WO2001066072A1

WO2001066072A1 - Oxidation dyeing composition for keratinous fibres and dyeing method using same

Info

Publication number: WO2001066072A1
Application number: PCT/FR2001/000663
Authority: WO
Inventors: Gérard Lang
Original assignee: L'oreal
Priority date: 2000-03-06
Filing date: 2001-03-06
Publication date: 2001-09-13
Also published as: PL352292A1; CZ20014324A3; CA2373099A1; HUP0202007A2; ZA200108983B; AU3934101A; BR0105561A; KR20010113913A; FR2805738A1; JP2003525889A; EP1181004A1; FR2805738B1; AU752948B2; CN1372457A

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

KERATINIC FIBER OXIDATION DYE COMPOSITION AND DYEING METHOD USING THE SAME

COMPOSITION

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 first oxidation base chosen from among certain substituted derivatives of paraphenylenediamine and their addition salts with an acid and at least a second selected oxidation base, 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 paraaminophenols, 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 combining them with couplers or color modifiers, the latter being chosen in particular from aromatic metadiamines, metaaminophenols, metadiphenols and certain heterocyclic compounds.

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 have good hold. facing 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 differently sensitized effect (ie damaged) between its tip and its root.

It has already been proposed, in particular in patent applications JP-11158046, JP-11158047 and JP-11158048, compositions for the oxidation dyeing of keratin fibers containing, as oxidation dye precursors, certain 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 dyes, capable of leading to colorations with varied shades, chromatic, powerful, aesthetic, not very selective and well resistant to the various aggressions which the fibers can undergo, by combining at least a first oxidation base chosen from certain derivatives of paraphenylenediamine of formula (I) defined below and their addition salts with an acid and at least one second oxidation base suitably selected.

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 medium suitable for dyeing: at least one first 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) 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, aryl radical or a heterocycle; or iii) Rι represents an alkyl or aryl radical or a heterocycle 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; iv) R-ι represents a radical - (CH ₂ CH ₂ O) _p R in which p is an integer between 2 and 8 inclusive, R and R ₂ , identical or different, represent a hydrogen atom, a radical alkyl, 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, nitrogen, sulfur oxygen; - R ₃ represents a halogen atom, an alkyl or aryl radical, a heterocycle, a heterocycle linked to the benzene ring of formula (I) by an ether or thio bond, a cyano, nitro, hydroxyl, carboxyl, sulfo radical, alkoxy, aryloxy, cyanoamino, amino, anilino, ureido, sulfamylamino, mono- or di-alkylsulfamylamino, alkylthio, arylthio, alkoxycarbonyiamino, sulfonamido, carbamyl, mono- or di-alkylcarbamylsulfamyl, sulfonyl, alkoxycarbonyl, azooxy or di-alkylcarbamyloxy, silyl, silyloxy, aryloxycarbonylamino, imido, sulfinyl, phosphonyl, aryloxycarbonyl, acyl or mercapto;

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 can 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 cycles 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 n 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 relative 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) when Ri and R ₂ have the meanings defined in point v), the groups R1 and R2 form a heterocycle different from piperazines and diazacycloheptanes.

- And at least one second oxidation base chosen from heterocyclic oxidation bases, double bases, paraaminophenols substituted, orthoaminophenols, paraphenylenediamine derivatives of formula (II) below, and their addition salts with an acid:

in which :

- R ₅ represents a hydrogen atom, an alkyl radical in CrC, monohydroxyalkyle in CC, polyhydroxyalkyle in C ₂ -C ₄ , alkoxy (d- C) alkyl (Cι-C ₄ ), alkyl in dC substituted by a nitrogen group , phenyl or 4'-aminophenyl; - Re represents a hydrogen atom, an alkyl radical in Cι-C ₄ , monohydroxyalkyle in CrC ₄ , polyhydroxyalkyle in C ₂ -C ₄ , alkoxy (Cr C ₄ ) alkyl (CC) or alkyl in Cι-C ₄ substituted by a nitrogen group;

