl) -2,6-dimethylpyrrolidine, 1- (4'-amino-3'-methylphenyl) -3-hydroxyethyloxypyrrolidine, 1- (4'amino-3). 1-methylphenyl) -4-hydroxy-2-methylpyrrolidone, 1- (4'-amino-3'-methylphenyl) -3-methylsulfonamidopyrrolidine, 1- (4'-amino-3'-phenoxyphenyl) -3-methylsulfonamidopyrrolidine, 3-n -butylpyrrolidine-1- (4'-amino-3'-phenylsulfonic acid), 1- (4'-amino-3'acetylaminophenyl) -3-hydroxymethylpyrrolidine, 7-amino-4- (2'-methyl) -pyrrolidinylbenzofuran, 1- (4'-aminophenyl) -2- (4'-aminophenoxymethyl) piperidine, 1- (4'-amino-3'acetylphenyl) -4-hydroxypiperidine, 1- (4'-aminophenyl) -2- (hydroxyethyl) piperidine, 1- (4'amino-3'-methoxyphenyl) -2,6-dihydroxymethylpiperidine, 1- (4'-amino-3'-isopropyloxyphenyl) -2,6-dimethylpiperidine, 1- (4'-amino -3'-isopropyloxyphenyl) -2-hydroxymethyl

piperidine, 1- (4'-amino-3'-isopropyloxyphenyl) -2-hydroxymethylpiperidine, 1- (4'-amino-3'-aminophenyl) -2-hydroxymethylpiperidine, 1- (4'-amino-3'-dimethylaminophenyl) ) -2-mercaptoethyloxyethylpiperidine, 1- (4'-amino-3 '- (2'-4'-dichloro) anilinophenyl) -4-methylpiperidine, 1- (4'-aminophenyl) -4-methylpiperidine, 1- (4 1-aminophenyl) -2,7-dimethylazacycloheptane, 1- (4'-amino-3'-methylphenyl) -2-methylazacycloheptane, 1- (4'-amino-3'ureidophenyl) -3-hydroxyazacycloheptane, 1- (4 1-amino-3'-sulfamoylaminophenyl) -2,7-dimethylazacycloheptane, 1- (4'-amino-3'-methylthiophenyl) -2,7-dimethylazacycloheptane, 1 -N-4'-hydroxybutyl-1 N-hydroxyethyloxyethyloxyethyl) -3 -isopropyl-paraphenylenediamine, 1-N-methyl-1-N- (hydroxyethyloxyethyloxyethyl) -paraphenylenediamine, 1-N-phenyl-1 -N- (hydroxyethyloxyethyl) -par-phenylenediamine, 1-N-benzyl-1-N- (hydroxyethyloxyethyloxyethyloxyethyloxyethyl) -3-trimethylsilyl-para-phenylenediamine, 1N-methyl-1H- (hydroxyethyloxyethyloxyethyloxyethyloxyethyloxyethyloxyethyloxyethyl) 3-trimethylsilyloxy-para-phenylenediamine n, 1-N-ethyl-1 N- (methoxyethyloxyethyloxyethyloxyethyloxyethyl) -3-phenoxycarbonylamino-para-phenylenediamine, 1-N-methyl-1 -N (methoxyethyloxyethyloxyethyl) -3- (2 ', 5'-dioxopyrrolidinyl) -para- phenylenediamine, 1-N-ethyl-1 -N- (hydroxyethyloxyethyloxyethyl-3,4'-pyridinylthio-para-phenylenediamine, 1 -Npropyl-1 -N- (hydroxyethyloxyethyloxyethyl) -3-sulfinyl-para-phenylenediamine, 1 -N-methyl-1- N- (hydroxyethyloxyethyl) -3-phenoxycarbonyl-para-phenylenediamine, 1-N, N-bis (hydroxyethyloxyethyloxyethyloxyethyl) -para-phenylenediamine, 1-N, N-bis (methoxyethyloxyethyloxyethyloxyethyl) -3-isopropyloxy-para-phenylenediamine, 1- N, N-bis (hydroxyethyloxyethyloxyethyl) -3-isopropyloxy-para-phenylenediamine, 1 -N, N-bis (hydroxyethyloxyethyloxyethyloxyethyl) -3-isopropyl-para-phenylenediamine, 1-N, N-bis (methoxyethyloxyethyloxyethyloxyethyloxyethyloxyethyloxyethyl) -3-methoxy -para-phenylenediamine, 1-N, N-bis (hydroxyethyloxyethyloxyethyloxyethyloxyethyloxyethyloxyethyloxyethyl) -3-methyl-para-phenylenediamine, 1 -N, N-bis (hydroxyethyloxyethyloxyethylox) yetethyl) -3-isopropyloxy-para-phenylenediamine, 1-N, N-bis (hydroxyethyloxyethyl) -3-mercaptoethyl-para-phenylenediamine, 1-N, N-bis (benzyloxyethyloxyethyloxyethyl) -3-isopropyl-para-phenylenediamine and their acid addition salts .

Preferably, the oxidation base is selected from the group consisting of 1- (4'-amino-3'-methylphenyl) -3-hydroxyethyloxypyrrolidine, 1- (4'-amino-3'-methylphenyl) -4-hydroxy-2-methylpyrrolidine, 1- ( 4'-amino-3'-methylphenyl) -3-methylsulfonamidopyrrolidine, 1- (4'amino-3'-phenoxyphenyl) -3-methylsulfonamidopyrrolidine, 1- (4'-aminophenyl) -2- (4-aminophenoxymethyl) piperidine, 1- (4'-aminophenyl) -2- (hydroxyethyl) piperidine, 1- (4'-amino3'-isopropylphenyl) -2-hydroxymethylpiperidine, 1- (4'-aminophenyl) -4-methylpiperidine, 19 9 *

(4'-aminophenyl) -2,7-dimethylazacycloheptane, 1- (4'-amino-3'-methylphenyl) -2-methylazacycloheptane, 1- (4'-amino-3'-ureidophenyl) -3-hydroxyazacycloheptane, 1 -N-4'-hydroxybutyl-1 -N- (hydroxyethyloxyethyloxyethyl) -3-isopropyl-para-phenylenediamine, 1 -Nmethyl-1 -N- (hydroxyethyloxyethyloxyethyl) para-phenylenediamine, 1 -N, N-bis (hydroxyethyloxyethyloxyethyloxyethyl) -Para-phenylenediamine, 1-N, N-bis (hydroxyethyloxyethyloxyethyloxyethyl) -3-isopropyl-para-phenylenediamine, 1-N, N-bis (hydroxyethyloxyethyloxyethyloxyethyl) -3-isopropyl-para-phenylenediamine, 1-N, N-bis (hydroxyethyloxyethyloxyethyloxyethyloxyethyloxyethyloxyethyloxyethyl) -3-methyl-para-phenylenediamine 1 -N, N-bis (benzyloxyethyloxyethyloxyethyl) -3-isopropyl-para-phenylenediamine and their acid addition salts.

The para-phenylenediamine derivatives of the formula I used as oxidizing bases in the dye compositions according to the invention are preferably 0.0001 to 20% by weight, more preferably 0.001 to 15% by weight and even more preferably 0.01 to 10% by weight relative to the total weight of the composition.

Among the para-phenylenediamines of the formula II which may be used as the second oxidizing base in the coloring agent according to the invention, mention may be made in particular of 2,3-dimethyl-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-paraphenylenediamine , 2,5-dimethyl-para-phenylenediamine, N, N-dimethyl-para-phenylenediamine, N, N-diethyl-para-phenylenediamine, Ν, Ν-dipropyl-para-phenylenediamine, 4-amino-N, N-diethyl-3 -methylaniline, N, N-bis (3-hydroxyethyl) -para-phenylenediamine, 4-N, N-bis (Phydroxyethyl) amino-2-methylaniline, 4-N, N-bis (p-hydroxyethyl) amino-2- chloraniline, 2β-hydroxyethyl-para-phenylenediamine, 2-fluoro-para-phenylenediamine, 2-isopropyl-paraphenylenediamine, N- (p-hydroxypropyl) -paraphenylenediamine, 2-hydroxymethyl-paraphenylenediamine, N, N-dimethyl-3- methyl-para-phenylenediamine, N, N- (ethyl, β-hydroxyethyl) -para-phenylenediamine, N - (4'-dihydroxypropyl) -para-phenylenediamine, N- (4'-aminophenyl) -para-phenylenediamine, N-phenyl-para -phenylenediamine, 2'-hydroxyethyloxypara-phenylenediamine, 2'-acetylaminoethyloxy-para- phenylenediamine, Ν- (β-methoxyethyl) -para-phenylenediamine and their acid addition salts.

