EP1263397A1

EP1263397A1 - Oxidation dyeing composition for keratinous fibres with a particular paraphenylenediamine derivative and a particular direct dyeing agent

Info

Publication number: EP1263397A1
Application number: EP01911846A
Authority: EP
Inventors: Gérard Lang
Original assignee: LOreal SA
Current assignee: LOreal SA
Priority date: 2000-03-06
Filing date: 2001-03-05
Publication date: 2002-12-11
Also published as: BR0109021A; JP2003528053A; WO2001066068A1; FR2805741B1; US20030159221A1; FR2805741A1; CA2400456A1; AU2001240768A1

Abstract

The invention concerns an oxidation dyeing composition for keratinous fibres, and in particular human keratinous fibres such as hair comprising, in a medium suitable for dyeing, at least an oxidation base selected among certain substituted paraphenylenediamine derivatives and their addition salts with an acid, and at least a synthetic direct dyeing agent selected among the azo, quinoid, triarylmethane, indoamino, azine dyes and/ or a natural dye. The invention also concerns a dyeing method using said composition.

Description

KERATIN FIBER OXIDATION DYE COMPOSITION WITH A PARTICULAR PARAPHENYLENEDIAMINE DERIVATIVE AND A

SPECIFIC DIRECT DYE

The subject of the invention is a composition for the oxidation dyeing of keratin fibers, and in particular human keratin fibers such as the hair comprising, in a medium suitable for dyeing, at least one oxidation base chosen from certain derivatives. substituted paraphenylenediamine and their addition salts with an acid and at least one particular synthetic direct dye and / or a natural dye, as well as the dyeing process using this composition.

It is known to dye keratin fibers and in particular human hair with dye compositions containing oxidation dye precursors, in particular ortho or paraphenylenediamines, ortho or paraaminophenois, heterocyclic bases, generally called oxidation bases. The precursors of oxidation dyes, or oxidation bases, are colorless or weakly colored compounds which, associated with oxidizing products, can give rise, through an oxidative condensation process, to colored and coloring compounds.

It is also known that the shades obtained with these oxidation bases can be varied by associating them with couplers or color modifiers, the latter being chosen in particular from aromatic metadiamines, meta-aminophenols, metadiphenois and certain compounds. heterocyclic.

The variety of molecules involved in the oxidation bases and couplers, allows obtaining a rich palette of colors.

The so-called "permanent" coloration obtained thanks to these oxidation dyes must moreover satisfy a certain number of requirements. Thus, it must make it possible to obtain nuances in the desired intensity and present good resistance to external agents (light, bad weather, washing, permanent waving, perspiration, friction). The dyes must also make it possible to cover white hair, and finally be the least selective possible, that is to say allow to obtain the smallest possible color differences throughout the same keratin fiber, which can be in differently sensitized effect (ie damaged) between its tip and its root.

It has already been proposed, in particular in patent applications JP-11-158046, JP-11-158047 and JP-11-158048, compositions for the oxidation dyeing of keratin fibers containing, as dye precursors d oxidation, substituted derivatives of paraphenylenediamine. However, the colorings obtained by using these compositions are not always powerful enough, chromatic, or resistant to the various aggressions that the hair can undergo.

Now, the Applicant has now discovered that it is possible to obtain new oxidation dyes, capable of leading to colorations with varied shades, chromatic, powerful, aesthetic, not very selective, and resistant well to the various aggressions that can undergo the fibers, by combining at least one oxidation base chosen from certain derivatives of paraphenylenediamine of formula (I) defined below and their addition salts with an acid and at least one particular direct dye and / or a dye natural.

This discovery is the basis of the present invention.

The first object of the invention is therefore a composition for the oxidation dyeing of keratin fibers and in particular human keratin fibers such as the hair, characterized in that it comprises, in a suitable medium for dyeing: - ( A) at least one oxidation base chosen from substituted derivatives of paraphenylenediamine of formula (I) below, and their addition salts with an acid: in which :

Ri and R ₂ can take one of the following meanings i) to v):

i) R _T and R ₂ simultaneously represent a radical - (CH ₂ ) ₂ CHOHCH ₂ OH; or ii) Ri represents a radical -CH ₂ (CHOH) CH ₂ OH and R ₂ represents a hydrogen atom, an alkyl radical, aryl or a heterocycle; or ili) Rι represents an alkyl, aryl or heterocycle radical and R ₂ represents an alkylene radical - (CH ₂ ) _m - in which m is an integer equal to 2 or 3, said alkylene radical forming a ring together with nitrogen atom, the carbon atom of the benzene ring carrying the nitrogen atom and one of the two carbon atoms of the benzene ring which are adjacent to it, it being understood that when R 1 is an alkyl or aryl radical, then either R 1 or said alkylene radical is substituted by a radical containing at least one nitrogen, oxygen or sulfur atom; iv) Rι represents a radical - (CH ₂ CH ₂ 0) _p R in which p is an integer between 2 and 8 inclusive, R and R ₂ , identical or different, represent a hydrogen atom, an alkyl radical, aryl or a heterocycle; v) Ri and R ₂ form, together with the nitrogen atom to which they are attached, a saturated 5, 6 or 7-membered heterocycle, said heterocycle being substituted by at least one radical containing at least one carbon atom, or nitrogen, or oxygen, or sulfur;

- R ₃ represents a halogen atom, an alkyl or aryl radical, a cyano, nitro, hydroxyl, carboxyl, sulfo, alkoxy, aryloxy, cyanoamino, amino, anilino, ureido, sulfamylamino, mono- or di-alkylsulfamylamino, alkylthio radical , arylthio, alkoxycarbonylamino, sulfonamido, carbamyl, mono- or di-alkylcarbamylsulfamyle, sulfonyl, alkoxycarbonyl, azo, acyloxy, carbamyloxy, mono- or di-alkylcarbamyloxy, silyl, silyloxy, aryloxycarbonylamino, imidoon, sulfonyl a heterocycle, a heterocycle linked to the benzene ring of formula (I) by an ether or thio bond;

said alkyl radicals having from 1 to 25 carbon atoms and which may be linear, branched or cyclic and be substituted by one or more radicals and then represent a mono or polyhydroxyalkyl, alkoxyalkyl, aminoalkyl radical optionally substituted on the nitrogen atom, carboxyalkyl , alkylcarboxyalkyle, thioalkyle, alkylthioalkyle, cyanoalkyle, trifluoroalkyle, sulfoalkyle, phosphoalkyle, or haloalkyle; said alkoxy radicals having from 1 to 25 carbon atoms and which may be linear, branched or cyclic; said aryl radicals containing from 6 to 26 carbon atoms and which may be substituted by one or more radicals chosen from alkyl, substituted alkyl or alkoxy radicals; the heterocycles being mono or polycyclic, each cycle comprising 3, 4, 5 or 6 members and possibly containing one or more heteroatoms, it being understood that in the case of polycyclic heterocycles, at least one of the rings contains at least one heteroatom such as N , O or S;

- n is an integer between 0 and 4; it being understood that when n is greater than 1, then the radicals R ₃ may be identical or different and form between them a saturated or unsaturated ring with 3, 4, 5, or 6 links;

provided that :

1) when Ri and R ₂ have the meanings defined in point v), then the compounds of formula (I) do not contain more than 3 hydroxyl radicals;

2) when Ri and R ₂ have the meanings defined in point v) and when Ri and R ₂ form a pyrrolidine ring substituted by a carbamoyl radical on the carbon in the alpha position of the nitrogen atom to which they are attached, then not is different from 0; or else the pyrrolidine ring carries at least two substituents; 3) when Ri and R ₂ have the meanings defined in point v) and when Ri and R ₂ form a pyrrolidine ring substituted by a hydroxymethyl radical on the carbon located in the alpha position relative to the nitrogen atom on which they are fixed, and that n = 0 or 1, then either said ring carries at least two additional substituents, or said cycle only has a second substituent different from a hydroxyl radical on the carbon located in position β relative to the atom nitrogen and with respect to the carbon carrying said hydroxymethyl substituent; or when Ri and R ₂ have the meanings defined in point v) and when Ri and R ₂ form a pyrrolidine ring substituted by a hydroxymethyl radical on the carbon located in the alpha position relative to the nitrogen atom on which they are fixed, and that n = 1, then R ₃ is different from an alkyl, mono- or polyhydroxyalkyl radical; 4) when Ri and R ₂ have the meanings defined in point iii) the compounds of formula (I) must fulfill at least one of the following four conditions: a) whatever the value of n, the alkylene ring formed by the radical R ₂ has a substituent in addition to the radical Ri; or b) n is greater than 1; or c) when n is equal to 1, then R ₃ represents an aryl radical or a heterocycle; or d) when n is equal to zero or to 1, then R 1 represents an aryl radical, a heterocycle or a substituted alkyl radical different from a monohydroxyalkyl radical; 5) Ri and R ₂ form a different cycle of piperazine and diazacycloheptane;

- (B) at least one synthetic direct dye chosen from azo, quinonics, triarylmethanics, indoamines or azinics and / or a natural dye.

The addition salts with an acid of the substituted para-phenylenediamine derivatives of formula (I) which can be used in dye compositions according to the invention are especially chosen from hydrochlorides, hydrobromides, sulphates, tartrates, lactates and acetates.

The dye composition in accordance with the invention thus defined, leads after mixing with an oxidizing composition, to colorings in various shades, chromatic, powerful, aesthetic, having a low selectivity and excellent resistance properties both to -vis atmospheric agents such as light and bad weather and vis-à-vis perspiration and different treatments that can undergo the hair.

Another subject of the invention relates to a ready-to-use composition for the oxidation dyeing of keratin fibers which comprises, in a medium suitable for dyeing, at least one substituted derivative of paraphenylenediamine of formula (I), at least one azo, quinone, triarylmethane, indoamine or azine synthetic direct dye and / or a natural dye and at least one oxidizing agent.