- R ₇ represents a hydrogen atom, a halogen atom such as a chlorine, bromine, iodine or fluorine atom, a C1-C4 alkyl radical, C ₁ -C ₄ monohydroxyalkyl, hydroxyalkoxy in dC ₄ , acetylaminoalkoxy in Cι-C ₄ , mesylaminoalkoxy in C1-C4 or carbamoylaminoalkoxy in Cι-C ₄ ,

- Rβ represents a hydrogen atom, a halogen atom or a Cι-C alkyl radical;

it being understood that when R ₅ , Rβ and Rs simultaneously represent a hydrogen atom, then R ₇ denotes neither a hydrogen atom, nor a chlorine atom, nor a methyl radical.

The dye composition in accordance with the invention leads to coloring in various shades, chromatic, powerful, aesthetic, having a low selectivity and excellent resistance properties both with respect to atmospheric agents such as light and bad weather. and with regard to perspiration and the various treatments that the hair can undergo. According to a particular embodiment, the oxidation base is 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):

î) 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 Cr. ₂ θ) _p R ₄ in which p is an integer between 2 and 8 inclusive, R ₄ and R, identical or different, represent a hydrogen atom, a alkyl radical; v) Ri and R ₂ together with ^the nitrogen atom to which they are attached a saturated 5, 6 or 7 membered ring, said heterocycle being substituted with 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 0, 1 or 2;

According to one embodiment of the invention, the groups R1 and R2 form a heterocycle comprising a single heteroatom, nitrogen, for example a pyrolidinic 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 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-propyloxy paraphenylenediamine, 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 paraphenylened iamine, 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, la 1-N, N-bis- (3 ', 4'-dihydroxybutyl) -3-n.octylthio paraphenylenediamine, 1 -N, N-bis- (3', 4'-dihydroxybutyl) -3-mercaptoethyl paraphenylenediamine, la 1-N, N-bis- (3 ', 4'-dihydroxybutyl) -3-mercaptoethyl thioparaphenylenediamine, la 1-N, N-bis- (3', 4'-dihydroxybutyl) -3- -hydrox yethyl thioparaphenylenediamine, la 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 paraph nylenediamine, 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, 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, 1-N- (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- 7-amino-1-methylindole, 1-N- (hydroxyethyloxyethyl ) -1-N- (2 ', 3', 4 ', 5', 6'-penta- hydroxyhexyl) -3-ethyl paraphenylenediamine, and their additive salts n with an acid.

Preferably, the oxidation base is 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) -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-para-phenylenediamine, 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-aminoindoiine, 6-methyl-2-hydroxyethyl-5-aminoindoline, 2-hydroxyethyloxyethyl-5-aminoindoline, 2-hydroxyethyloxyethyloxyethyloxy- ethyl-5-aminoindoline, 2-hydroxyethyloxyethyloxyethyloxyethyloxy-ethyloxyethyl-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'-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-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 - (hydrox yethyloxyethyloxyethyloxyethyl) -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- (hydroxyethyloxy-ethyloxyethyloxyethyl)) - 2,2,3,7-tetramethyl-1, 2,3,4-tetrahydroquinoline,