Of the para-phenylenediamines of formula II above, 2-isopropyl-para-phenylenediamine, 2'-hydroxyethyl-para-phenylenediamine, 2-β-hydroxyethyloxy-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-diethylpara are particularly preferred. -phenylenediamine, 2,3-dimethyl-para-phenylenediamine, N, N-bis (4-hydroxyethyl) -para 12

Phenylenediamine, 2-3-acetylaminoethyloxy-para-phenylenediamine and their acid addition salts.

Of the para-phenylenediamines of formula II above, even more preferred are 2-β-hydroxyethyl-para-phenylenediamine, N, N-bis (3-hydroxyethyl) para-phenylenediamine and their acid addition salts.

The term "double base" is to be understood as meaning compounds containing at least two aromatic rings that carry amino and / or hydroxyl groups.

The double bases which can be used as the second oxidation bases according to the invention are, in particular, the compounds corresponding to the following general formula III and their acid addition salts.

where:

Z 1 and Z ₂ , which are the same or different, represent a hydroxyl group or an -NH ₂ group which may be substituted by a C 1 -C 4 alkyl group or a Y bonding group;

a bonding group Y represents a linear or branched alkylene chain of 1 to 14 carbon atoms which may be interrupted or which may be terminated by one or more nitrogen-containing groups and / or by one or more heteroatoms such as oxygen, sulfur or nitrogen, and optionally substituted once or more hydroxyl groups or C 1 -C 6 alkoxy groups;

R 8 and R 10 represent a hydrogen atom, a C 1 -C 4 alkyl group, a monohydroxy (C 1 -C 4) alkyl group, a polyhydroxy (C ₂ -C 4) alkyl group, an amino (C 1 -C 4) alkyl group or a Y bonding group

R 11, R 12, R 13, R 14, R 15 and R 16, which are the same or different, represent a hydrogen atom, a Y-bonding group or a C 1 -C 4 alkyl group;

it being understood that the compound of formula III contains only one binding group Y per molecule;

Among the nitrogen-containing groups of the general formula III above, mention may be made in particular of amino, (C1-C4) alkylamino, (C1-C4) dialkylamino, (C1-C4) trialkylamino, monohydroxy (C1-C4) alkylamino, imidazolinium and ammonium.

Among the double bases of formula III above, N, N'-bis (p hydroxyethyl) -N, N'-bis (4'-aminophenyl) -1,3-diaminopropanol, N, N'-bis (p- hydroxyethyl) -N, N'-bis- (4'-aminophenyl) ethylenediamine, N, N'-bis (4-aminophenyl) tetramethylenediamine, Ν, N'-bis (p-hydroxyethyl) -N, N'-bis ( 4-aminophenyl) tetramethylenediamine, Ν, N bis (4-methylaminophenyl) tetramethylenediamine, N, N'-bis (ethyl) -N, N'-bis (4'-amino-3'methylphenyl) ethylenediamine, 1,8-bis (2,5-diaminophenoxy) -3,5-dioxaoctane and their acid addition salts.

Of the double bases of formula III, N, N'-bis (p-hydroxyethyl) -N, N'-bis (4'-aminophenyl) -1,3-diaminopropanol, 1,8-bis (2,5- diaminophenoxy) 3,5-dioxaoctane and their acid addition salts.

Among the substituted para-aminophenols which can be used as oxidizing bases in the dye compositions of the invention, the following are mentioned in particular here: IV and their acid addition salts:

where:

R 11 represents a hydrogen or halogen atom, a C 1 -C 4 alkyl group, a monohydroxy (C 1 -C 4) alkyl group, a (C 1 -C 4) alkoxy (C 1 -C 4) alkyl group, an amino (C 1 -C 4) alkyl group or a hydroxy (C 1 -C 4) C4) alkylamino (C1-C4) alkyl,

Ris is hydrogen or a halogen atom, a C1-C4 alkyl, monohydroxy (C ₄₎ alkyl, polyhydroxy (C2-C4) alkyl, amino (Ci-C4) alkyl, cyano (Ci-C4) alkyl or a (C 1 -C 4) alkoxy (C 1 -C 4) alkyl group, provided that at least one of R 17 and R 18 is different from hydrogen.

Among the para-aminophenols of formula IV above, mention may be made in particular of para-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 4-amino-3-hydroxymethylphenol, 4-amino-2-methylphenol, 4- amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol, 4-amino-2- (3-hydroxyethylaminomethyl) phenol, 4-amino-2-fluorophenol and their acid addition salts.

Among the ortho-aminophenols which can be used as oxidizing bases in the dye compositions according to the invention, mention may be made, for example, of 2-aminophenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol and 5-acetamido-2-aminophenol and their addition salts with acid.

Among the heterocyclic bases which can be used as oxidation bases in the dye compositions according to the invention, mention may be made, for example, of pyridine derivatives, pyrimidine derivatives, pyrazole derivatives and their acid addition salts.

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

Among the pyrimidine derivatives, mention may be made in particular of the compounds described, for example, in German patent DE 2 359 399 or Japanese patents JP 88-169 571, JP 05 163 124; EP 0 770 375 or WO 96/15765, such as 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2 , 4-dihydroxy-5,6-diaminopyrimidine, 2,5,6-triaminopyrimidine, and pyrazolopyrimidine derivatives such as those disclosed in patent application FR-A-2 750 048, of 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-Aminopyrazolo [1,5-a] pyrimidin-7-ol; 3-aminopyrazolo [1,5-a] pyrimidin-5-ol; 2- (3-Aminopyrazolo [1,5-a] pyrimidin-7-ylamino) ethanol, 2- (7-Aminopyrazolo [1,5-a] pyrimidin-3-ylamino) ethanol, 2 - [(3-aminopyrazolo [ 1,5-a] pyrimidin-7-yl) - (2-hydroxyethyl) amino] ethanol, 2 - [(7-aminopyrazolo [1,5a] pyrimidin-3-yl) - (2-hydroxyethyl) amino] ethanol, 5,6-dimethylpyrazolo [1,5-a] pyrimidine-3,7-diamine, 2,6-dimethylpyrazolo [1,5-a] pyrimidine-3,7-diamine, 2,5, N7, N7-tetramethylpyrazolo [ 1,5-a] pyrimidine-3,7-diamine and 3-amino-5-methyl-7-imidazolylpropyl [eta] < 5 > aminopyrazolo [1,5-a] pyrimidine, their acid addition salts and possible tautomeric forms.

Among the pyrazole derivatives there are mentioned in particular the compounds described in patents DE 3,843,892 and DE 4,133,957 and in patent applications WO 94/08969, WO 94/08970, FR-A-2 733 749 and DE 195 43 988, such as 4, 5-Diamino-1-methylpyrazole

3,4-diaminopyrazole, 4,5-diamino-1- (4'-chlorobenzyl) pyrazole, 4,5-diamino-1,3-dimethylpyrazole, 4,5-diamino-1- (p-hydroxyethyl) pyrazole, 4,5 -diamino-3-methyl-1-phenylpyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 4-amino-1,3-dimethyl-5-hydrazinopyrazole, 1-benzyl-4,5-diamino-3 -methylpyrazole, 4,5-diamino-3-tert-butyl-1-methylpyrazole, 4,5-diamino-1-tert-butyl-3-methylpyrazosole, 4,5-diamino-1- (β-hydroxyethyl) 3- methylpyrazole, 4,5-diamino-1-ethyl-3-methylpyrazole, 4,5-diamino-1-ethyl-3- (4'-methoxyphenyl) pyrazole, 4,5-diamino-1-ethyl-3-hydroxymethylpyrazole, 4 , 5-diamino-3-hydroxymethyl-1-methylpyrazole, 4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole,

4,5-diamino-3-methyl-1-isopropylpyrazole, 4-amino-5- (2'-aminomethyl) amino-1,3-dimethylpyrazole, 3,4,5-triaminopyrazole, 1-methyl-3,4,5-triaminopyrazole a3 5-diamino-1-methyl-4-methylaminopyrazole, 3,5-diamino-4- (4-hydroxyethyl) amino-1-methylpyrazole and their acid addition salts.