By ready-to-use composition is meant within the meaning of the present invention, any composition intended to be applied immediately to keratin fibers.

The invention also relates to a process for the oxidation dyeing of keratin fibers, and in particular human keratin fibers such as the hair, consisting in applying to the fibers a coloring composition containing, in a medium suitable for dyeing, at least one substituted para-phenylenediamine derivative of formula (I) in combination with at least one synthetic azo, quinone, triarylmethane, indoamine or azine direct dye and / or a natural dye, the color being revealed at alkaline, neutral or acidic pH, using of a composition containing at least one oxidizing agent, which is mixed just at the time of use with the coloring composition or which is applied sequentially without intermediate rinsing.

The invention also relates to a dyeing device with several compartments or "kit" for the oxidation dyeing of keratin fibers, in particular of human keratin fibers such as the hair, which comprises at least one compartment containing at least one substituted derivative of paraphenylenediamine of formula (I) and at least one direct synthetic dye azo, quinonic, triarylmethane, indoaminic or azine and / or a dye natural, and at least one other compartment containing at least one oxidizing agent.

Another multi-compartment dyeing device comprises at least one compartment containing at least one substituted paraphenylenediamine derivative of formula (I), at least one compartment containing at least one synthetic azo, quinonic, triarylmethane, indoaminic or azine direct dye and / or a natural dye, and at least one other compartment containing at least one oxidizing agent.

However, other characteristics, aspects, objects and advantages of the invention will appear even more clearly on reading the description and the examples which follow.

According to the present invention, it is preferred to use the substituted derivatives of paraphenylenediamine of formula (I) above in which:

- Ri and R ₂ can take one of the following meanings i) to v):

i) Ri and R ₂ simultaneously represent a radical - (CH ₂ ) 2CHOHCH ₂ OH; or ii) Ri represents a radical -CH ₂ (CHOH) ₄ CH ₂ OH and R ₂ represents a hydrogen atom, an alkyl radical; or iv) Rι represents a radical - (CH ₂ CH ₂ 0) pR ₄ in which p is an integer between 2 and 8 inclusive, R and R ₂ , identical or different, represent a hydrogen atom, an alkyl radical ; v) Ri and R ₂ form, together with the nitrogen atom to which they are attached, a saturated 5, 6 or 7-membered heterocycle, said heterocycle being substituted by at least one radical containing at least one carbon atom, or WO 01/66068 PCT / FR01 / 00644

nitrogen, or oxygen, not located in the meta position relative to the nitrogen atom of the heterocycle;

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

- n is an integer equal to 0, 1 or 2;

More particularly according to the invention, in formula (I), Ri and R ₂ form a pyrroiidinic heterocycle.

Among the substituted paraphenylenediamine derivatives of formula (I) above, mention may be made particularly of 1-N, N-bis- (3 ', 4'-dihydroxybutyl) paraphenylenediamine, 1-N, N-bis- ( 3 ', 4'-dihydroxybutyl) -3-methyl ppaarraapphhéénnyyllèènneeddiiaammiinnee ,, llaa 1-N, N-bis- (3', 4'-dihydroxybutyl) -3-ethyl paraphenylenediamine, 1-N, N-bis- (3 ', 4'-dihydroxybutyl) -3-propyl paraphenylenediamine, 1-N, N-bis- (3', 4'-dihydroxybutyl) -3-methoxy paraphenylenediamine, 1 -N, N-bis- (3 ', 4'-d ihyd roxybutyl) -3-ethoxy paraphenylenediamine, 1-N, N-bis- (3 ', 4'-dihydroxybutyl) -3-propyloxy ppaarraapphhénényllylleneneeddiiaammiinnee ,, llaa 1-N, N-bis- (3' , 4'-dihydroxybutyl) -3-hexyloxy paraphenylenediamine, 1-N, N-bis- (3 ', 4'-dihydroxybutyl) -3- (1 "-N-3", 5 "- dimethylpyrazolyl paraphenylenediamine, 1 -N, N-bis- (3 ', 4'-dihydroxybutyl) -3- ureido paraphenylenediamine, 1-N, N-bis- (3', 4'-dihydroxybutyl) -3-trimethyl 1 ", 3", 3 "-ureido paraphenylenediamine, 1-N, N-bis- (3 ', 4'-dihydroxybutyl) -3- dimethylamino paraphenylenediamine, 1-N, N-bis- (3', 4'-dihydroxybutyl) -3- methylthio paraphenylenediamine, 1-N, N-bis- (3 ', 4'-dihydroxybutyl) -3-ethylthio paraphenylenediamine, 1-N, N-bis- (3 ', 4'-dihydroxybutyl) -3-mercapto paraphenylenediamine 1-N, N-bis- (3', 4'- dihydroxybutyl) -3-n.butylthio paraphenylenediamine, 1-N, N-bis- (3 ', 4'-dihydroxybutyl) -3-n.octylthio paraphenylenediamine, 1-N, N-bis- (3', 4 '-dihydroxybutyl) -3-mercaptoethyl paraphenylenediamine, 1 -N, N-bis- (3', 4'-dihydroxybutyl) -3-mercaptoethyl thioparaphenylenediamine, 1-N, N-bis- (3 ', 4'- dihydroxybutyl) -3-β-hydroxyethyl thioparaphenylenediamine, 1-N- (2 ', 3', 4 ', 5', 6'-pentahydroxyhexyl) paraphenylenediamine, 1-N- (2 ', 3', 4 ', 5', 6'-pentahydroxyhexyl) -3-methyl paraphenylenediamine, 1-N- (2 ', 3', 4 ', 5', 6 '-pentahydroxyhexyl) -3-isopropyl paraphenylenediamine, 1-N- (2', 3 ', 4', 5 ', 6'-pentahydroxyhexyl) -3-methoxy paraphenylenediamine, 1-N- (2', 3 ' , 4 ', 5', 6'-pentahydroxyhexyl) -1-N- (4 "- N" methylpiperidyl) -3-ethoxy paraphenylenediamine, 1-N- (2 ', 3', 4 ', 5', 6 '- pentahydroxyhexyl) -3-isopropyloxy paraphenylenediamine, 1-N- (2', 3 ', 4', 5 ', 6'- pentahydroxyhexyl) -3-dimethylamino paraphenylenediamine, 1-N- (2', 3 ' , 4 ', 5', 6'- pentahydroxyhexyl) -3-methyl thioparaphenylenediamine, 1-N- (2 ', 3', 4 ', 5', 6'- pentahydroxyhexyl) -3-mercapto paraphenylenediamine, 1- N- (hexyl) -1-N- (2 ', 3', 4 ', 5', 6'-pentahydroxyhexyl) -3-isopropyl paraphenylenediamine, la

1-N- (methyl) -1-N- (2 ', 3', 4 ', 5', 6'-pentahydroxyhexyl) -3-isooctyloxy paraphenylenediamine, 1-N- (methyl) -1-N- ( 2 ', 3', 4 ', 5', 6'-pentahydroxyhexyl) -3- isopropyloxy paraphenylenediamine, 1-N- (methyl) -1-N- (2 ', 3', 4 ', 5', 6 '- pentahydroxyhexyl) -3-methyl paraphenylene diamine, 1-N- (methyl) -1-N- (2', 3 ', 4', 5 ', 6'-pentahydroxyhexyl) -3-ethyl paraphenylenediamine, lN- (methyl) - 1-N- (2 ', 3', 4 ', 5', 6'-pentahydroxyhexyl) -3-hydroxyethyloxy paraphenylenediamine, 1-N- (methyl) -1-N- (2 ' , 3 ', 4', 5 ', 6'-pentahydroxyhexyl) -3-mercaptoethyloxy paraphenylenediamine, 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 paraphenylenediamine, 1-N- (4 "- N-methylpiperidyl) -1-N- (2 ', 3', 4 ', 5', 6'- pentahydroxyhexyl) -3-ethyloxy paraphenylenediamine, 4-N- (methyl) -4-N- (2 ', 3 ', 4', 5 ', 6'-pentahydroxyhexyl) -amino-7amino-1-méthyiindole, la 1-N-

(hydroxyethyloxyethyl) -1-N- (2 ', 3', 4 ', 5', 6'-pentahydroxyhexyl) -3-ethyl paraphenylenediamine, and their addition salts with an acid,

and which we particularly prefer among them

1-N, N-bis- (3 ', 4'-dihydroxybutyl) paraphenylenediamine, 1-N, N-bis- (3', 4'- dihydroxybutyl) -3-methyl paraphenylenediamine, 1-N, N -bis- (3 ', 4'- dihydroxybutyl) -3-ethyl paraphenylenediamine, 1-N, N-bis- (3', 4'-dihydroxybutyl) - 3-propyl paraphenylenediamine, 1-N- (2 ' , 3 ', 4', 5 ', 6'-pentahydroxyhexyl) paraphenylenediamine, 1-N- (2', 3 ', 4', 5 ', 6'-pentahydroxyhexyl) -3-methyl paraphenylenediamine, 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 paraphenylene-diamine, 1-N- (methyl) -1-N- (2 ', 3', 4 ' , 5 ', 6'-pentahydroxyhexyl) -3-ethyl paraphenylenediamine, lN- (methyl) - 1-N- (2', 3 ', 4', 5 ', 6'-pentahydroxyhexyl) paraphenylenediamine, 1-N - (hydroxyethyloxyethyl) -1-N- (2 ', 3', 4 ', 5', 6'-pentahydroxyhexyl) -3-ethyl paraphenylenediamine, and their addition salts with an acid.