1- (carboxymethyl) -2,2,3,7-tetramethyl-1,2,3,4-tetrahydro-quinoline, the

1 - (hydroxypropyl) -2,2,3-trimethyl-7-methoxy-1,2,3,4-tetrahydro-quinoline, 6-amino-1- (hydroxyethyloxyethyloxyethyl) -2,2,3-trimethyl-7 -isopropyl-1,2,3,4-tetrahydroquinoin, 6-amino-1- (hydroxyethyloxyethyloxyethyloxyethyloxy-ethyloxyethyloxyethyloxyethyl) -2,2,3-trimethyl-7-isopropyl-1,2,3,4-tetrahydroquinoline, 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-quinoin, 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-ethyloxyeth yloxyethyloxyethyloxyethyloxyethyloxyethyloxyethyl) -2,2-dimethyl-4-hydroxymethyl-7-isopropyl-1, 2,3,4-tetrahydroquinoin, 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- (hydroxy-ethyloxyethyloxyethyloxyethyloxyethyloxyethyl) -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-tetra-hydroquinoline, 6-amino-1 - (hydroxyethyloxyethyloxyethyloxyethyl) -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- (hydroxyethylethyloxyethyloxyethyloxyethyl) -4- (hydroxyethyloxyethyioxyethyloxyethyl) -2,2,7- trimethyl-1 , 2,3,4-tetrahydro-quinoline, 6-amino-1- (hydroxyethyloxyethyloxy-ethyloxyethyl) -2,2-dimethyl-7-isopropyl-1, 2,3,4-tetra-hydroquinoline, 6-amino - 1- (2 ', 3', 4 ', 5', 6 ' -pentahydroxy-hexyl) -2,2,4-trimethyl-7-isopropyl-1,2,3,4-tetra-hydroquinoline, 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, acid

6-amino-2,2-dimethyl-7-chloro-1,2,3,4-tetrahydroquinoline-1-propyisulfonique, la 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 salts of 'addition with an acid.

Mention may also be made most 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 acid 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 ' -isopropyl-oxyphenyl) -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 '" - 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- (hydroxyethyloxyé thyloxyethyl) -3- isopropyl paraphenylenediamine, 1-N-methyl-1-N- (hydroxyethyloxyethyloxyethyl) paraphenylene diamine, 1-N-phenyl-1-N- (hydroxyethyloxyethyl) paraphenylenediamine, 1-N-benzyl -1-N- (hydroxyethyloxyethyloxyethyloxyethylethylethyl) -3-trimethylsilyl paraphenylenediamine, 1-N-methyl-1-N- (hydroxyethyloxyethyloxyethyloxyethyloxyethyloxyethyloxyethyloxyethyl) -3- trimethylsilyloxy paraphenylenediamine, 1-N-ethyl-1-Noxy ethyloxyethyloxyethyloxyethyl) -3-phenoxycarbonylamino paraphenylenediamine, 1-N-methyl-1-N- (methoxyethyloxyethyloxyethyl) -3- (2 ', 5'- dioxopyrrolidinyl) paraphenylene diamine, 1-N-ethyl-1-N- ( hydroxyethyloxy- ethyloxyethyl) -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- (hydroxyethyloxyethyloxy thyloxyethyl) paraphenylenediamine, 1-N, N-bis- (methoxyethyloxyethyloxyethyloxyethyl) -3-isopropyloxy paraphenylenediamine, 1-N, N-bis- (hydroxyethyloxyethyloxyethyl) -3-isopropyloxy paraphenylenediamine, 1-N, N-bis- ( hydroxyethyloxyethyloxyethyloxyethyl) -3- isopropyl paraphenylene diamine, 1-N, N-bis- (hydroxyethyloxyethyloxy- ethyloxyethyl) -3-isopropyl paraphenylenediamine, 1-N, N-bis- (methoxy-ethyioxyethyloxyethyloxyethyloxyethyloxyethyloxyethyl) -3-methoxyaphine 1 -N, N-bis- (hydroxyethyloxyethyloxyethyloxyethyloxy- ethyloxyethyloxyethyloxyethyl) -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.

Preferably, the oxidation base is 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'-aminophényi) -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-NN-bis- (hydroxyethyloxy-ethyloxyethyloxyethyl) paraphenylenediamine, 1-N, N-bis- (hydroxyethyloxyethyioxyethyloxyethyl) -3-isopropyl paraphenylene diamine, 1- NN-bis- (hydroxyethyloxyethyloxyethyloxyethyl) -3-isopropyl paraphenylenediamine, 1-N, N-bis-

(hydroxyethyloxyethyloxyethyloxyethyloxyethyloxyethyloxyethyloxyethyl) -3-methyl paraphenylenediamine, 1-N, N-bis- (benzyloxyethyloxy-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 according to the invention preferably represent from 0.0001 to 20% by weight approximately, more preferably from 0.001 to 15% weight and even more preferably from 0.01 to 10% by weight relative to the total weight of the composition.