The oxidation bases used as the second oxidation base preferably represent 0.0005 to 12% by weight of the total weight of the coloring composition, and even more preferably 0.005 to 6% by weight of the coloring agent.

According to a preferred embodiment of the invention, the colorant comprises at least one coupling agent.

Coupling agents that may be used in the oxidative dye compositions of the present invention may be selected from the group consisting of, for example, m-phenylenediamines, meta-aminophenols, meta-diphenols, and heterocyclic coupling agents such as indole derivatives, indoline derivatives, benzimidazole derivatives , benzomorpholine derivatives, sesamol derivatives, pyridine derivatives, pyrimidine derivatives and pyrazole derivatives and their acid addition salts.

These coupling agents are particularly selected from the group consisting of 2-methyl-5-aminophenol, 5-N- (hydroxymethyl) amino-2-methylphenol, 3-aminophenol, 1,3-dihydroxybenzene, 1,3-dihydroxy-2. methylbenzene, 4-chloro-1,3-dihydroxybenzene, 2,4-diamino-1 (4-hydroxyethyloxy) benzene, 2-amino-4- (4-hydroxyethylamino) -1-methoxy-

benzene, 1,3-diaminobenzene, 1,3-bis (2,4-diaminophenoxy) propane, sesamol, 1-amino-2 methoxy-4,5-methylenedioxybenzene, α-naphthol, 2-methyl-1-naphthol, 6 -hydroxyindole, 4-hydroxyindole, 4-hydroxy-N-methylindole, 6-hydroxyindoline, 2,6-dihydroxy-4-methylpyridine, 1H-3-methylpyrazol-5-one and 1-phenyl-3-methylpyrazole-5- he and their acid addition salts.

If used, the coupling agents preferably comprise from 0.0001 to 15% by weight of the total weight of the colorant.

The dye compositions of the invention may further comprise one or more additional oxidizing bases other than those described above and / or one or more direct dyes.

Other oxidation bases which may be used according to the invention include para-phenylenediamines other than those of formula I or II as defined above, for example para-phenylenediamine, para-tolylendiamine, 2-chloro-para-phenylenediamine and paraaminophenols other than those of formula IV as defined above, such as 4-aminophenol and their acid addition salts.

If used, other oxidizing bases preferably represent from 0.0001 to 15% by weight of the total weight of the colorant.

In general, the acid addition salts which can be used in the coloring compositions of the invention are selected in particular from the group consisting of hydrochlorides, hydrobromides, sulfates, tartarates, lactates and acetates.

An environment suitable for coloring (or promoting) usually consists of water or a mixture of water and at least one organic solvent to dissolve compounds that do not sufficiently dissolve in water. As organic solvents, for example, C1-C4 alkanols such as ethanol and isopropanol can be used; glycerol; glycols and glycol ethers such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and monomethyl ether, as well as aromatic alcohols such as benzyl alcohol or phenoxyethanol, similar products and mixtures thereof.

Said solvents may be present in an amount between 1 and 40 wt. based on the total weight of the colorant and more preferably in an amount of between 5 and 30% by weight.

The pH of the colorant according to the invention is usually between 3 and 12. It can be adjusted to the desired value using acidifying or alkalinizing agents usually used for dyeing keratin fibers.

«* •» * ♦ ► I ·

Among the acidifying agents are, for example, inorganic or organic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid, lactic acid and sulfonic acid.

Among the alkalizing agents are, for example, aqueous ammonia, alkali carbonates, and fiber laminates, such as mono- and triethanolamines and derivatives thereof, oxyethylated and / or oxypropylenated ethylenediamines and hydroxyalkylamines, sodium hydroxide, potassium hydroxide, and compounds of formula V below:

N-R-N (V) wherein R is a propylene radical optionally substituted by a hydroxyl group or a C 1 -C 4 alkyl group; R 19, R 20, R 21 and R 22, which are the same or different, represent a hydrogen atom, a C 1 -C 4 alkyl or a C 1 -C 4 hydroxyalkyl radical.

The dye compositions of the invention may also contain various adjuvants commonly used in hair dye compositions such as anionic, cationic, nonionic, amphoteric or zwitterionic surfactants or mixtures thereof, anionic, cationic, nonionic or zwitterionic polymers or mixtures thereof, inorganic or organic thickening agents, antioxidants, penetrating agents, masking agents, fragrances, buffers, dispersing agents, conditioners such as silicones, film forming agents, preservatives, opacifying agents, silicone or non-silicone UV-shielding agents, vitamins and provitamins.

In particular, the reducing agents or antioxidants may be selected from sodium sulfite, thioglycolic acid, thiol acetic acid, sodium bisulfite, dehydroascorbic acid, hydroquinone, 2-methylhydroquinone, tert-butylhydroquinone and homogentisic acid, and are generally present in an amount which may vary between 0, 05 to 1.5 wt. based on the total weight of the composition.

Preferably, the colorant according to the invention comprises at least one nonionic surfactant in an amount of 0.1 to 20% by weight. based on the total weight of the composition and at least one cationic or amphoteric

9 ···

% substantive polymer in an amount of from 0.05 to 10 wt. based on the total weight of the composition.

Preferably, the colorant according to the invention comprises at least one thickening polymer comprising at least one hydrophilic unit and at least one fatty acid chain in an amount of 0.05 to 10% by weight. based on the total weight of the composition.

It should further be appreciated that one skilled in the art may optionally select other compounds such that the advantageous properties associated with the coloring composition of the invention are not or substantially not adversely affected by their addition.

The colorant according to the invention may be in various forms, for example in the form of liquids, creams or gels or in any other form suitable for dyeing keratin fibers, in particular human hair.

A further object of the invention is a method of oxidative dyeing of keratin fibers, and in particular human keratin fibers, such as hair, using a dye composition as defined above.

According to this method, at least one coloring agent as defined above is applied to the fibers, the color is developed at an acidic, neutral or alkaline pH with an oxidizing agent which is added only at the time of use to the coloring agent or is present in the oxidizing agent applied simultaneously or sequentially in a separate form.

According to a particularly preferred embodiment of the dyeing process according to the invention, the dyeing composition described above is admixed at the time of use with an oxidizing agent comprising in the medium suitable for dyeing at least one oxidizing agent present in an amount sufficient to develop coloration. The resulting mixture is applied to the keratin fibers and allowed to act for about 3 to 50 minutes, preferably about 5 to 30 minutes, and then the fibers are rinsed, washed with shampoo, rinsed and dried.

The oxidizing agent may be selected from the oxidizing agents commonly used in the oxidative dyeing of keratin fibers, including, but not limited to, hydrogen peroxide, urea peroxide, alkali metal bromates and persalts such as perborates and persulfates, and enzymes such as peroxidases, laccases, tyrosinases, and oxidoreductases, particularly mentioning pyranosoxidases, glucose oxidases, glycerol oxidases, lactate oxidases, pyruvate oxidases and uricases, said enzymes optionally being combined with their respective donors.

The pH of the oxidizing agent containing the above oxidizing agent is such that upon mixing with the coloring agent, the pH of the resulting composition is applied to the keratin fibers preferably between about 3 and 12, respectively. more preferably between 5 and 11. The pH can be adjusted to the desired value by the above defined acidic or basic agents usually used in dyeing keratin fibers.

The oxidizing agent as defined above may also contain various adjuvants commonly used in hair dyeing.

The composition which is ultimately applied to the keratin fibers can be supplied in various forms, such as in the form of liquids, creams or gels, or in any other form suitable for dyeing keratin fibers and especially human hair.

A further object of the invention is a multi-compartment coloring kit or device or any multi-compartment packaging system which in the first compartment comprises a coloring agent as defined above and in the second compartment comprises an oxidizing agent as defined above. These devices may be provided with means for delivering the desired hair composition, such as the device described in FR-2 586 913 granted to the applicant.

The examples which follow are given by way of illustration only and are not intended to limit the scope of the invention in any way.