Mention may also very particularly be made of 1-N- (3 ', 4'-dihydroxybutyl) -5- aminoindoline, 1- (2'-hydroxyethyl) -2methyl-5-aminoindoline, 1-methyl-2-hydroxymethyl- 5-aminoindoline, 6-methyl-2-hydroxyethyl-5-aminoindoline, 2-hydroxyethyloxyethyl-5-aminoindoline, 2-hydroxyethyloxyethyloxyethyloxy-ethyl-5-aminoindoline, 2-hydroxyethyloxyethyloxyethyloxyethyloxyethyloxyethyl-6-isopropyl-5-aminoindoline, 2-hydroxyethyl-3-methyl-5-aminoindoiine, 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'-pentahydroxy-hexyl) -5-aminoindoline, 1-N- ( 2'-mercaptoethyl) -5 aminoindoline, the dimethyl ester 6-amino-1-methyl-1,2,3,4-tetrahydro-furo- [2,3, h] -quinoiine 4-methylester of phosphoric acid, 6-amino-1,2,2-trimethyl-4-trimethylsilanyloxy-1,2,3,4-tetrahydroqu inoline, 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- (hydroxyethyloxy-ethyloxyethyloxyethyl) -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- (ethyl-bis-

(hydroxyethyloxyethyloxyethyloxyethyl)) - 2,2,3,7-tetramethyl-1,2,3,4- tetrahydroquinoline, 1- (carboxymethyl) -2,2,3,7-tetramethyl-1,2,3,4- 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- (hydroxyethyloxyethyloxyethyloxy- ethyloxyethyioxyethyloxyethyloxyethyl) -2,2,3-trimethyl-7-isopropyl-1,2,3,4-tetra-hydroquinoline, 6-amino-1 - (hydroxyethyloxyethyloxyethyloxyethyloxyethyloxy-ethyloxyethyloxyethyl) -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-tetrahydro-quinoline, 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-hydroxymethyl-7-isopropyl- 1,2,3,4-tetrahydroquinoline, 6-amino-1 - (3-hydroxypropyl) -2,2-dimethyl-4-hydroxymethyl-7-isopropyl-1, 2,3,4-tetrahydro-quinoline, 6-amino-1- (hydroxy-ethyloxyethyloxyethyloxyethyloxyethyloxyethyloxyethyloxyethylethyl ) -2,2-dimethyl-4-hydroxymethyl-7-isopropyl-1, 2,3,4-tetrahydroquinoline, 6-amino-1- (hydroxyethylethylethylethyloxyethyloxyethyl) -2,2-dimethyl-4-hydroxymethyl-7isopropyl -1 , 2,3,4-tetrahydroquinoline, 6-amino-1- (hydroxyethyloxyethyloxyethyloxyethylethyloxyethyl) -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-

(hydroxyethyloxyethyioxyethyloxyethyl) -2,2-dimethyl-7-isopropyl-1,2,3,4-tetrahydroquinoline, 6-amino-1- (hydroxyethyloxyethyloxyethyioxyethyl) -4,4- dimethyl-1,2,3,4-tetra -hydroquinoline, 6-amino-1- (3 ', 4'-dihydroxybutyl) -2,2- dimethyl-7-isopropyl-1,2,3,4-tetrahydroquinoline, 6-amino-1- (hydroxy- ethyloxyethyloxyethyloxyethyl) -4- (hydroxyethyloxyethyloxyethyloxyethyl) -2,2,7- trimethyl-1,2,3,4-tetrahydro-quinoline, 6-amino-1- (hydroxyethyloxy-ethyloxyethyloxyethyl) -2,2-dimethyl-7- isopropyl-1, 2,3,4-tetra-hydroquinoline, 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 -tetrahydro-quinoline, 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 acid 7-chloro-1,2,3,4-tetrahydroquinoline-1-propylsulfonic, 6-amino-1- (4'-pyridinyl) -2,2,7-trimethyl-1,2,3,4-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-tetramethyl-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 addition salts with an acid.

Mention may also be made very particularly of 1- (4'-amino-3'-isopropyloxyphenyl) -2,6-dimethyl pyrrolidine, 1- (4'-amino-3'-methylphenyl) -3- hydroxyethyloxy pyrrolidine, 1- (4'-amino-3'-methylphenyl) -4-hydroxy-2-methyl pyrrolidine, 1- (4'-amino-3'-methylphenyl) -3-methylsulfonamido pyrrolidine, 1- (4'- amino-3'-phenoxyphenyl) -3-methylsulfonamido pyrrolidine, 3-n.butyl pyrrolidine 1- (4'-amino-3'-phenylsulfonic) acid, 1- (4'-amino-3'-acetylaminophenyl) - 3-hydroxymethyl pyrrolidine, 7-amino-4- (2'-methyl) -pyrrolydinyl-benzofuran, 1- (4'-aminophenyl) -2- (4 "-aminophenoxymethyl) piperidine, 1- (4 ' -amino-3'- acetylphenyl) -4-hydroxy piperidine, 1- (4'-aminophenyl) -2- (hydroxyethyl) piperidine, 1- (4'-amino-3'-methoxyphenyl) -2,6- dihydroxymethyl piperidine, 1- (4'-amino-3'-isopropyloxyphenyl) -2,6-dimethyl piperidine, 1- (4'-amino-3'-isopropylphenyl) -2-hydroxymethyl piperidine, 1- (4 '-amino-3'- isopropyloxyphenyl) -2-hyd roxymethyl piperidine, 1- (4'-amino-3'-aminophenyl) - 2-hydroxymethyl piperidine, 1- (4'-amino-3'-dimethylaminophenyl) -2- mercaptoethyloxyethyl piperidine, 1- (4'- amino-3 '(- 2 "', 4" '- dichloro) anilinophenyl) -4-methyl piperidine, 1- (4'-aminophenyl) -4-methyl piperidine, 1- (4'-aminophenyl) -2 , 7-dimethyl azacycloheptane, 1- (4'-amino-3'-methylphenyl) -2-methyl azacycloheptane, 1- (4'-amino-3'-ureidophenyl) -3- hydroxy azacycloheptane, 1- ( 4'-amino-3'-sulfamoylaminophenyl) -2,7-dimethyl azacycloheptane, 1- (4'-amino-3'-methylthiophenyl) -2,7-dimethyl azacycloheptane, 1 -N-4'-hydroxybutyl- 1-N- (hydroxyethyloxyethyloxyethyl) -3- isopropyl paraphenylenediamine, 1-N-methyl-1-N- (hydroxyethyloxyethyloxyethyl) paraphenylene diamine, 1-N-phenyl-1-N- (hydroxyethyloxyethyl) paraphenylenediamine, 1 -N-benzyl-1 -N- (hydroxyethyloxyethyloxyethyloxyethylethyloxyethyl) -3-trimethylsilyl paraphenylenediamine, 1-N-methyl-1-N- (hydroxy - ethyloxyethylyxyxyethyloxyethyloxyethyloxyethyloxyethyloxyethyl) -3- trimethylsilyloxy paraphenylenediamine, 1-N-ethyl-1-N-

(Méthoxyéthyloxyéthyloxyéthyloxy-éthyloxyéthyl) -3-phenoxycarbonylamino paraphenylenediamine, 1-N-methyl-1-N- (methoxyethyloxyethyloxyethyl) -3- (2 ', 5'-dioxopyrrolidinyl) paraphenylene diamine, 1-N-ethyl-1-N-

(hydroxyethyloxyethyloxyethyl) -3-4'pyhdinylthio paraphenylenediamine, 1-N-propyl-1-N- (hydroxyethyloxyethyloxyethyl) -3-sulfinyl paraphenylenediamine, 1- N-methyl-1 -N- (hydroxyethyloxyethyl) -3-phenoxycarbonyl paraphenylenediamine , 1-N, N-bis- (hydroxyethyloxy-ethyloxyethyloxyethyl) paraphenylenediamine, 1- N, N-bis- (methoxyethyloxy-ethyloxyethyloxyethyl) -3-isopropyloxy paraphenylenediamine, 1-N, N-bis- (hydroxyethyloxyethyloxyethyl) - 3- isopropyloxy paraphenylenediamine, 1-N, N-bis- (hydroxyethyloxyethyloxyethyloxyethyl) -3-isopropyl paraphenylene diamine, 1- N, N-bis- (hydroxyethyloxyethyloxyethyloxyethyl) -3-isopropyl paraphenylenediamine, 1-N, N- bis- (methoxyethyloxyethyloxyethyloxyethyloxyethylethyloxyethyloxyethyl) -3-methoxy paraphenylenediamine, 1-N, N-bis- (hydroxyethyloxyethyloxyethyloxyethyloxyethyloxyethyloxyethyloxyethyl) -3-methyl paraphenylenediamine, 1-N, N-bis- (hydroxyethyloxy-ethyloxyethyloxy yethyl) -3- isopropyloxy paraphenylenediamine, 1-N, N-bis- (hydroxyethyloxyethyl) -3- mercaptoethyl paraphenylenediamine, 1-N, N-bis- (benzyloxyethyloxyethylethyloxyethyl) -3-isopropyl paraphenylenediamine, and their salts d 'addition with an acid,

and which are more particularly preferred among them

1- (4'-amino-3'-methylphenyl) -3-hydroxyethyloxy pyrrolidine, 1- (4'-amino-3'-methylphenyl) -4-hydroxy-2-methyl pyrrolidine, 1- (4 ' -amino-3'-methylphenyl) -3- methylsulfonamido pyrrolidine, 1- (4'-amino-3'-phenoxyphenyl) -3- methylsulfonamido pyrrolidine, 1- (4'-aminophenyl) -2- (4 "- aminophéπoxyméthyl) pipéridine, 1- (4'-aminophenyl) -2- (hydroxyethyl) piperidine, 1- (4'-amino-3'- isopropylphenyl) -2-hydroxymethyl piperidine, 1- (4'-aminophenyl) -4-methyl piperidine, 1- (4'-aminophenyl) -2,7-dimethyl azacycloheptane, 1- (4'-amino-3'-methylphenyl) -2-methyl azacycloheptane, 1- (4'- amino-3'-ureidophenyl) -3- hydroxy azacycloheptane, 1-N-4'-hydroxybutyl-1-N-

(hydroxyethylioxyethyloxyethyl) -3-isopropyl paraphenylenediamine, 1-N-methyl-1N- (hydroxyethyloxyethyloxy-ethyl) paraphenylene diamine, 1-N, N-bis- (hydroxyethyloxy-ethyloxyethyloxyethyl) paraphenylenediamine, 1-N, N-bis- (hydroxyethyloxyethyloxyethyloxyethyl) -3-isopropyl paraphenylene diamine, 1- N, N-bis- (hydroxyethyloxyethyloxyethyloxyethyl) -3-isopropyl paraphenylenediamine, 1-N, N-bis- (hydroxyethyloxyethyloxyethyloxyethyloxyethyloxyethyloxyethyloxyethyl) -3-methyl paraphenylenediamine, 1-N, N-bis- (benzyloxyethyioxy-ethyloxyethyl) -3- isopropyl paraphenylenediamine, and their addition salts with an acid.