Among the paraphenylenediamines of formula (II) which can be used as a second oxidation base in the dye composition according to the invention, it is possible to more particularly mention 2,3-dimethyl paraphenylenediamine, 2,6-dimethyl paraphenylenediamine, 2,6-diethyl paraphenylenediamine, 2,5-dimethyl paraphenylenediamine, N, N-dimethyl paraphenylenediamine, N, N-diethyl paraphenylenediamine , N, N-dipropyl paraphenylenediamine, 4-amino N, N-diethyl 3-methyl aniline, N, N-bis- (β-hydroxyethyl) paraphenylenediamine, 4-N, N-bis- (β-hydroxyethyl ) amino 2-methyl aniline, 4-N, N-bis- (β-hydroxyethyl) amino 2-chloro aniline,

2-β-hydroxyethyl paraphenylenediamine, 2-fluoro paraphenylenediamine, 2-isopropyl paraphenylenediamine, N- (β-hydroxypropyl) paraphenylenediamine, 2-hydroxymethyl paraphenylenediamine, N, N-dimethyl 3-methyl paraphenylenediamine - (ethyl, β-hydroxyethyl) paraphenylenediamine, N- (β, γ-dihydroxypropyl) paraphenylenediamine, N- (4'-aminophenyl) paraphenylenediamine, N-phenyl paraphenylenediamine, 2-β-hydroxyethyloxy paraphenylenediamine β-acetylaminoethyloxy paraphenylenediamine, N- (β-methoxyethyl) paraphenylenediamine, and their addition salts with an acid.

Among the paraphenylenediamines of formula (II) above, very particularly preferred is 2-isopropyl paraphenylenediamine, 2-β-hydroxyethyl paraphenylenediamine, 2-β-hydroxyethyloxy paraphenylenediamine, 2,6-dimethyl paraphenylenediamine, 2,6 -diethyl paraphenylenediamine, 2,3-dimethyl paraphenylenediamine, N, N-bis- (β-hydroxyethyl) paraphenylenediamine, 2-β-acetylaminoethyloxy paraphenylenediamine, and their addition salts with an acid.

Even more preferably, among the paraphenylenediamines of formula (II) above, 2-β-hydroxyethyl paraphenylenediamine, N, N-bis- (β-hydroxyethyl) paraphenylenediamine and their addition salts with an acid are preferred.

According to the invention, the term “double bases” is intended to mean compounds comprising at least two aromatic rings on which are carried amino and / or hydroxyl groups. Among the double bases which can be used as second oxidation base in the dye composition in accordance with the invention, mention may in particular be made of the compounds of formula (III) below, and their addition salts with an acid:

in which :

- Zi and Z ₂ , identical or different, represent a hydroxyl radical or -NH _{2 which} can be substituted by an alkyl radical in CC or by a linking arm

Y; - the link arm Y represents an alkylene chain comprising from 1 to 14 carbon atoms, linear or branched which can be interrupted or terminated by one or more nitrogen groups and / or by one or more heteroatoms such as oxygen atoms, sulfur or nitrogen, and optionally substituted with one or more Cι-C ₆ hydroxyl or alkoxy radicals;

- R ₉ and Rio represent a hydrogen or halogen atom, an alkyl radical in Cι-C ₄ , monohydroxyalkyl in CrC, polyhydroxyalkyl in C ₂ -C, aminoalkyl in dC ₄ or a link arm Y;

- R11, R12, R-I3, Ru, R15 and Rι ₆ , identical or different, represent a hydrogen atom, a connecting arm Y or a Cι-C alkyl radical;

it being understood that the compounds of formula (III) have only one linker arm Y per molecule.