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EXAMPLES OF THE INVENTION ^(*)

Examples 1 to 5

According to the invention, the following dye compositions are prepared:

Examples 1 2 3 4 5 1- (4'-Amino-3'-methylphenyl) dihydrochloride - 2x10 ³ 2x10 ' ³ 2x10 ' ³ 2x10 ' ³ 2x10 ' ³ 4-hydroxy-2-methylpyrrolidine (substituted a para-phenylenediamine derivative of the formula I according to invention) mol mol mol mol mol 2-Methyl-5-aminophenol (coupling agent) 3x10 ' ³ mol 3x10 ³ mol 3x10 ' ³ mol 3x10 ³ mol 3x10 ' ³ mol 4-Amino-3-methylphenol (second oxidation base) 10 ' ³ mol N, N-bis (3-hydroxyethyl) -para- phenylenediamine (second oxidation base) 10 ' ³ mol T etrahy drugs chloride N, N '-bis (P-hydroxyethyl) - N, N'-bis (4-aminophenyl) -1,3-diaminopropanol (second oxidation base) ΊΑ mol 4,5-Diamino-1-methylpyrazole dihydrochloride (second oxidation base) ΊΑ mol Ortho-aminophenol (second oxidation base) 10 ' ³ mol General dye carrier O O O O O Demineralized water qs 100 g 100 g 100 g 100 g 100 g

(*) General dye carrier:

C 5 -C 10 alkyl polyglucoside in aqueous solution, 60%, sold under the name

ORAMIX CG 110® by SEPPIC 5.4 g

Ethanol 18.0 g

Benzyl alcohol 1.8 g

Polyethylene glycol 400 2.7 g 4 9 9 4 4 4444

Pentasodium salt of diethylenetriaminepentaacetic acid in aqueous solution,

40%, sold under the name DISSOLUNIE D-40® by AKZO 1.08 g

Sodium metabisulphite 0.205 g

Aqueous ammonia containing 20.5% NH3 10.0 g

At the time of use, the coloring composition described above is mixed with 20 volumes of a solution of hydrogen peroxide (6% by weight) pH 3.

The resulting mixture is applied for 30 minutes on curls of permanently wavy gray hair containing 90% white hair. The curls are then rinsed, washed with standard shampoo, rinsed again and dried.

The shades obtained are shown in the following table:

Examples Shades obtained 1 Strong red-purple 2 Strong purple 3 Strong purple 4 Strong red 5 Strong reddish-brown

Claims (26)