The para-phenylenediamine derivative (s) of formula (I) used as oxidation base in the dye composition in accordance with the invention are present at concentrations varying from 0.0001 to 20%, preferably from 0.001 to 15% and even more particularly from 0.01 to 10% by weight relative to the total weight of the composition.

The synthetic direct dyes which can be used according to the invention can be nonionic, anionic or cationic.

Among the azo synthetic direct dyes which can be used according to the invention, mention may be made of the cationic azo dyes described in patent applications WO 95/15144, WO-95/01772 and EP-714954, the content of which forms an integral part of the invention.

One can also cite among the azo direct dyes the following dyes, described in the COLOR INDEX INTERNATIONAL 3 ^rd edition:

-Disperse Red 17 -Acid Yellow 9

-Acid Black 1

-Basic Red 22

-Basic Red 76

-Basic Yellow 57 -Basic Brown 16

-Acid Yellow 36

-Acid Orange 7

-Acid Red 33 -Acid Red 35 -Basic Brown 17 -Acid Yellow 23 -Acid Orange 24 -Disperse Black 9.

Mention may also be made, among them, of 1- (4'-aminodiphenylazo) -2-methyl-4-bis- (β-hydroxyethyl) -aminobenzene and 4-hydroxy-3- (2-methoxyphenylazo) acid -1- naphthalene sulfonic.

Among the quinone synthetic direct dyes, the following may be mentioned:

-Disperse Red 15

-Follow Violet 13

-Acid Violet 43

-Disperse Violet 1 -Disperse Violet 4

-Disperse Blue 1

-Disperse Violet 8

-Disperse Blue 3

-Disperse Red 11 -Acid Blue 62

-Disperse Blue 7

-Basic Blue 22

-Disperse Violet 15

-Basic Blue 99, as well as the compounds:

-1-N-méthylmorpholiniumpropylamino-4-hydroxyanthraquinone,

-1-aminopropylamino-4-méthylaminoanthraquinone,

-1-aminopropylaminoanthraquinone,

-5-β-hydroxyethyl-1,4-diaminoanthraquinone, -2-aminoethylaminoanthraquinone,

-1,4-bis (β, γ-dihydroxypropylamino) anthraquinone.

Among the synthetic direct azine dyes, the following may be mentioned: -Basic Blue 17 -Basic Red 2.

Among the synthetic direct triarylmethane dyes which can be used according to the invention, the following may be mentioned: -Basic Green 1 -Acid blue 9 -Basic Violet 3 -Basic Violet 14 -Basic Blue 7 -Acid Violet 49 -Basic Blue 26 -Acid Blue 7

Among the synthetic indoamine direct dyes which can be used according to the invention, the following may be mentioned:

-2-β-hydroxyethylamino-5- [bis- (β-4'-hydroxyethyl) -amino] -anilino-1, 4-benzoquinone

-2-β-hydroxyethylamino-5- (2'-methoxy-4'-amino) -anilino-1, 4-benzoquinone -3-N (2'-chloro-4'-hydroxy) -phenyl-acetylamino-6- 1,4-methoxy-benzoquinone imine

-3-N (3'-chloro-4'-methylamino) -phenyl-ureido-6-methyl-1, 4-benzoquinone imine

-3- [4'-N- (ethyl, carbamylmethyl) -amino] -phenyl-ureido-6-methyl-1, 4-benzoquinone imine.

By natural dye is meant within the meaning of the invention, the compounds which exist in nature whether they have been obtained by extraction or reproduced via chemistry. Among the natural direct dyes which can be used according to the invention, mention may be made of lawsone, juglone, alizarin, purpurin, carminic acid, kermesic acid, purpurogallin, protocatechaldehyde, indigo, isatin , curcumin, spinulosin, apigenidine. One can also use extracts or decoctions containing these natural dyes and in particular poultices or extracts based on henna. The synthetic direct dye (s) according to the invention and / or the natural dye (s) represent from 0.001 to 20% by weight approximately of the total weight of the composition and even more preferably from 0.005 to 10% by weight approximately.

Preferably, the compositions of the invention contain at least one coupler. Among these couplers, mention may in particular be made of metaphenylenediamines, meta-aminophenols, metadiphenols and heterocyclic couplers such as, for example, indole derivatives, indoline derivatives, benzimidazole derivatives, benzomorpholine derivatives, sesamol derivatives, pyridine, pyrimidine and pyrazole derivatives, and their addition salts with an acid.

These couplers are more particularly chosen from 2-methyl-5-amino-phenol, 5-N- (β-hydroxyethyl) -amino2-methyl-phenol, 3-amino-phenol, 1,3-dihydroxy-benzene , 1, 3-dihydroxy-2-methyl-benzene, 4-chloro-1,3-dihydroxy-benzene, 2,4-diamino-1- (β-hydroxyethyloxy) -benzene, 2-amino 4- (β-hydroxyethylamino) -1-methoxy-benzene, 1, 3-diamino-benzene, 1, 3-bis- (2,4-diaminophenoxy) -propane, sesamol, 1-amino-2-methoxy- 4,5-methylenedioxy-benzene, α-naphthol, 2-methyl-1-naphthol, 6-hydroxy indole, 4-hydroxyindole, 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, and their salts addition with an acid.

The coupler (s) may be present in the said composition according to the invention at a concentration of between 0.0001 and 15% by weight relative to the total weight of the composition.

The dye composition in accordance with the invention may, in addition, contain at least one additional oxidation base different from the substituted paraphenylenediamine derivatives of formula (I) and / or at least one direct dye different from those of the present invention. Among the additional oxidation bases which can be used according to the invention, there may be mentioned paraphenylenediamine, paratoluylenediamine, 2-hydroxyethyl-paraphenylenediamine, 1-N, N-bis (2-hydroxyethyl) -paraphenylenediamine, para-aminophenols such as 3-methyl-4-aminophenol and 4-aminophenol, orthophenylenes diamines, orthoaminophenols, double bases, heterocyclic bases such as pyrimidines such as 2,4,5,6-tetraaminopyrimidine or as pyrazoles such as 1- (2-hydroxyethyl) -4,5-diamino-pyrazole.

The additional oxidation base (s) may be present at a concentration of between 0.0001 and 15% by weight relative to the total weight of said composition.

The medium of the composition suitable for dyeing is preferably an aqueous medium consisting of water and may advantageously contain cosmetically acceptable organic solvents, including more particularly alcohols such as ethyl alcohol, alcohol isopropyl, benzyl alcohol, and phenylethyl alcohol, or glycols or glycol ethers such as, for example, the monomethyl, monoethyl and monobutyl ethers of ethylene glycol, propylene glycol or its ethers such as, for example, the monomethyl ether of propylene glycol, butylene glycol, dipropylene glycol as well as the diethylene glycol alkyl ethers such as, for example, the monoethyl ether or the monobutyl ether of diethylene glycol, in concentrations of between approximately 1 and 40% and, preferably, between approximately 2 and 10% by weight per relative to the total weight of the composition.

The composition according to the invention may also contain an effective amount of other agents, also known previously in oxidation dyeing, such as various usual adjuvants such as sequestrants such as EDTA and etidronic acid, UV filters, waxes, silicones, volatile or not, cyclic or linear or branched, organomodified (in particular by amino groups) or not, preservatives, ceramides, pseudoceramides, vegetable, mineral or synthetic oils, vitamins or provitamins such as panthenol, opacifiers, thickening agents such as crosslinked polyacrylic acids or hydroxyalkylcelluloses, etc.

Said composition can also contain reducing or antioxidant agents. These can be chosen in particular from sodium sulfite, thioglycolic acid, thiolactic acid, sodium bisulfite, dehydroascorbic acid, hydroquinone, 2-methyl-hydroquinone, ter-butyl- hydroquinone and homogentisic acid, and they are then generally present in amounts ranging from approximately 0.05 to 1.5% by weight relative to the total weight of the composition.

The composition according to the invention may also contain one or more fatty alcohols, these fatty alcohols being introduced in pure form or as a mixture. Mention may be made among them more particularly of lauric, cetyl, stearyl and oleic alcohols and their mixtures. These fatty alcohols can represent from 0.001 to 20% by weight approximately of the total weight of the composition.

Preferably, the composition of the invention contains at least one nonionic, anionic, cationic or amphoteric surfactant in the proportion of about 0.1 to 20% by weight. Even more preferably, said composition contains at least one nonionic surfactant.