Among the nitrogen groups of formula (III) above, there may be mentioned in particular the amino, monoalkyl (Cι-C) amino, dialkyl (Cι-C) amino, trialkyl (Cι-C ₄ ) amino, monohydroxyalkyl (Cι) radicals -C ₄ ) amino, imidazolinium and ammonium. Among the double bases of formula (III) above, there may be more particularly mentioned N, N'-bis- (β-hydroxyethyl) N, N'-bis- (4'-aminophenyl) 1, 3-diamino propanol , N, N'-bis- (β-hydroxyethyl) N, N'-bis- (4'-aminophenyl) ethylenediamine, N, N'-bis- (4-aminophenyl) tetramethylenediamine, N, N'- bis- (β-hydroxyethyl) N, N'-bis- (4-aminophenyl) tetramethylenediamine, N, N'-bis- (4-methyl-aminophenyl) tetramethylenediamine, N, N'-bis- (ethyl) N , N'-bis- (4'-amino, 3'-methylphenyl) ethylenediamine, 1, 8-bis- (2,5-diaminophenoxy) -3,5-dioxaoctane, and their addition salts with an acid.

Among these double bases of formula (III), N, N'-bis- (β-hydroxyethyl) N, N'-bis- (4'-aminophenyl) 1, 3-diamino propanol, 1, 8-bis- (2,5-diaminophenoxy) -3,5-dioxaoctane or one of their addition salts with an acid are particularly preferred.

Among the substituted para-aminophenols which can be used as a second oxidation base in the dye composition in accordance with the invention, mention may in particular be made of the compounds of formula (IV) below, and their addition salts with an acid:

OH

R 17

(Iv)

R 18

NH ₂ in which:

- Rι ₇ represents a hydrogen or halogen atom, an alkyl radical in CC ₄ , monohydroxyalkyl in C1-C4, alkoxy (C ₁ -C ₄ ) alkyl (C ₁ -C), aminoalkyl in CC ₄ or hydroxyalkyl ( CrC ₄ ) C1-C4 aminoalkyl,

- Ris represents a hydrogen or halogen atom, an alkyl radical DC monohydroxyalkyl, C ₁ -C ₄ polyhydroxyalkyl, C ₂ -C ₄ aminoalkyl, C 1 -C ₄ cyanoalkyl or alkoxy CC (Cι- C ₄ ) alkyl (Cι-C ₄ ), it being understood that at least one of the radicals R17 or Rι ₈ is different from a hydrogen atom. Among the para-aminophenols of formula (IV) above, mention may more particularly be made of para-aminophenol, 4-amino 3-methyl phenol, 4-amino 3-fluoro phenol, 4-amino 3-hydroxymethyl phenol , 4-amino 2-methyl phenol, 4-amino 2-hydroxymethyl phenol, 4-amino 2-methoxymethyl phenol, 4-amino 2-aminomethyl phenol, 4-amino 2- (β-hydroxyethyl aminomethyl) phenol , 4-amino 2-fluoro phenol, and their acid addition salts.

Among the orthoaminophenols which can be used as oxidation bases in the dye compositions in accordance with the invention, mention may more particularly be made of 2-amino phenol, 2-amino 5-methyl phenol, 2-amino 6-methyl phenol, 5-acetamido 2-amino phenol, and their addition salts with an acid.

Among the heterocyclic bases which can be used as oxidation bases in the dye compositions in accordance with the invention, mention may more particularly be made of pyridine derivatives, pyrimidine derivatives, pyrazole derivatives, and their addition salts with an acid.