PATENT CLAIMS 1,3-bis (2,4-diaminophenoxy) propane, sesamol, 1-amino-2-methoxy-4,5-methylenedioxybenzene, α-naphthol, 2-methyl-1-naphthol, 6-hydroxyindole, 4-hydroxyindole, 4-hydroxy-N-methylindole, 6-hydroxyindoline, 2,6-dihydroxy-4-methylpyridine, 1H-3-methylpyrazol-5-one, 1-phenyl-3-methylpyrazol-5-one and their acid addition salts . 1,8-bis (2,5-diaminophenoxy) -3,5-dioxaoctane and their acid addition salts. • · · · »· t t * t 1- N- (hydroxyethyloxyethyl) -1-N- (2 ', 3', 4 ', 5', 6'-pentahydroxyhexyl) -3-ethyl-para-phenylenediamine, and their acid addition salts. 1-N- (2 ', 3', 4 ', 5', 6'-pentahydroxyhexyl) -3-methoxy-para-phenylenediamine, 1-N (2', 3 ', 4', 5 ', 6'-pentahydroxyhexyl) 1-N- (4 ', N' -methylpiperidyl) -3-ethoxy-para-phenylenediamine, 1-N- (2 ', 3', 4 ', 5', 6'-pentahydroxyhexyl) -3- Isopropyloxy-para-phenylenediamine, 1-N- (2 ', 3 ^' , 4 ', 5', 6'-pentahydroxyhexyl) -3-dimethylamino-para-phenylenediamine, 1-N- (2 ', 3', 4 ' 5 ', 6'-pentahydroxyhexyl) -3-methylthio-para-phenylenediamine, 1-N (2', 3 ', 4', 5 ', 6'-pentahydroxyhexyl) -3-mercapto-para-phenylenediamine, 1- N- (hexyl) -1-N (2 ', 3', 4 ', 5', 6'-pentahydroxyhexyl) -3-isopropyl-para-phenylenediamine, 1-N- (methyl) -1-N (2 ' 3 ', 4', 5 ', 6'-pentahydroxyhexyl) -3-isooctyloxy-para-phenylenediamine, 1-N- (methyl) -1N- (2', 3 ', 4', 5 ', 6'- pentahydroxyhexyl) -3-isopropyloxy-para-phenylenediamine, 1-N- (methyl) -1-N- (2 ', 3', 4 ', 5', 6'-pentahydroxyhexyl) -3-methyl-para-phenylenediamine, 1-N- (methyl) -1-N- (2 ', 3', 4 ', 5', 6'-pentahydroxyhexyl) -3-ethyl-para-phenylenediamine, 1-N- (me27 ··· ·· 1-N- (2 ', 3', 4 ', 5', 6'-pentahydroxyhexyl) -3-hydroxyethyloxy-para-phenyl ndiamine, 1 N- (methyl) -1-N- (2 ', 3', 4 ', 5', 6'-pentahydroxyhexyl) -3-mercaptoethyloxy-para-phenylenediamine, 1 N- (methyl) -1-N- ( 2 ', 3', 4 ', 5', 6'-pentahydroxyhexyl) para-phenylenediamine, 1-N- (phenyl) -1-N- (2 ', 3', 4 ', 5', 6'- pentahydroxyhexyl) -3-ethyloxy-para-phenylenediamine, 1-N- (4'-N-methylpiperidyl) -1-N- (2 ', 3', 4 ', 5', 6'-pentahydroxyhexyl) -3-ethyloxy -Para-phenylenediamine, 4-N- (methyl) -4-N- (2 ', 3', 4 ', 5', 6'-pentahydroxyhexyl) amino-7-amino-1-methylindole, 1 N- (hydroxyethyloxyethyl) -1 -N- (2 ', 3', 4 ', 5', 6'-pentahydroxyhexyl) -3-ethyl-para-phenylenediamine 1-N- (3 ', 4'-dihydroxybutyl) -5-aminoindoline, 1- ( 2'hydroxyethyl) -2-methyl-5-aminoindoline, 1-methyl-2-hydroxymethyl-5-aminoindoline, 6methyl-2-hydroxyethyl-5-aminoindoline, 2-hydroxyethyloxyethyl-5-aminoindoline, 2-hydroxyethyloxyethyloxyethyloxyethyl-5-aminoindoline , 2-hydroxyethyloxyethyloxyethyloxyethyloxyethyloxyethyl-6-isopropyl-5-aminoindoline, 2-hydroxyethyl-3-methyl-5-aminoindoline, 2-hydroxyethyloxyethyloxyethyl-5-aminoindoline, 1-carboxymethyl-2,3,3-trimethyl-5-aminoindole 1'-methylsulfonamidoethyl-3-methyl-5-aminoindoline, 1-ureidoethyl-6-methoxy-5-aminoindoline, 1- (2 ', 3', 4 ', 5', 6'-pentahydroxyhexyl) -5-aminoindoline, 1-N- (2'-mercaptoethyl) -5-aminoindoline, 6-amino-1-methyl-1,2,3,4-tetrahydrofuro [2,3, h] quinoline 4-methylphosphoric acid dimethyl ester, 6-amino1,2, 2-trimethyl-4-trimethylsilanyloxy-1,2,3,4-tetrahydroquinoline, 6-amino-1-hexyl-2,2,7-trimethyl-4-mercaptomethyl-1,2,3,4-tetrahydroquinoline, 6-amino- 1- (3 ', 4'-dihydroxybutyl) -2,2,3-trimethyl-1,2,3,4-tetrahydroquinoline, 6-amino-1- (ethoxyethoxyethoxyethoxy-3', 4'-dihydroxybutyl) -2, 2,3,7-tetramethyl-1,2,3,4-tetrahydroquinoline, 6 amino-1- (hydroxyethyloxyethyloxyethyloxyethyl) -2,2,3-trimethyl-1,2,3,4-tetrahydroquinoline, 6-amino-1- (hydroxyethyloxyethyl) -2,2,3-trimethyl-1,2,3,4-tetrahydroquinoline, 6-amino-1- (ethylbis (hydroxyethyloxyethyloxyethyloxyethyl)) - 2,2,3,7-tetramethyl1,2.3.4-tetrahydroquinoline 1- (carboxymethyl) -2,2,3,7-tetramethyl-1,2,3,4-tetrahydroquinoline, 1- (hydroxypropyl) -2,2,3-trime thyl-7-methoxy-1,2,3,4-tetrahydroquinoline, 6 amino-1- (hydroxyethyloxyethyloxyethyl) -2,2,3-trimethyl-7-isopropyl-1,2,3,4-tetrahydroquinoline, 6-amino- 1- (hydroxyethyloxyethyloxyethyloxyethyloxyethyloxyethyloxyethyloxyethyl) -2,2,3-trimethyl-7-isopropyl-1,2,3,4-tetrahydroquinoline, 6-amino-1- (hydroxyethyloxyethyloxyethyloxyethyloxyethyloxyethyloxyethyloxyethyl) -2,2,3-trimethyl-1,2,3, 4-tetrahydroquinoline, 6-amino-1- (mercaptoethyl) -1,2,3,4-tetrahydroquinoline, 6-amino-1- (3 ', 4'-dihydroxybutyl) -2,2,3-trimethyl-7- Isopropyl-1,2,3,4-tetrahydroquinoline, 6-amino-1- (3 ', 4'-dihydroxybutyl) -2,2,7-trimethyl-4-hydroxymethyl-1,2,3,4-tetrahydroquinoline, 6- Amino-1- (3 ', 4'-dihydroxybutyl) -2,2-dimethyl-4-hydroxy28 · f · f · f · f f Methyl-7-isopropyl-1,2,3,4-tetrahydroquinoline, 6-amino-1 - (-) - - - - - - - - - - - - - 3-hydroxypropyl) -2,2-dimethyl-4-hydroxymethyl-7-isopropyl-1,2,3,4-tetrahydroquinoline n, 6-amino-1- (hydroxyethyloxyethyloxyethyloxyethyloxyethyloxyethyloxyethyloxyethyl) -2,2-dimethyl-4-hydroxymethyl-7-isopropyl-1,2,3,4-tetrahydroquinoline, 6-amino-1- (hydroxyethyloxyethyloxyethyloxyethyl) -2,2- dimethyl-4-hydroxymethyl-7-isopropyl-1,2,3,4-tetrahydroquinoline, 6-amino-1- (hydroxyethyloxyethyloxyethyloxyethyloxyethyl) -2,2-dimethyl-7-isopropyl-1,2,3,4-tetrahydroquinoline, 6-amino-1- (hydroxyethyloxyethyloxyethyloxyethyloxyethyloxyethyl) -2,2-dimethyl-7-isopropyl-1,2,3,4-tetrahydroquinoline, 6 amino-1- (hydroxyethyloxyethyl) -2,2-dimethyl-1,2,3, 4-tetrahydroquinoline, 6-amino-1,2,2,4,7-pentamethyl-3-hydroxy-1,2,3,4-tetrahydroquinoline, 6-amino-1- (3'-hydroxypropyl) -4- (hydroxyethyloxyethyloxyethyloxyethyl) -2,2-dimethyl-7-isopropyl-1,2,3,4-tetrahydroquinoline, 6-amino-1- (hydroxyethyloxyethyloxyethyloxyethyl) -4,4-dimethyl-1,2,3,4-tetrahydroquinoline, 6-amino-1- ( 3 ', 4'-dihydroxybutyl) -2,2-dimethyl-7-isopropyl-1,2,3,4-tetrahydroquinoline, 6-amino-1- (hydroxyethyloxyethyloxyethyloxyethyl) -4- (hydroxy ethyloxyethyloxyethyloxyethyl) -2,2,7-trimethyl-1,2,3,4-tetrahydroquinoline, 6-amino-1- (hydroxyethyloxyethyloxyethyloxyethyl) -2,2-dimethyl-7-isopropyl-1,2,3,4-tetrahydroquinoline 6-amino-1- (2 ', 3', 4 ', 5', 6'-pentahydroxyhexyl) -2,2,4-trimethyl-7-isopropyl-1,2,3,4-tetrahydroquinoline; amino-1- (mercaptoethyl) -2,2,4-trimethyl-7- (2 ', 3'-dihydroxypropyloxy) -1,2,3,4-tetrahydroquinoline, 6-amino-1- (3', 4 ' -dihydroxybutyl) -2,2,7-trimethyl-3-mercaptomethyl-1,2,3,4-tetrahydroquinoline, 6-amino-1- (ureidoethyl) -2,2,4-trimethyl-1,2,3,4-tetrahydroquinoline, 6-amino-2,2-dimethyl-7-chloro-1,2,3,4-tetrahydroquinoline-1-propylsulfonic acid, 6-amino-1- (4'-pyridinyl) -2,2,7-trimethyl, 2,3,4-tetrahydroquinoline, 6-amino-1- (3 ', 4'-dihydroxybutyl) -2,2,4,7-tetramethyl-1,2,3,4-tetrahydroquinoline, 6-amino-1,7- diisopropyl-2,2-dimethyl-4-trimethylsilanyloxy-1,2,3,4-tetrahydroquinoline, 6-amino-1,2,2,4-teramethyl-3-hydroxy-1,2,3,4-tetrahydroquinoline, 6- amino-1-bromo-2,2'-dimethyl-4-mercapto-7-isopropyloxy-1,2,3,4-tetrahydro quinoline, 1- (4'-amino-3'-isopropyloxyphenyl) -2,6-dimethylpyrrolidine, 1- (4'-amino3'-methylphenyl) -3-hydroxyethyloxypyrrolidine, 1- (4'-amino-3'-methylphenyl) ) -4-hydroxy-2-methylpyrrolidone, 1- (4'-amino-3'-methylphenyl) -3-methylsulfonamidopyrrolidine, 1- (4'amino-3'-phenoxyphenyl) -3-methylsulfonamidopyrrolidine, 3-n-butylpyrrolidin-1 - (4'-amino-3'-phenylsulfonic acid), 1- (4'-amino-3'-acetylaminophenyl) -3-hydroxymethylpyrrolidine, 7-amino-4- (2'-methyl) -pyrrolidinylbenzofuran, 1- (4 ' aminophenyl) -2- (4'-aminophenoxymethyl) piperidine, 1- (4'-amino-3'-acetylphenyl) -4-hydroxypiperidine, 1- (4'aminophenyl) -2- (hydroxyethyl) piperidine, 