The composition according to the invention preferably contains at least one cationic or amphoteric substantive polymer in the proportion of approximately 0.05 to 10% by weight.

Of course, those skilled in the art will take care to choose the optional compound (s) mentioned above, in such a way that the advantageous properties intrinsically attached to the oxidation dye composition according to the invention are not, or not substantially, altered by the planned addition (s).

In the oxidizing composition, the oxidizing agent is preferably chosen from hydrogen peroxide, urea peroxide, bromates or ferricyanides of alkali metals, persalts such as perborates and persulfates. The use of hydrogen peroxide is particularly preferred. This oxidizing agent advantageously consists of a solution of hydrogen peroxide, the titer of which can vary, more particularly, from approximately 1 to 40 volumes, and even more preferably from approximately 5 to 40.

It is also possible to use, as oxidizing agent, one or more redox enzymes such as laccases, peroxidases and oxidoreductases with 2 electrons (such as uricase), where appropriate in the presence of their respective donor or cofactor.

The pH of the coloring composition or of the ready-to-use composition applied to the keratin fibers [composition resulting from the mixture of the coloring composition according to the invention and the oxidizing composition] is generally between the values 4 and 12 It is preferably between 6 and 11, and can be adjusted to the desired value by means of acidifying or basifying agents well known from the state of the art in dyeing keratin fibers.

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, hydroxyalkylamines and ethylenediamines oxyethylenated and / or oxypropylenes, sodium or potassium hydroxides and the compounds of formula (II) below:

⁵ \ R ₇

N -W- N (")

/ R. in which, W is a propylene residue optionally substituted by a hydroxyl group or an alkyl radical in CrC ₄ ; R5, Re, R and R _8, identical or different, represent a hydrogen atom, an alkyl radical with Cι-C ₄ hydroxyalkyl or Cι-C _4. The acidifying agents are conventionally, for example, mineral or organic acids such as hydrochloric acid, orthophosphoric acid, carboxylic acids such as tartaric acid, citric acid, lactic acid, or acids sulfonic.

The dye composition in accordance with the invention can be in various forms, such as in the form of liquids, powders, creams, gels, optionally pressurized, or in any other form suitable for dyeing keratin fibers, and especially human hair.

The dyeing process according to the invention preferably consists in applying the ready-to-use composition, produced extemporaneously at the time of use, from the coloring composition according to the invention and the oxidizing composition described above. , on the dry or wet keratin fibers, and to let it act for a pause time varying, preferably, from 1 to 60 minutes approximately, and more preferably from 10 to 45 minutes approximately, rinsing the fibers, then optionally wash with shampoo, then rinse again, and dry them.

The following examples are intended to illustrate the invention.

EXAMPLES

The following dye compositions were prepared, in accordance with the invention

H Dye support

- Alkyl C ₈ -Cιo polyglucoside in aqueous solution at 60%, sold under the name ORAMIX CG 110 ® by the company SEPPIC 3.24 g MA * - Ethanol 18.0 g

- Benzyic alcohol 1, 8 g

- Polyethylene glycol 400 2.7 g

- Pentasodium salt of diethylene triamine pentacetic acid in 40% aqueous solution, sold under the name DISSOLUINE D-40 ® by the company AKZO 0.43 g MA *

- Sodium metabisulfite 0.205 g

- Ammonia at 20.5% NH ₃ 10.0 g

MA ^* stands for Active Matter At the time of use, the dye compositions described above were mixed weight for weight with a 20 volume hydrogen peroxide solution (6% by weight).

The mixtures thus produced were applied for 30 minutes to locks of permanent natural gray hair containing 90% white hairs. The locks were then rinsed, washed with a standard shampoo, rinsed again and then dried.

The hair was dyed in a purplish blue shade sustained from composition 1 and in a deep purple shade sustained from composition 2.

Claims

1. Composition for the oxidation dyeing of keratin fibers and in particular human keratin fibers such as the hair, characterized in that it comprises, in a medium suitable for dyeing: - (A) at least one base d oxidation chosen from the substituted paraphenylenediamine derivatives of formula (I) below, and their addition salts with an acid:

in which :

- Ri and R ₂ can take one of the following meanings i) to v):

i) Ri and R ₂ simultaneously represent a radical - (CH ₂ ) 2CHOHCH ₂ OH; or ii) Ri represents a -CH ₂ (CHOH) ₄ CH ₂ OH radical and R ₂ represents a hydrogen atom, an alkyl or aryl radical or a heterocycle; or iii) Rι represents an alkyl, aryl or heterocycle radical and R ₂ represents an alkylene radical - (CH ₂ ) _m - in which m is an integer equal to 2 or 3, said alkylene radical forming a ring together with nitrogen atom, the carbon atom of the benzene ring carrying the nitrogen atom and one of the two carbon atoms of the benzene ring which are adjacent to it, it being understood that when R 1 is an alkyl or aryl radical, then either Ri or said alkylene radical is substituted by a radical containing at least one nitrogen, oxygen or sulfur atom;

ÈVJR _T represents a radical - (CH ₂ CH ₂ 0) _p R ₄ in which p is an integer between 2 and 8 inclusive, R and R ₂ , identical or different, represent a hydrogen atom, an alkyl or aryl radical or a heterocycle; v) Ri and R ₂ form, together with the nitrogen atom to which they are attached, a saturated 5, 6 or 7-membered heterocycle, said heterocycle being substituted by at least one radical containing at least one carbon atom, or nitrogen, or oxygen, or sulfur;

- R ₃ represents a halogen atom, an alkyl or aryl radical, a cyano, nitro, hydroxyl, carboxyl, sulfo, alkoxy, aryloxy, cyanoamino, amino, anilino, ureido, sulfamylamino, mono- or di-alkylsulfamylamino, alkylthio radical , arylthio, alkoxycarbonyiamino, sulfonamido, carbamyl, mono- or di-alkylcarbamylsulfamyle, sulfonyl, alkoxycarbonyl, azo, acyloxy, carbamyloxy, mono- or di-alkylcarbamyloxy, silyl, silyloxy, aryloxycarbonylamino, imonyl acylcarbonyl, aryloxycarbonyl , a heterocycle, a heterocycle linked to the benzene ring of formula (I) by an ether or thio bond;

said alkyl radicals having from 1 to 25 carbon atoms and which may be linear, branched or cyclic and be substituted by one or more radicals and then represent a mono or polyhydroxyalkyl, alkoxyalkyl, aminoalkyl radical optionally substituted on the nitrogen atom, carboxyaikyl , alkylcarboxyalkyle, thioalkyle, alkylthioalkyie, cyanoalkyle, trifluoroalkyle, sulfoalkyle, phosphoalkyle, or haloalkyle; said alkoxy radicals having from 1 to 25 carbon atoms and which may be linear, branched or cyclic; said aryl radicals containing from 6 to 26 carbon atoms and which may be substituted by one or more radicals chosen from alkyl, substituted alkyl or alkoxy radicals; the heterocycles being mono or polycyclic, each cycle comprising 3, 4, 5 or 6 members and which may contain one or more heteroatoms, it being understood that in the case of polycyclic heterocycles, at least one of the rings contains at least one heteroatom such as N , O or S; - n is an integer between 0 and 4; it being understood that when n is greater than 1, then the radicals R ₃ may be identical or different and form between them a saturated or unsaturated ring with 3, 4, 5, or 6 links;

provided that :

2) when Ri and R ₂ have the meanings defined in point v) and when Ri and R ₂ form a pyrridine ring substituted by a carbamoyl radical on the carbon in the alpha position of the nitrogen atom to which they are attached, then n is different from 0; or else the pyrrolidine ring carries at least two substituents;

3) when R and R ₂ have the meanings defined in point v) and when Ri and R ₂ form a pyrrolidine ring substituted by a hydroxymethyl radical on the carbon located in the alpha position relative to the nitrogen atom on which they are fixed, and that n = 0 or 1, then either said ring carries at least two additional substituents, or said cycle only has a second substituent different from a hydroxyl radical on the carbon located in position β relative to the atom nitrogen and with respect to the carbon carrying said hydroxymethyl substituent; or when Ri and R ₂ have the meanings defined in point v) and when Ri and R ₂ form a pyrrolidine ring substituted by a hydroxymethyl radical on the carbon located in the alpha position relative to the nitrogen atom on which they are fixed, and that n = 1, then R ₃ is different from an alkyl, mono- or polyhydroxyalkyl radical; 4) when Ri and R ₂ have the meanings defined in point iii) the compounds of formula (I) must fulfill at least one of the following four conditions: a) whatever the value of n, the alkylene ring formed by the radical R ₂ has a substituent in addition to the radical Ri; or b) n is greater than 1; or c) when n is equal to 1, then R ₃ represents an aryl radical or a heterocycle; or d) when n is equal to zero or to 1, then Ri represents an aryl radical, a heterocycle or a substituted alkyl radical different from a monohydroxyalkyl radical; 5) Ri and R ₂ form a different cycle of piperazine and diazacycloheptane;

2. Composition according to claim 1, characterized in that in formula (I), Ri and R ₂ take one of the following meanings i) to v):

i) Ri and R ₂ simultaneously represent a radical - (CH ₂ ) ₂ CHOHCH ₂ OH; or ii) Ri represents a radical -CH ₂ (CHOH) ₄ CH ₂ OH and R ₂ represents a hydrogen atom, an alkyl radical; or iv) Rι represents a radical - (CH ₂ CH ₂ 0) _p R ₄ in which p is an integer between 2 and 8 inclusive, R ₄ and R ₂ , identical or different, represent a hydrogen atom, a alkyl radical; v) Ri and R ₂ form, together with the nitrogen atom to which they are attached, a saturated 5, 6 or 7-membered heterocycle, said heterocycle being substituted by at least one radical containing at least one carbon atom, or nitrogen, or oxygen, not located in the meta position relative to the nitrogen atom of the heterocycle;

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

- n is an integer equal to 0, 1 or 2.