Among the pyridine derivatives, mention may more particularly be made of the compounds described, for example, in patents GB 1 026 978 and GB 1 153 196, such as 2,5-diamino pyridine, 2- (4-methoxyphenyl) amino 3-amino pyridine , 2,3-diamino 6-methoxy pyridine, 2- (β-methoxyethyl) amino 3-amino 6-methoxy pyridine, 3,4-diamino pyridine, and their addition salts with an acid.

Among the pyrimidine derivatives, mention may more particularly be made of the compounds described for example in patents DE 2,359,399; JP 88-169,571; JP 05 163 124; EP 0 770 375 or patent application WO 96/15765 such as 2,4,5,6-tetra-aminopyrimidine, 4-hydroxy 2,5,6-triaminopyrimidine, 2-hydroxy 4,5,6-triaminopyrimidine, 6-hydroxy 2,4,5-triaminopyrimidine, 2,4-dihydroxy 5,6-diaminopyrimidine, 2,5,6-triaminopyrimidine, and pyrazolo-pyrimidine derivatives such as those mentioned in the patent application FR-A-2 750 048 and among which mention may be made of pyrazolo- [1,5-a] -pyrimidine-3,7-diamine; 2,5-dimethyl pyrazolo- [1,5-a] -pyrimidine-3,7-diamine; pyrazolo- [1,5-a] -pyrimidine-3,5-diamine; 2,7-dimethyl pyrazolo- [1,5-a] - pyrimidine-3,5-diamine; 3-amino pyrazolo- [1,5-a] -pyrimidin-7-ol; 3-amino pyrazolo- [1,5-a] -pyrimidin-5-ol; 2- (3-amino pyrazolo- [1,5-a] -pyrimidin-7-ylamino) -ethanol, 2- (7-amino pyrazolo- [1,5-a] -pyrimidin-3-ylamino) - ethanol, 2 - [(3-amino-pyrazolo [1, 5-a] pyrimidin-7-yl) - (2-hydroxy-ethyl) -amino] -ethanol, 2 - [(7-amino-pyrazolo [ 1, 5-a] pyrimidin-3-yl) - (2-hydroxy-ethyl) -amino] -ethanol, 5,6-dimethyl pyrazolo- [1,5-a] -pyrimidine-3,7-diamine, 2,6-dimethyl pyrazolo- [1,5-a] -pyrimidine-3,7-diamine, 2,5,5 N 7, N 7-tetramethyl pyrazolo- [1,5-a] - pyrimidine-3, 7-diamine, 3-amino-5-methyl-7-imidazolylpropylamino pyrazolo- [1,5-a] -pyrimidine, their addition salts with an acid, and their tautomeric forms, when there is a tautomeric equilibrium.

Among the pyrazole derivatives, mention may more particularly be made of the compounds described in patents DE 3 843 892, DE 4 133 957 and patent applications WO 94/08969, WO 94/08970, FR-A-2 733 749 and DE 195 43 988 such as 4,5-diamino 1-methyl pyrazole, 3,4-diamino pyrazole, 4,5-diamino 1- (4'-chlorobenzyl) pyrazole, 4,5-diamino 1, 3-dimethyl pyrazole, 4,5-diamino 1 - (β-hydroxyethyl) pyrazole, 4,5-diamino 3-methyl 1-phenyl pyrazole, 4,5-diamino 1-methyl 3-phenyl pyrazole, 4-amino 1, 3 -dimethyl 5-hydrazino pyrazole, 1-benzyl 4,5-diamino 3-methyl pyrazole, 4,5-diamino 3-tert-butyl 1-methyl pyrazole, 4,5-diamino 1-tert-butyl 3- methyl pyrazole, 4,5-diamino l- (β-hydroxyethyl) 3-methyl pyrazole, 4,5-diamino 1 -ethyl 3-methyl pyrazole, 4,5-diamino 1 -ethyl 3- (4'- methoxyphenyl) pyrazole, 4,5-diamino 1 -ethyl 3-hydroxymethyl pyrazole, 4,5-diamino 3-hydroxymethyl 1-methyl pyrazole, 4,5-diamino 3-hydroxymethyl 1 -isopropyl pyrazole, 4,5-diamino 3-methyl 1 -isopropyl pyrazole, 4-amino 5- (2'-aminoethyl) amino 1, 3-dimethyl pyrazole, 3,4,5-triamino pyrazole, 1-methyl 3,4,5-triamino pyrazole, 3,5-diamino 1-methyl 4-methylamino pyrazole, 3,5-diamino 4- (β-hydroxyethyl) amino 1-methyl pyrazole, and their addition salts with a acid. The oxidation base (s) used as second oxidation base preferably represent from 0.0005 to 12% by weight approximately of the total weight of the dye composition, and even more preferably from 0.005 to 6% by weight approximately this weight.