1- (4 1'-amino-3'-methoxyphenyl) -2,6-dihydroxy 29 methyl 1-piperidine, 1- (4'-amino-3'-isopropyloxyphenyl) -2,6-dimethylpiperidine, 1- (4'-amino-3 ' 1- (4'-amino-3'-isopropyloxyphenyl) -2-hydroxymethylpiperidine, 1- (4'-amino-3'-aminophenyl) -2-hydroxymethylpiperidine, 1- (4'-amino- 3'-dimethylaminophenyl) -2-mercaptoethyloxyethylpiperidine, 1- (4'-amino-3 '(2'-4'-dic) (chloro) anilinophenyl) -4-methylpiperidine, 1- (4'-aminophenyl) -4-methylpiperidine, 1- (4'-aminophenyl) -2,7-dimethylazacycloheptane, 1- (4'-amino-3'-methylphenyl) 1- (4'-amino-3'-amino-3'-ureidophenyl) -3-hydroxyazacycloheptane, 1- (4'-amino-3'-sulfamoylaminophenyl) -2,7-dimethylazacycloheptane, 1- (4'-amino-3) 1-methylthiophenyl) -2,7-dimethylazacycloheptane, 1-N-4'-hydroxybutyl-1-N-hydroxyethyloxyethyloxyethyl) -3-isopropyl-para-phenylenediamine, 1-N-methyl-1 -N- (hydroxyethyloxyethyloxyethyl) -para- phenylenediamine, 1-N-phenyl-1-N- (hydroxyethyloxyethyl) -par-phenylenediamine, 1-N-benzyl-1 -N- (hydroxyethyloxyethyloxyethyloxyethyloxyethyl) -3-trimethylsilyl-para-phenylenediamine, 1 N-methyl-1 -N - (hydroxyethyloxyethyloxyethyloxyethyloxyethyloxyethyloxyethyloxyethyl) -3-trimethylsilyloxy-para-phenylenediamine, 1-Methyl-1 N- (methoxyethyloxyethyloxyethyloxyethyloxyethyl) -3-phenoxycarbonylaminopara-phenylenediamine, 1-N-methyl-1 -N- (methoxyethyloxyethyloxyethyl) -3- (2 ', 5') (-dioxopyrrolidinyl) -para-phenylenediamine, 1-N-ethyl- 1-N- (hydroxyethyloxyethyloxyethyl) 3,4'-pyridinylthio-para-phenylenediamine, 1-N-propyl-1-N- (hydroxyethyloxyethyloxyethyl) 3-sulfinyl-para-phenylenediamine, 1-N-methyl-1 -N- (hydroxyethyloxyethyl) -3-Phenoxycarbonyl-para-phenylenediamine, 1-N, N-bis (hydroxyethyloxyethyloxyethyloxyethyl) -paraphenylenediamine, 1-N, N-bis (methoxyethyloxyethyloxyethyloxyethyl) -3-isopropyloxy-paraphenylenediamine, 1-N, N-bis (hydroxyethyloxyethyloxyethyl) - 3-isopropyloxy-para-phenylenediamine, 1-N, N-bis (hydroxyethyloxyethyloxyethyloxyethyl) -3-isopropyl-paraphenylenediamine, 1-N, N-bis (methoxyethyloxyethyloxyethyloxyethyloxyethyloxyethyloxyethyl) -3-methoxy-para-phenylenediamine, 1-N, N- bis (hydroxyethyloxyethyloxyethyloxyethyloxyethyloxyethyloxyethyloxyethyl) -3-methyl-para-phenylenediamine, 1-N, N-bis (hydroxyethyloxyethyloxyethyloxyethyl) -3-isopropyloxy-para-phenylenediamine, 1 -N, Nbis (hydroxyethyloxyethyl) -3-mercaptoethyl-para-phenylenediamine, 1 -N, N-bis (benzyloxyethyloxyethyloxyethyl) -3-isopropyl-para-phenylenediamine and their acid addition salts. 1) when R 1 and R ₂ have the meanings defined in (v), then the compounds of formula I contain no more than 3 hydroxyl groups; A composition for the oxidative dyeing of keratin fibers, in particular human keratin fibers, such as hair, comprising, in a suitable dyeing environment: - at least a first oxidation base selected from substituted para-phenylenediamine derivatives of the following general formula I and their acid addition salts: - (R _{3) n} O) nh ₂ wherein - R 1 and R ₂ have one of the following meanings (i) to (v): i) R 1 and R ₂ simultaneously represent - (CH ₂ ) ₂ CHOHCH ₂ OH; or ii) R 1 is -CH ₂ (CHOH) 4 CH ₂ OH and R ₂ is hydrogen, alkyl or aryl or heterocycle; or iii) R 1 is an alkyl or aryl group or a heterocycle and R ₂ is an alkylene group - (CH ₂ ) _m - wherein m is an integer of 2 or 3, wherein when the alkylene group forms a ring together with a nitrogen atom, the carbon atom of the benzene ring bearing a nitrogen atom and one of the two carbon atoms of the benzene ring adjacent to it should be understood that when R 1 is an alkyl or aryl group, either R 1 or said alkylene group is substituted with a group containing at least one nitrogen atom, oxygen or sulfur; iv) R 1 is - (CH ₂ CH ₂ O) _P R 4, wherein p is an integer between 2 and 8 inclusive, R ₄ and R ₂ , which are the same or different, represent a hydrogen atom, an alkyl or aryl group or a heterocycle; v) R and R ₂ form, together with the nitrogen atom to which they are attached form a 5-, 6- or 7-membered saturated heterocycle, wherein said heterocycle is substituted with at least one group containing at least one carbon, nitrogen, oxygen, or sulfur; R3 represents a halogen atom, an alkyl or aryl group, a heterocycle, a heterocycle bonded to the benzene ring of formula I by an ether or thio bond, cyano, nitro, hydroxyl, carboxyl, sulfo, alkoxy, aryloxy, cyanamino, amino, anilino, ureido, sulfamylamino, mono- or dilakylsulfamylamino, alkylthio, arylthio, alkoxycarbonylamino, sulfonamido, carbamyl, mono or dialkylcarbamylsulfamyl, sulfonyl, alkoxycarbonyl, azo, acyloxy, carbamyloxy, carbamyloxy, or carbamyloxy, a silyloxy, aryloxycarbonylamino, imido, sulfinyl, phosphonyl, aryloxycarbonyl, acyl or mercaptic group; said alkyl groups having 1 to 25 atoms and are linear, branched or cyclic and are substituted with one or more groups selected from mono or polyhydroxyalkyl, alkoxyalkyl, aminoalkyl, optionally substituted on nitrogen, carboxyalkyl, alkylcarboxyalkyl, thioalkyl, alkylthioalkyl, cyanoalkyl, trifluoroalkyl, sulfoalkyl, phosphoalkyl or haloalkyl; said alkoxy group having 1 to 25 carbon atoms and is linear, branched or cyclic; said aryl groups containing from 6 to 26 carbon atoms and may be substituted with one or more groups selected from the group consisting of alkyl, substituted alkyl, or alkoxy; the heterocycle may be mono- or polycyclic and each ring contains 3, 4, 5 or 6 members and may contain one or more heteroatoms, provided that for polycyclic heterocycles, at least one ring contains at least one heteroatom such as N, O or S; n is an integer from 0 to 4; it is to be understood that when n is greater than 1, then the R ₃ groups may be the same or different and may form a 3-, 4-, 5- or 6-membered saturated or unsaturated ring with each other; with the proviso that: Composition according to claim 1, characterized in that the oxidation base is selected from substituted para-phenylenediamine derivatives of the following general formula (I) and its acid addition salts: where: wherein - R 1 and R ₂ have one of the following values i) to v): i) R ₁ and R ₂ simultaneously represent - (CH ₂ ) ₂ CHOHCH ₂ OH; or ii) R 1 is -CH ₂ (CHOH) 4 CH ₂ OH and R ₂ is hydrogen, alkyl; or iv) R 1 is - (CH ₂ CH ₂ O) _P R 4, wherein p is an integer between 2 and 8 inclusive, R ₄ and R ₂ , which are the same or different, are hydrogen, alkyl; v) R 1 and R ₂ form, together with the nitrogen atom to which they are attached form a 5-, 6- or 7-membered saturated heterocycle, wherein said heterocycle is substituted with at least one group containing at least one carbon atom, nitrogen or oxygen, which are not in meta-position with respect to the nitrogen atom of the heterocycle; R 3 represents a halogen atom, an alkyl or aryl group or a heterocycle; n is an integer of 0, 1 or 2. 