3. Composition according to claim 1 or 2, characterized in that in formula (I), Ri and R ₂ form a pyrroiidin heterocycle.

4. Composition according to Claim 1 or 2, characterized in that the substituted derivative (s) of paraphenylenediamine of formula (I) are chosen from: 1-N, N-bis- (3 ', 4'-dihydroxybutyl) paraphenylenediamine , 1-N, N-bis- (3 ', 4'- dihydroxybutyl) -3-methyl paraphenylenediamine, 1-N, N-bis- (3', 4'- dihydroxybutyl) -3-ethyl paraphenylenediamine, 1-N, N-bis- (3 ', 4'-dihydroxybutyl) - 3-propyl paraphenylenediamine, 1-N, N-bis- (3', 4'-dihydroxybutyl) -3-methoxy paraphenylenediamine, 1- N, N-bis- (3 ', 4'-dihydroxybutyl) -3-ethoxy paraphenylenediamine, 1-N, N-bis- (3', 4'-dihydroxybutyl) -3-propyioxy paraphenylenediamine, 1-N, N-bis- (3 ', 4'-dihydroxybutyl) -3-hexyloxy paraphenylenediamine, 1-N, N-bis- (3', 4'-dihydroxybutyl) -3- (1 "-N-3", 5 "- dimethyipyrazolyl paraphenylenediamine, 1-N, N-bis- (3 ', 4'-dihydroxybutyl) -3- ureido paraphenylenediamine, 1-N, N-bis- (3', 4'-dihydroxybutyl) -3- trimethyl 1 ", 3", 3 "-ureido paraphenylenediamine, 1-N, N-bis- (3 ', 4 '-dihydroxybutyl) -3- dimethylamino paraphenylenediamine, 1-N, N-bis- (3', 4'-dihydroxybutyl) -3- methylthio paraphenylenediamine, 1-N, N-bis- (3 ', 4'- dihydroxybutyl) -3-ethylthio paraphenylenediamine, 1-N, N-bis- (3 ', 4'-dihydroxybutyl) -3-mercapto paraphenylenediamine 1-N, N-bis- (3', 4'-dihydroxybutyl) - 3-n.butylthio paraphenylenediamine, 1-N, N-bis- (3 ', 4'-dihydroxybutyl) -3-n.octylthio paraphenylenediamine, 1-N, N-bis- (3', 4'-dihydroxybutyl ) -3-mercaptoethyl paraphenylenediamine, 1-N, N-bis- (3 ', 4'-dihydroxybutyl) -3-mercaptoethyl thioparaphenylenediamine, 1-N, N-bis- (3', 4'-dihydroxybutyl) - 3-β-hydroxyethyl thioparaphenylenediamine 1-N- (2 ', 3', 4 ', 5', 6'-pentahydroxyhexyl) paraphenylenediamine, 1-N- (2 ', 3', 4 ', 5', 6 '-pentahydroxyhexyl) -3-methyl paraphenylenediamine, 1-N- (2', 3 ', 4', 5 ', 6'-pentahydroxyhexyl) -3-isopropyl paraphenylenediamine, 1-N- (2', 3 ' , 4 ', 5', 6'-pentahydroxyhexyl) -3-methoxy paraphenylenediamine, 1-N- (2 ', 3', 4 ', 5', 6'-pentahydroxyhe xyl) -1-N- (4 "-

N "methylpiperidyl) -3-ethoxy paraphenylenediamine, 1-N- (2 ', 3', 4 ', 5', 6'- pentahydroxyhexyl) -3-isopropyloxy paraphenylenediamine, 1-N- (2 ', 3' , 4 ', 5', 6'- pentahydroxyhexyl) -3-dimethylamino paraphenylenediamine, 1-N- (2 ', 3', 4 ', 5', 6'- pentahydroxyhexyl) -3-methyl thioparaphenylenediamine, 1- N- (2 ', 3', 4 ', 5', 6'- pentahydroxyhexyl) -3-mercapto paraphenylenediamine, 1-N- (hexyl) -1-N- (2 ', 3', 4 ', 5 ', 6'-pentahydroxyhexyl) -3-isopropyl paraphenylenediamine, la

1-N- (methyl) -1-N- (2 ', 3', 4 ', 5', 6'-pentahydroxyhexyl) -3-isooctyloxy paraphenylenediamine, 1-N- (methyl) -1-N- (2 ', 3', 4 ', 5', 6'-pentahydroxyhexyl) -3- isopropyloxy paraphenylenediamine, 1-N- (methyl) -1- N- (2 ', 3', 4 ', 5', 6'- pentahydroxyhexyl) -3-methyl paraphenylene-diamine, 1-N- (methyl) -1-N- (2 ', 3', 4 ' , 5 ', 6'-pentahydroxyhexyl) -3-ethyl paraphenylenediamine, lN- (methyl) - lN- (2', 3 ', 4', 5 ', 6'-pentahydroxyhexyl) -3-hydroxyethyloxy paraphenylenediamine, lN - (methyl) -1-N- (2 ', 3', 4 ', 5', 6'-pentahydroxyhexyl) -3-mercaptoethyloxy paraphenylenediamine, 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 paraphenylenediamine, 1-N- (4 "-N-methylpiperidyl) -1-N- (2 ', 3', 4 ', 5', 6'- pentahydroxyhexyl) -3-ethyloxy paraphenylenediamine, 4-N- (methyl) -4-N- (2 ', 3', 4 ', 5', 6'-pentahydroxyhexyl) -amino-7amino-1-methylindole, 1-N-

(hydroxyethyloxyethyl) -1-N- (2 ', 3', 4 ', 5', 6'-pentahydroxyhexyl) -3-ethyl paraphenylenediamine, 1-N- (3 ', 4'-dihydroxybutyl) -5-aminoindoline , 1- (2'-hydroxyethyl) -2methyl-5-aminoindoline, 1-methyl-2-hydroxymethyl-5-aminoindoline, 6-methyl-2-hydroxyethyl-5-aminoindoline,

2-hydroxyethyloxyethyl-5-aminoindoline, 2-hydroxyethyloxyethyloxyethyloxyethyl-5-aminoindoline, 2-hydroxyethyloxyethyloxyethyloxyethyloxy-ethyloxyethyl-6-isopropyl-5-aminoindoline, 2-hydroxyethyl-3-methyl-5-aminoindoline, 2- hydroxyethyloxyethyloxyethyl) -5-aminoindoline, 1-carboxymethyl-2,3,3-thmethyl-5-aminoindoline, 1-methylsulfonamidoethyl-3-methyl-5-aminoindoline, 1-ureidoethyl-6-methoxy-5-aminoindoline, 1- (2 ', 3', 4 ', 5', 6'-pentahydroxy-hexyl) -5-aminoindoline, 1-N- (2'-mercaptoethyl) -5 aminoindoline, dimethyl ester 6-amino- 1-methyl-1,2,3,4-tetrahydro-furo- [2,3, h] - quinoline 4-methylester of phosphoric acid, 6-amino-1,2,2-trimethyl-4-trimethylsilanyioxy -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-

(3'-ethoxyethoxyethoxyethoxy-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- (ethyl- bis-