According to a preferred embodiment of the invention, the dye composition contains at least one coupler.

These couplers can in particular be chosen from metaphenylenediamines, meta-aminophenols, metadiphenols and heterocyclic couplers such as, for example, indole derivatives, indoline derivatives, benzimidazole derivatives, benzomorpholine derivatives, sesamol derivatives, derivatives pyridinics, pyrimidinics and pyrazolics, and their acid addition salts.

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

When they are present, the coupler (s) preferably represent from 0.0001 to 15% by weight approximately relative to the total weight of the composition.

The dye composition according to the invention may, in addition, contain one or more additional oxidation bases different from the oxidation bases described above and / or one or more direct dyes. Among the additional oxidation bases which can be used according to the invention, mention may be made of paraphenylenediamines other than those of formula (I) and (II) defined above, such as for example paraphenylenediamine, paratoluylenediamine, 2-chloro paraphenylenediamine, and paraaminophenols other than those of formula (IV) defined above, such as 4-amino phenol, and their addition salts with an acid.

When they are present, the additional oxidation base (s) preferably represent from 0.0001 to 15% by weight approximately relative to the total weight of the composition.

In general, the addition salts with an acid which can be used in the context of the dye compositions of the invention are in particular chosen from hydrochlorides, hydrobromides, sulfates, tartrates, lactates and acetates.

The medium suitable for dyeing (or support) generally consists of water or a mixture of water and at least one organic solvent to dissolve the compounds which are not sufficiently soluble in water. Mention may be made, as organic solvent, of lower CrC ₄ alkanols, such as ethanol and isopropanol; glycerol, glycols and glycol ethers such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, monoethyl ether and monomethyl ether of diethylene glycol, as well as aromatic alcohols such as benzyl alcohol or phenoxyethanol, analogues and their mixtures.

The solvents may be present in proportions preferably of between 1 and 40% by weight approximately relative to the total weight of the dye composition, and even more preferably between 5 and 30% by weight approximately.

The pH of the dye composition according to the invention is generally between 3 and 12. It can be adjusted to the desired value using agents acidifying or basifying agents usually used in dyeing keratin fibers.

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

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

in which R is a propylene residue optionally substituted by a hydroxyl group or a Cι-C ₄ alkyl radical; R19, R ₂ o. R 21 and R _22, identical or different, represent a hydrogen atom, an alkyl radical in C1-C4 or hydroxyalkyl, C1-C4.

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 may also contain various adjuvants conventionally used in compositions for dyeing the hair, such as anionic, cationic, nonionic, amphoteric, zwitterionic surfactants or mixtures thereof, anionic polymers, cationic, non-ionic, amphoteric, zwitterionic or mixtures thereof, mineral or organic thickening agents, agents reducing agents or antioxidants, penetration agents, sequestering agents, perfumes, buffers, dispersing agents, conditioning agents such as for example silicones, film-forming agents, preserving agents, opacifying agents, silicone UV filters or not silicones, vitamins or provitamins.

The reducing or antioxidant agents 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 which can vary between 0.05 and 1.5% by weight approximately relative to the total weight of the composition.