2) when R 1 and R ₂ have the meanings defined in (v) and R 1 and R ₂ form a pyrrolidine ring substituted by a carbamoyl group on the carbon atom in the alpha position with respect to the nitrogen atom to which they are bound, then n is different from zero; or alternatively, the pyrrolidine ring carries at least two substituents; A composition according to claim 1 or 2, wherein the substituted para-phenylenediamine derivatives of formula (I) are selected from the group consisting of 1-N, N-bis (3 ', 4'-dihydroxybutyl) para-phenylenediamine, 1-N, N-bis (3 ', 4'-dihydroxybutyl) -3-methyl-para-phenylenediamine), 1-N, N-bis (3', 4'-dihydroxybutyl) -3-ethylpara-phenylenediamine, 1 -N, N-bis (3 ', 4'-dihydroxybutyl) -3-propyl-para-phenylenediamine, 1N, N-bis (3', 4'-dihydroxybutyl) -3-methoxy-para-phenylenediamine, 1 -N N-bis (3 ', 4'-dihydroxybutyl) -3-ethoxy-para-phenylenediamine, 1-N, N-bis (3', 4'-dihydroxybutyl) -3-propyloxy-para-phenylenediamine, 1-N , N-bis (3 ', 4'-dihydroxybutyl) -3-hexyloxy-para-phenylenediamine, 1-N, N-bis (3', 4'-dihydroxybutyl) -3- (1 '-N-3'), 5'-dimethylpyrazole-para-phenylenediamine, 1-N, N-bis (3 ', 4'-dihydroxybutyl) -3-ureido-para-phenylenediamine, 1-N, N-bis (3', 4'-dihydroxybutyl) ) -3-trimethyl-1, 3 ', 3' -ureido-para-phenylenediamine, 1-N, Nbis (3 ', 4'-dihydroxybutyl) -3-dimethylamino-para-phenylenediamine, 1-N, N -bis (3 ', 4'-dihydroxybutyl) -3-methylthio-p ara-phenylenediamine, 1-N, N-bis (3 ', 4'-dihydroxybutyl) -3-ethylthio-para-phenylenediamine, 1-N, N-bis (3', 4'-dihydroxybutyl) -3-mercapto-para- phenylenediamine, 1-N, N-bis (3 ', 4'-dihydroxybutyl) -3-n-butylthio-para-phenylenediamine, 1-N, Nbis (3', 4'-dihydroxybutyl) -3-n-octylthio- para-phenylenediamine, 1-N, N-bis (3 ', 4'-dihydroxybutyl) -3-mercaptoethyl-para-phenylenediamine, 1-N, N-bis (3', 4'-dihydroxybutyl) -3-mercaptoethylthio- para-phenylenediamine, 1-N, N-bis (3 ', 4'-dihydroxybutyl) -3-hydroxyethylthio-para-phenylenediamine, 1-N- (2', 3 ', 4', 5 ', 6'-pentahydroxyhexyl) ) -Para-phenylenediamine, 1-N- (2 ', 3', 4 ', 5', 6'-pentahydroxyhexyl) -3-methyl-para-phenylenediamine, 1-N (2 ', 3', 4 ', 5 ', 6'-pentahydroxyhexyl) -3-isopropyl-para-phenylenediamine, (3) when R 1 and R ₂ have the meanings defined in (v), and R 1 and R ₂ form a pyrrolidine ring substituted with a hydroxymethyl group on a carbon atom located at the alpha position relative to the nitrogen atom to which they are bound, and n is 0 or 1; said ring carries at least two additional substituents or said ring contains only a second substituent other than a hydroxyl group on the carbon atom in β • · 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 4-amino-3-hydroxymethylphenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4 amino- 2-aminomethylphenol, 4-amino-2- (β-hydroxyethylaminomethyl) phenol, 4-amino-2-fluorophenol and their acid addition salts. Composition according to any one of the preceding claims, characterized in that the oxidation base is selected from the group consisting of 1-N, N-bis (3 ', 4'-dihydro30) 4 · 4 4 4 4 44 (4) (4) (4) (4-xylbutyl) para-phenylenediamine, 1-N, N-bis (3 ', 4'-dihydroxybutyl) -3-methyl-para-phenylenediamine), 1-N, N- bis (3 ', 4'-dihydroxybutyl) -3-ethyl-para-phenylenediamine, 1-N, N-bis (3', 4'-dihydroxybutyl) -3-propyl-para-phenylenediamine, 1-N- (2 1 ', 3', 4 ', 5', 6'-pentahydroxyhexyl) -paraphenylenediamine, 1-N- (2 ', 3', 4 ', 5', 6'-pentahydroxyhexyl) -3-methyl-para-phenylenediamine, 1 -N- (2 ', 3', 4 ', 5', 6'-pentahydroxyhexyl) -3-isopropyl-paraphenylenediamine, 1-N- (hexyl) -1-N- (2 ', 3', 4 ', 5 ', 6'-pentahydroxyhexyl) -3-isopropyl-paraphenylenediamine, 1-N- (methyl) -1-N- (2', 3 ', 4', 5 ', 6'-pentahydroxyhexyl) -3-methyl- para-phenylenediamine, 1 N- (methyl) -1-N- (2 ', 3', 4 ', 5', 6'-pentahydroxyhexyl) -3-ethyl-para-phenylenediamine, 1-N- (methyl) -1 -N- (2 ', 3', 4 ', 5', 6'-pentahydroxyhexyl) -paraphenylenediamine, (4) when R ₁ and R ₂ have the meanings defined in (iii), the compounds of formula I must satisfy at least one of the following conditions: a) irrespective of the value of n alkylene ring formed by R ₂ contains a substituent in addition to RI; or b) n is greater than 1; or c) when n is 1, then R ₃ represents an aryl group or a heterocycle; or d) when n is zero or one, then R 1 represents an aryl group, a heterocycle or a substituted alkyl group other than a monohydroxyalkyl group; Composition according to any one of claims 1 to 3, characterized in that the oxidation base is selected from the group consisting of 1- (4'-amino-3'-methylphenyl) -3-hydroxyethyloxypyrrolidine, 1- (4'-amino) -3'-methylphenyl) -4-hydroxy-2-methylpyrrolidine, 1- (4'-amino-3'-methylphenyl) -3-methylsulfonamidopyrrolidine, 1- (4'-amino-3'-phenoxyphenyl) -3-methylsulfonamidopyrrolidine, 1- (4'-Aminophenyl) -2- (4-aminophenoxymethyl) piperidine, 1- (4'-Aminophenyl) -2- (hydroxyethyl) piperidine, 1- (4'-Amino-3'-isopropylphenyl) 2- hydroxymethylpiperidine 1- (4'-aminophenyl) -4-methylpiperidine, 1- (4'-aminophenyl) -2,7-dimethylazacycloheptane, 1- (4'-amino-3'-methylphenyl) -2-methylazacycloheptane, 1- (4 ' amino-3'-ureidophenyl) -3-hydroxyazacycloheptane, 1-N-4'-hydroxybutyl-1-N- (hydroxyethyloxyethyloxyethyl) -3-isopropyl-para-phenylenediamine, 1-N-methyl-1 -N- (hydroxyethyloxyethyloxyethyl) -para-phenylenediamine, 1-N, N-bis (hydroxyethyloxyethyloxyethyloxyethyl) -para-phenylenediamine, 1-N, N-bis (hydroxyethyloxyethyloxyethyloxyethyl) 3-isopropyl-par α-phenylenediamine, 1-N, N-bis (hydroxyethyloxyethyloxyethyloxyethyl) -3-isopropyl-para-phenylenediamine, 1-N, N-bis (hydroxyethyloxyethyloxyethyloxyethyloxyethyloxyethyloxyethyloxyethyl) -3-methyl-para-phenylenediamine, 1 -N, N-bis (benzyloxyethyloxyethyloxyethyl) -3-Isopropyl-para-phenylenediamine and their acid addition salts. 5) when R ₁ and R ₂ have the meanings defined in (v), then R ₁ and R ₂ form a heterocycle which is different from the piperazines and diazacycloheptanes. - and at least a second oxidation base selected from heterocyclic oxidation bases, double bases, substituted para-aminophenols, ortho-aminophenols, paraphenylenediamine derivatives of the following general formula II and their acid addition salts: where: R ₅ represents a hydrogen atom, C 1 -C 4 alkyl, C 1 -C 4 monohydroxyalkyl, C ₂ -C ₄ polyhydroxyalkyl, (C 1 -C 4) alkoxy (C 1 -C 4) alkyl, C 1 -C 4 alkyl substituted with a nitrogen-containing group, phenyl group or 4 ' an aminophenyl group; R ₆ represents hydrogen, C 1 -C 4 alkyl, C 1 -C 4 monohydroxyalkyl, C ₂ -C ₄ polyhydroxyalkyl, (C 1 -C 4) alkoxy (C 1 -C 4) alkyl, C 1 -C 4 alkyl substituted with a nitrogen-containing group; R ₇ represents a hydrogen atom, a halogen atom such as chlorine, bromine, iodine or fluorine, C 1 -C 4 alkyl, C 1 -C 4 monohydroxyalkyl, C 1 -C 4 hydroxyalkoxy, C 1 -C 4 acetylaminoalkoxy, C 1 -C ₄ mesylaminoalkoxy or C 1 -C 4 carbamoylaminoalkoxy; R ₈ represents a hydrogen atom, a halogen atom or a C 1 -C 4 alkyl group; provided that when R 5, R 6 and R 6 simultaneously represent a hydrogen atom, then R _{7 is} not a hydrogen atom, a chlorine atom or a methyl group. Composition according to any one of the preceding claims, characterized in that the para-phenylenediamine derivatives of the general formula I represent 0.0001 to 20% by weight, based on the total weight of the composition. · Φ φ φ φ φ <φ φ <φ φ <<φ φ φ φ φ φ φ φ <φ <φ 7. A composition according to claim 1 or 2 wherein R1 and R2 form a pyrrolidine heterocycle. • · · • · · «8 • · · • · · · • »8 • 8 8 8 « • • · • · 8 8 «· 8 · «· 8 · 8 8 8 (III) where: Z 1 and Z ₂ , which are the same or different, represent a hydroxyl group or an -NH 2 group which may be substituted by a C 1 -C 4 alkyl group or a Y linking group; a bonding group Y represents a linear or branched alkylene chain of 1 to 14 carbon atoms which may be interrupted or which may be terminated by one or more nitrogen-containing groups and / or by one or more heteroatoms such as oxygen, sulfur or nitrogen, and optionally substituted once or more hydroxyl groups or C 