(hydroxyethyloxyethyloxyethyloxyethyl)) - 2,2,3,7-tetramethyl-1,2,3,4- tetrahydroquinoline, 1- (carboxymethyl) -2,2,3,7-tetramethyl-1,2,3,4- tetrahydro- quinoline, 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- (hydroxyethyloxy-ethyloxyethyloxyethyloxyethyioxyethyloxyethyloxyethyl) -2,2,3-trimethyl-7-isopropyl-1, 2,3,4-tetra -hydroquinoline, 6-amino-1- (hydroxyethyloxyethylethyloxyethyloxyethyloxyethyloxy-ethyloxyethyloxyethyl) -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-hydroxymethyl-7-isopropyl-1, 2,3,4-tetrahydroquinoline, 6-amino-1- (3-hydroxypropyl) -2,2-dimethyl-4-hydroxymethyl -7-isopropyl-1, 2,3,4-tetrahydroquinoline, 6-amino-1- (hyd roxyethyloxyethyloxyethyloxyethylethyloxyethyloxyethyloxyethyloxyethyl) -2,2-dimethyl-4-hydroxymethyl-7-isopropyl- 1,2,3,4-tetrahydroquinoline, 6-amino-1- (hydroxy-ethyloxyethyloxyethyloxyethyl) - 2,2-dimethyl-4- hydroxymethyl-7isopropyl-1, 2,3,4-tetrahydroquinoline, 6-amino- 1- (hydroxyethyloxyethyloxyethyloxy-ethyloxyethyl) -2,2-dimethyl-7-isopropyl- 1, 2,3,4-tetrahydroquinoline, 6- amino-1- (hydroxyethyloxyethyloxyethyloxy-ethyloxyethyloxyethyl) -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- (hydroxyethyloxyethyloxy-ethyloxyethyl) -4,4-dimethyl-1, 2 , 3,4-tetra-hydroquinoline, 6-amino-1- (3 ', 4'- dihydroxybutyl) -2,2-dimethyl-7-iso propyl-1,2,3,4-tetrahydroquinoline, 6-amino- 1- (hydroxyethyloxyethyloxyethyloxyethyl) -4- (hydroxyethyloxyethyloxyethyloxyethyl) -2,2,7-trimethyl-1,2,3,4-tetrahydro-quinoline , 6-amino-1- (hydroxyethyloxy-ethyloxyethyloxyethyl) -2,2-dimethyl-7-isopropyl-1, 2,3,4-tetra-hydroquinoline, 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-tetrahydro-quinoline, 6-amino-1- (3', 4'- dihydroxybutyi) -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- acid amino-2,2-dimethyl-7-chloro-1, 2,3,4-tetrahydroquinoline-1-propylsulfonic, 6-amino-1- (4'-pyridinyl) -2,2,7-trimethyl-1, 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-trimethylsiianyloxy-1, 2,3,4-tetrahydroquinoline, 6-amino-1,2,2,4-tetramethyl-3-hydroxy-1,2,3 , 4-tetrahydroquinoline, 6-amino-1- bromo-2,2-dimethyl-4-mercapto-7-isopropyloxy-1, 2,3,4-tetrahydroquinoline, 1- (4'-amino-3'- isopropyloxyphenyl) -2,6-dimethyl pyrrolidine, 1- (4'-amino-3'-methylphenyl) -3-hydroxyethyloxy pyrrolidine, 1- (4'-amino-3'-methylphenyl) -4- hydroxy-2 -methyl pyrrolidine, 1- (4'-amino-3'-methylphenyl) -3- methylsulfonamido pyrrolidine, 1- (4'-amino-3'-phenoxyphenyl) -3- methylsulfonamido pyrrolidine, 3-n acid .butyl pyrrolidine 1- (4'-amino-3'-phenylsulfonic), 1- (4'-amino-3'-acetylaminophenyl) -3-hydroxymethyl pyrrolidine, 7-amino-4- ( 2'-methyl) -pyrrolydinyl-benzofuran, 1- (4'- aminophenyl) -2- (4 "-aminophenoxymethyl) piperidine, 1- (4'-amino-3'- acetylphenyl) -4-hydroxy piperidine, 1- (4'-aminophenyl) -2- (hydroxyethyl) piperidine, 1- (4'-amino-3'-methoxyphenyl) -2,6-dihydroxymethyl piperidine, 1- (4'-amino-3 ' -isopropyloxyphenyl) -2,6-dimethyl piperidine, 1- (4'-amino-3'- isopropylphenyl) -2-hydroxymethyl piperidine, 1- (4'-amino-3'- isopropyloxyphenyl) -2-hydroxymethyl piperidine , 1- (4'-amino-3'-aminophenyl) - 2-hydroxymethyl piperidine, 1- (4'-amino-3'-dimethylaminophenyl) -2- mercaptoethyloxyethyl piperidine, 1- (4'-amino- 3 '(- 2 "', 4"'- dich! Oro) anilinophenyl) -4-methyl piperidine, 1- (4'-aminophenyl) -4-methyl piperidine, 1- (4'-aminophenyl) -2 , 7-dimethyl azacycloheptane, 1- (4'-amino-3'-methylphenyl) -2-methyl azacycloheptane, 1- (4'-amino-3'-ureidophenyl) -3- hydroxy azacycloheptane, 1- ( 4'-amino-3'-sulfamoylaminophenyl) -2,7-dimethyl azacycloheptan e, 1- (4'-amino-3'-methylthiophenyl) -2,7-dimethyl azacycloheptane, 1 -N-4'-hydroxybutyl-1 -N- (hydroxyethyloxyethyloxyethyl) -3- isopropyl paraphenylenediamine, 1- N-methyl-1-N- (hydroxyethyloxyethyloxyethyl) paraphenylene diamine, 1-N-phenyl-1-N- (hydroxyethyloxyethyl) paraphenylenediamine, 1-N-benzyl-1-N- (hydroxyethyloxyethyloxyethyloxyethylethyloxyethyl) - 3-trimethylsilyl paraphenylenediamine, 1-N-methyl-1-N- (hydroxy-ethylyethyloxyethyloxyethyloxyethyloxyethyloxyethylpxyethyl) -3-trimethylsilyloxy paraphenylenediamine, 1-N-ethyl-1-N- (methoxyethyloxyethyloxyethyloxy- ethyloxyethyl) -3-phenoxycarbonylamino paraphenylenediamine, 1-N-methyl-1- N- (methoxyethyloxyethyloxyethyl) -3- (2 ', 5'-dioxopyrrolidinyl) paraphenylenediamine, 1-N-ethyl-1-N- (hydroxyethyloxyethyloxyethyl) -3-4'pyridinylthio paraphenylenediamine, 1 -N-propyl-1 -N- (hydroxyethyloxyethyloxyethyl) -3- sulfinyl paraphenylenediamine, 1-N-methyl-1-N- (hydroxyethyloxyethyl) -3- phenoxycarbonyl paraphenylenediamine, 1 -N, N-bis- (hydroxyethyloxy-ethyloxyethyloxyethyl) paraphenylenediamine, 1-N, N-bis- (methoxyethyloxy-ethyloxyethyloxyethyl) -3-isopropyloxy paraphenylenediamine, 1-N, N-bis- (hydroxyethyloxyethyloxyethy) -3-isopropyloxy paraphenylenediamine, 1-N, N-bis- (hydroxyethyloxyethyloxyethyloxyethyl) -3-isopropyl paraphenylenediamine, 1-N, N-bis- (hydroxyethyloxyethyloxyethyloxyethyl) -3-isopropyl paraphenylenediamine, 1-N, N-bis- (methoxyethyloxyethyloxyoxyoxyoxyoxy ethyloxyethyloxyethyl) -3-methoxy paraphen ylenediamine, 1-N, N-bis- (hydroxyethyloxyethyloxyethyloxyethyloxyethyloxyethyloxyethyloxyethyl) -3-methyl paraphenylenediamine, 1-N, N-bis- (hydroxyethyloxyethyloxyethyloxyethyl) -3- isopropyloxy paraphenylenediamine, 1-N, N-bis- (hydroxyethyloxyethyl) -3- mercaptoethyl paraphenylenediamine, 1-N, N-bis-

(benzyloxyethyloxyethyloxyethyl) -3-isopropyl paraphenylenediamine, and their addition salts with an acid.

5. Composition according to claim 4, characterized in that they are chosen from: 1-N, N-bis- (3 ', 4'-dihydroxybutyl) paraphenylenediamine, 1-N, N-bis- (3 ', 4'- dihydroxybutyl) -3-methyl paraphenylenediamine, 1-N, N-bis- (3', 4'- dihydroxybutyl) -3-ethyl paraphenylenediamine, 1-N, N-bis- (3 ', 4'-dihydroxybutyl) - 3-propyl paraphenylenediamine, 1-N- (2 ', 3', 4 ', 5', 6'-pentahydroxyhexyl) paraphenylenediamine, 1-N- (2 ', 3', 4 ' , 5 ', 6'-pentahydroxyhexyl) -3-methyl paraphenylenediamine, 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 paraphenylene diamine, 1-N- (methyl) -1-N- (2 ', 3', 4 ', 5', 6'-pentahydroxyhexyl ) -3-ethyl paraphenylenediamine, lN- (methyl) - 1-N- (2 ', 3', 4 ', 5', 6'-pentahydroxyhexyl) paraphenylenediamine, 1-N- (hydroxyethyloxyethyl) -1-N- (2 ', 3', 4 ', 5', 6'-pentahydroxyhexyl) -3-ethyl paraphenylenediamine, and their addition salts with an acid.

6. Composition according to claim 4, characterized in that they are chosen from: 1- (4'-amino-3'-methylphenyl) -3-hydroxyethyloxy pyrrolidine, 1- (4'-amino-3 ' - methylphenyl) -4-hydroxy-2-methyl pyrrolidine, 1- (4'-amino-3'-methylphenyl) -3- methylsulfonamido pyrrolidine, 1- (4'-amino-3'-phenoxyphenyl) -3- methylsulfonamido pyrrolidine, 1- (4'-aminophenyl) -2- (4 "-aminophenoxymethyl) piperidine, 1- (4'-aminophenyl) -2- (hydroxyethyl) piperidine, 1- (4'-amino-3 '- isopropylphenyl) -2-hydroxymethyl piperidine, 1- (4'-aminophenyl) -4-methyl piperidine, 1- (4'-aminophenyl) -2,7-dimethyl azacycloheptane, 1- (4'-amino -3'- methylphenyl) -2-methyl azacycloheptane, 1- (4'-amino-3'-ureidophenyl) -3- hydroxy azacycloheptane, 1-N-4'-hydroxybutyl-1-N- (hydroxyethyloxyethyloxyethyl) - 3-isopropyl paraphenylenediamine, 1-N-methyl-1N- (hydroxyethyloxyethyloxy-ethyl) paraphenylene diamine, 1-N, N-bis- (hydroxyethyloxy-ethyloxyet hyloxyethyl) paraphenylenediamine, 1-N, N-bis- (hydroxyethyloxyethyloxyethyloxyethyl) -3-isopropyl paraphenylene diamine, 1- N, N-bis- (hydroxyethyloxyethyloxyethyloxyethyl) -3-isopropyl paraphenylenediamine, 1-N, N-bis -

(hydroxyethyloxyethyloxyethyloxyethyloxyethyloxyethyloxyethyloxyethyl) -3-methyl paraphenylenediamine, 1-N, N-bis- (benzyloxyethyloxy-ethyloxyethyl) -3- isopropyl paraphenylenediamine.

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

8. Composition according to any one of the preceding claims, characterized in that the substituted derivative or derivatives of paraphenylenediamine of formula (I) and / or the addition salt or their salts with an acid represent from 0.0001 to 20% by weight of the total weight of the composition.

9. Composition according to claim 8, characterized in that the substituted derivative (s) of paraphenylenediamine of formula (I) and / or the addition salt (s) with an acid represent from 0.001 to 15% by weight of the total weight of the composition.

10. Composition according to Claim 9, characterized in that the substituted derivative (s) of paraphenylenediamine of formula (I) and / or the addition salt (s) with an acid represent from 0.01 to 10% by weight of the weight total of the composition.

11. Composition according to any one of the preceding claims, characterized in that the azo synthetic direct dye (s) are nonionic, anionic or cationic.

12. Composition according to Claim 11, characterized in that the azo synthetic direct dye (s) are chosen from -Disperse Red 17 - Acid Yellow 9 - Acid Black 1 - Basic Red 22 - Basic Red 76 - Basic Yellow 57 - Basic Brown 16 - Acid Yellow 36 - Acid Orange 7 - Acid Red 33 - Acid Red 35 - Basic Brown 17 - Acid Yellow 23 - Acid Orange 24 - Disperse Black 9,

- 1- (4'-aminodiphenylazo) -2-methyl-4-bis- (β-hydroxyethyl) -aminobenzene and -4-hydroxy-3- (2-methoxyphenylazo) -1-naphthalene sulfonic acid.

13. Composition according to any one of claims 1 to 10, characterized in that the quinone synthetic direct dye (s) are chosen from -Disperse Red 15 - Solvent Violet 13 - Acid Violet 43 - Disperse Violet 1

- Disperse Violet 4 - Disperse Blue 1 - Disperse Violet 8 - Disperse Blue 3 - Disperse Red 11 - Acid Blue 62 - Disperse Blue 7 - Basic Blue 22 - Disperse Violet 15 - Basic Blue 99, -1 -N-methylmorpholiniumpropylamino-4- hydroxyanthraquinone, -1-aminopropylamino-4-methylaminoanthraquinone, -1-aminopropylaminoanthraquinone, -5-β-hydroxyethyl-1, 4-diaminoanthraquinone, -2-aminoethylaminoanthraquinone, -1, 4-bis- (βγ-dihydroxypropylamino) -anthraquinone.

14. Composition according to any one of claims 1 to 10, characterized in that the synthetic direct azine dye (s) are chosen from Basic Blue 17 and Basic Red 2.

15. Composition according to any one of claims 1 to 10, characterized in that the synthetic direct dye (s) triarylmethane are chosen from - Basic Green 1 - Acid blue 9 - Basic Violet 3 - Basic Violet 14 - Basic Blue 7 - Acid Violet 49 - Basic Blue 26 - Acid Blue 7.

16. Composition according to any one of claims 1 to 10, characterized in that the indoamine synthetic direct dye (s) are chosen from 2-β-hydroxyethylamino-5- [bis- (β-4'-hydroxyethyl) - amino] -anilino-1, 4-benzoquinone, 2-β-hydroxyethylamino-5- (2'-methoxy-4'-amino) -aniiino-1, 4-benzoquinone, 3-N (2'-chloro-4 ' -hydroxy) -phenyl-acetylamino-6-methoxy-1, 4-benzoquinone imine, 3-N (3'-chloro-4'-methylamino) -phenyl-ureido-6-methyl-1, 4-benzoquinone imine, 3 - [4'-N- (ethyl, carbamylmethyl) -amino] -phenyl-ureido-6-methyl-1, 4-benzoquinone imine.

17. Composition according to any one of claims 1 to 10, characterized in that the natural dye (s) are chosen from lawsone, juglone, alizarin, purpurin, carminic acid, kermesic acid, purpurogallin, protocatechaldehyde, indigo, isatin, curcumin, spinulosin, apigenidine, extracts or decoctions containing these natural dyes and in particular poultices or henna-based extracts.

18. Composition according to any one of the preceding claims, characterized in that the synthetic direct dye (s) according to the invention and / or the natural dye (s) represent from 0.001 to 20% by weight of the total weight of the composition.

19. Composition according to Claim 18, characterized in that the synthetic direct dye (s) according to the invention and / or the natural dye (s) represent from 0.005 to 10% by weight of the total weight of the composition.

20. Composition according to any one of the preceding claims, characterized in that it contains at least one coupler.

21. Composition according to Claim 20, characterized in that the coupler or couplers are chosen from metaphenylenediamines, meta-aminophenols, metadiphenols and heterocyclic couplers such as, for example, indole derivatives, indolinic derivatives, benzimidazole derivatives , benzomorpholine derivatives, sesamol derivatives, pyridine, pyrimidine and pyrazole derivatives, and their addition salts with an acid.

22. Composition according to Claims 20 and 21, characterized in that the coupler (s) are chosen from 2-methyl-5-amino-phenol, 5-N- (β-hydroxyethyl) -amino2-methyl-phenol, 3-amino-phenol, 1, 3-dihydroxy-benzene, 1, 3-dihydroxy-2-methyl-benzene, 4-chloro-1, 3-dihydroxy-benzene, 2,4-diamino-1 - (β-hydroxyethyloxy) -benzene, 2-amino 4- (β- hydroxyethylamino) -1-methoxy-benzene, 1, 3-diamino-benzene, 1, 3-bis- (2,4- diaminophenoxy) -propane, sesamol, 1-amino-2-methoxy-4,5-methylenedioxybenzene, α-naphthol, 2-methyl-1-naphthol, 6-hydroxy indole, 4-hydroxyindole, 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, and their addition salts with an acid.

23. Composition according to any one of claims 20 to 22, characterized in that the coupler (s) are present at a concentration of between 0.0001 and 15% by weight relative to the total weight of the composition.

24. Composition according to any one of the preceding claims, characterized in that it contains at least one additional oxidation base.

25. Composition according to Claim 24, characterized in that the additional oxidation base or bases are chosen from paraphenylenediamine, paratoluylenediamine, 2-hydroxyethyl-paraphenylenediamine, 1-N, N-bis (2-hydroxyethyl) -paraphenylenediamine, para-aminophenols, orthophenylenes diamines, orthoaminophenols, double bases, heterocyclic bases.

26. Composition according to claims 24 or 25, characterized in that the additional oxidation base (s) are present at a concentration of between 0.0001 and 15% by weight relative to the total weight of the composition.

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

28. Composition according to Claim 27, characterized in that the solvents are present in proportions of between 1 and 40% by weight relative to the total weight of the composition.

29. Composition according to any one of the preceding claims, characterized in that it contains sequestering agents, UV filters, waxes, volatile or non-volatile, cyclic or linear or branched silicones, organomodified (in particular by amino groups) or not, preservatives, ceramides, pseudoceramides, vegetable, mineral or synthetic oils, vitamins or provitamins, opacifiers, thickening agents, reducing or antioxidant agents, fatty alcohols, alkalizing or acidifying agents.

30. Composition according to any one of the preceding claims, characterized in that it contains at least one anionic, nonionic, cationic or amphoteric surfactant and preferably nonionic in a proportion ranging from 0.1 to 20% by weight.

31. Composition according to any one of the preceding claims, characterized in that it contains at least one cationic or amphoteric polymer in a proportion ranging from 0.05 to 10% by weight.

32. Ready-to-use composition for the oxidation dyeing of keratin fibers, in particular human keratin fibers such as the hair, characterized in that it is obtained by mixing a composition as defined in any one of claims 1 to 31 and of a composition containing at least one oxidizing agent.

33. Composition according to claim 32, characterized in that the pH is between the values 4 and 12 and preferably between 6 and 11.

34. Composition according to any one of the preceding claims, characterized in that it is in the form of liquids, powders, creams, gels, optionally pressurized, or in any other form suitable for dyeing the fibers. keratin, and in particular human hair.

35. Composition according to claim 32, characterized in that the oxidizing agent is chosen from hydrogen peroxide, urea peroxide, bramates or ferricyanides of alkali metals, persalts such as perborates and persulfates, redox enzymes such as laccases, peroxidases and oxidoreductases with 2 electrons, where appropriate in the presence of their respective donor or cofactor.

36. Composition according to claim 35, characterized in that the oxidizing agent consists of a solution of hydrogen peroxide whose titer varies from 1 to 40 volumes, and preferably from 5 to 40 volumes.

37. Process for the oxidation dyeing of keratin fibers, and in particular human keratin fibers such as the hair, consisting in applying to the fibers a composition consisting in applying to the fibers a coloring composition containing, in a medium suitable for dyeing, at least one substituted derivative of paraphenylenediamine of formula (I) defined in any one of claims 1 to 10, in association with at at least one azo, quinone, triarylmethane, indoamine or azine synthetic direct dye and / or a natural dye defined in any one of claims 11 to 17, the color being revealed at alkaline, neutral or acidic pH, using a composition containing at least one oxidizing agent, which is mixed just at the time of use with the coloring composition or which is applied sequentially without intermediate rinsing.

38. Method according to claim 37, characterized in that it consists in applying the ready-to-use composition, produced extemporaneously at the time of use from the composition according to the invention and the oxidizing composition, on dry or wet keratin fibers, and to let it act for a pause time varying, preferably from 1 to 60 minutes approximately, and more preferably from 10 to 45 minutes approximately, rinsing the fibers, then optionally washing them with shampoo, then rinse them again, and dry them.

39. Device with several compartments or "kit" for the oxidation dyeing of keratin fibers, in particular human keratin fibers such as the hair, which comprises at least one compartment containing at least one substituted derivative of paraphenylenediamine of formula (I) defined according to any one of claims 1 to 10 and at least one azo, quinonic, triarylmethane, indoamine or azine synthetic direct dye and / or a natural dye, and at least one other compartment containing at least one oxidizing agent.

40. Device with several compartments or "kit" for the oxidation dyeing of keratin fibers, in particular human keratin fibers such as the hair, which comprises at least one compartment containing at least one substituted derivative of paraphenylenediamine of formula (I) defined according to any one of claims 1 to 10, at least one compartment containing at least one azo, quinone, triarylmethane, indoamine synthetic direct dye or azine and / or a natural dye, and at least one other compartment containing at least one oxidizing agent.