1 -C 6 alkoxy groups; R 8 and R 10 represent a hydrogen atom, a halogen atom, a C 1 -C 4 alkyl group, a monohydroxy (C 1 -C ₄ ) alkyl group, a polyhydroxy (C ₂ -C ₄ ) alkyl group, an amino (C 1 -C 4) alkyl group or a Y bonding group R 11, R 12, R 13, R 14, R 15 and R 16, which are the same or different, represent a hydrogen atom, a Y-bonding group or a C 1 -C 4 alkyl group; bearing in mind that the compound of formula (III) contains only one Y group per molecule. Composition according to any one of the preceding claims, characterized in that the para-phenylenediamines of the general formula II are selected from the group consisting of 2,3-dimethyl-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-paraphenylenediamine, 2,5-dimethyl-para-phenylenediamine, N, N-dimethyl-para-phenylenediamine, Ν, Ν-diethyl-para-phenylenediamine, Ν, Ν-dipropyl-para-phenylenediamine, 4- amino-N, N-diethyl-3-methylaniline, N, N-bis (p-hydroxyethyl) para-phenylenediamine, 4-N, N-bis (p-hydroxyethyl) amino-2-methylaniline, 4-N, N -bis (p-hydroxyethyl) amino-2-chloroaniline, 2-p-hydroxyethyl-para-phenylenediamine, 2-fluoro-para-phenylenediamine, 2-isopropyl-para-phenylenediamine, N- (p-hydroxypropyl) -para-phenylenediamine , 2-hydroxymethyl-para-phenylenediamine, N, N-dimethyl-3-methyl-para-phenylenediamine, N, N- (ethyl, p-hydroxyethyl) -paraphenylenediamine, N- (P, γ-dihydroxypropyl) -para-phenylenediamine , N- (4'-aminophenyl) -paraphenylenediamine, N-phenyl-para-phenylenediamine, 2-p-hydroxyethyloxy-para-phenylenediamine, 2-p-acetylamino ethyloxy-para-phenylenediamine, N- (p-methoxyethyl) -para-phenylenediamine and their acid addition salts. 9 9 9 9 9 9 9 «· · · * * * * · · · · · · · · · A composition according to claim 8, wherein the para-phenylenediamines of formula (II) are selected from the group consisting of 2-isopropyl-paraphenylenediamine, 2-p-hydroxyethyl-para-phenylenediamine, 2-p-hydroxyethyloxy-paraphenylenediamine, , 6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, N, N-bis (β-hydroxyethyl) -paraphenylenediamine, 2-p-acetylaminoethyloxy-para- phenylenediamine and their acid addition salts. 10. A composition according to claim 9 wherein the para-phenylenediamines of formula (II) are selected from the group consisting of 2-p-hydroxyethyl-para-phenylenediamine, N, N-bis (p-hydroxyethyl) -phenyl-phenylenediamine, and addition salts thereof. salts with an acid. Composition according to any one of claims 1 to 7, characterized in that the double base is selected from the compounds of the following general formula IIIa and their acid addition salts. 12. A composition according to claim 11 wherein the double base of formula III is selected from the group consisting of N, N'-bis (3-hydroxyethyl) -N, N'bis (4). 1'-aminophenyl) -1,3-diaminopropanol, N, N'-bis (p-hydroxyethyl) -N, N'-bis- (4'-aminophenyl) ethylenediamine, N, N'-bis (4-aminophenyl) tetramethylenediamine, N N, N'-bis (p-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, Composition according to any one of claims 1 to 7, characterized in that the substituted para-aminophenols are selected from compounds of the following general formula IV and their acid addition salts: OH NH ₂ where: R17 is hydrogen, halogen, C1-C4 alkyl, monohydroxy (C1-C4) alkyl, (C1-C4) alkoxy (C1-C4) alkyl, amino (C1-C4) alkyl or hydroxy (C1-C4) an alkylamino (C 1 -C 4) alkyl group, R 18 represents a hydrogen or halogen atom, a C 1 -C 4 alkyl group, a monohydroxy (C 1 -C 4) alkyl group, a polyhydroxy (C 2 -C 4) alkyl group, an amino (C 1 -C 4) alkyl group, a cyano (C 1 -C 4) alkyl group or A (C 1 -C ₄ ) alkoxy (C 1 -C 4) alkyl group, provided that at least one of R 17 and R 18 is different from hydrogen. 14. A composition according to claim 13, wherein the paraaminophenols of formula IV are selected from the group consisting of para-aminophenol, A composition according to any one of claims 1 to 7, wherein the ortho-aminophenols are selected from the group consisting of 2-aminophenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol, and 5-acetamido-2-aminophenoids and their acid addition salts. • ·· fc · · · · · · · · · Composition according to any one of claims 1 to 7, characterized in that the heterocyclic bases are selected from the group consisting of pyridine derivatives, pyrimidine derivatives, pyrazole derivatives and acid addition salts thereof. Composition according to any one of the preceding claims, characterized in that the oxidation base used as the second oxidation comprises 0.0005 to 12% by weight of the total weight of the colorant. Composition according to claim 17, characterized in that the oxidation base used as second oxidation base constitutes 0.005 to 6% by weight of the total weight of the colorant. Composition according to any one of the preceding claims, characterized in that it comprises at least one coupling agent selected from the group consisting of meta-phenylenediamines, meta-aminophenols, meta-diphenols and heterocyclic coupling agents and their acid addition salts. A composition according to claim 19, wherein the coupling agents are selected from the group consisting of 2-methyl-5-aminophenol, 5-N- (3-hydroxymethyl) amino-2-methylphenol, 3-aminophenol, 1-methylphenol, 2-methylphenyl 3-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene, 4-chloro-1,3-dihydroxybenzene, 2,4-diamino-1- (p-hydroxyethyloxy) benzene, 2-amino-4- (p-hydroxyethylamino) -1- methoxybenzene, 1,3-diaminobenzene, 21. A composition according to claim 19 or 20, wherein the coupling agents comprise from 0.0001 to 15% by weight of the total weight of the colorant. Composition according to any one of the preceding claims, characterized in that it comprises one or more further oxidizing bases selected from the group consisting of: ** ** * which consists of para-phenylenediamine, para-tolylendiamine, 2-chloro-para -phenylenediamine, 4aminophenol and their acid addition salts. Composition according to any one of the preceding claims, characterized in that the acid addition salts are selected from the group consisting of hydrochlorides, hydrobromides, sulphates, tartarates, lactates and acetates. 24. A method for oxidative dyeing of keratin fibers, in particular human keratin fibers such as hair, characterized in that at least one coloring agent as defined in claims 1 to 23 is applied to said fibers, the color is developed at an acidic, neutral or alkaline pH with an oxidizing agent which is added only at the time of use to the coloring agent or which is present in the oxidizing agent applied simultaneously or sequentially in separate form. 24 position relative to the nitrogen atom and to the carbon atom bearing the hydroxymethyl substituent; or alternatively, when R ₁ and R ₂ have the meanings defined in (v) and R ₁ and R ₂ form a pyrrolidine ring substituted with a hydroxymethyl group on the carbon atom situated at the alpha position relative to the nitrogen atom to which they are bound, and n = 1, then R ₃ is different from alkyl, mono- or polyhydroxyalkyl; 25. The process of claim 24, wherein the oxidizing agent is selected from the group consisting of hydrogen peroxide, urea peroxide, alkali metal bromates and persalts, and oxidizing enzymes. 26. A multi-compartment dyeing kit or device, characterized in that in the first compartment it comprises a coloring agent as defined in any one of claims 1 to 23 and in the second compartment it comprises an oxidizing agent.