Preferably, the dye composition in accordance with the invention contains at least one nonionic surfactant in a proportion preferably varying between 0.1 and 20% by weight approximately relative to the total weight of the composition, and at least a cationic or amphoteric substantive polymer in a proportion preferably varying between 0.05 and 10% by weight relative to the total weight of the composition.

Preferably, the dye composition in accordance with the invention contains at least one thickening polymer comprising at least one hydrophilic unit and at least one fatty chain in a proportion preferably varying between 0.05 and 10% by weight relative to the total weight of the composition.

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 dye composition according to the invention are not, or not substantially, altered. by the addition (s) envisaged.

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

Another subject of the invention is a process for the oxidation dyeing of keratin fibers and in particular human keratin fibers such as the hair, using the dye composition as defined above.

According to this process, at least one dye composition as defined above is applied to the fibers, the color being revealed at acidic, neutral or alkaline pH using an oxidizing agent which is added just at the time of use. the dye composition or which is present in an oxidizing composition applied simultaneously or sequentially separately.

According to a particularly preferred embodiment of the dyeing method according to the invention, the dye composition as defined above is mixed, at the time of use, with an oxidizing composition containing, in a medium suitable for dyeing. , at least one oxidizing agent present in an amount sufficient to develop a coloration. The mixture obtained is then applied to the keratin fibers and left to stand for 3 to 50 minutes approximately, preferably 5 to 30 minutes approximately, after which it is rinsed, washed with shampoo, rinsed again and dried.

The oxidizing agent can be chosen from the oxidizing agents conventionally used for the oxidation dyeing of keratin fibers, and among which mention may be made of hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as as perborates and persulfates, and oxidative enzymes such as peroxidases, laccases, tyrosynases and oxidoreductases among which there may be mentioned in particular pyranose oxidases, glucose oxidases, glycerol oxidases, lactate oxidases, pyruvate oxidases, and uricases, said enzymes being optionally associated with their respective donors. The pH of the oxidizing composition containing the oxidizing agent as defined above is such that after mixing with the dye composition, the pH of the resulting composition applied to the keratin fibers preferably varies between 3 and 12 approximately and even more preferably between 5 and 11. It is adjusted to the desired value by means of acidifying or basifying agents usually used in dyeing keratin fibers and as defined above.

The oxidizing composition as defined above may also contain various adjuvants conventionally used in compositions for dyeing the hair and as defined above.

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

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

The following examples are intended to illustrate the invention. EXAMPLES 1 TO 5 OF DYEING

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

(*) Common dye support:

Alkyl Cβ-Cio polyglucoside in 60% aqueous solution, sold under the name ORAMIX CG 110 ® by the company SEPPIC 5.4 g

Ethanol 18.0 g

Benzyl 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 AKZO 1.08 g

Sodium metabisulfite 0.205 g

20.5% NH ₃ ammonia 10.0 g

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 the following shades

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:

at least one first 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) 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, aryl radical or a heterocycle; or iii) Rι represents an alkyl or aryl radical or a heterocycle 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; iv) Rι represents a radical - (CH ₂ CH ₂ O) _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, 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, nitrogen, oxygen, sulfur;

- R ₃ represents a halogen atom, an alkyl or aryl radical, a heterocycle, a heterocycle linked to the benzene ring of formula (I) by an ether or thio bond, a cyano, nitro, hydroxyl, carboxyl, sulfo radical, alkoxy, aryloxy, cyanoamino, amino, anilino, ureido, sulfamylamino, mono- or di-alkylsulfamylamino, alkylthio, arylthio, alkoxycarbonylamino, sulfonamido, carbamyl, mono- or di-alkylcarbamylsulfamyl, sulfonyl, alkoxycarbonoxy, carboxyoxy or di-alkylcarbamyloxy, silyl, silyloxy, aryloxycarbonylamino, imido, sulfinyl, phosphonyl, aryloxycarbonyl, acyl or mercapto;

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, trifiuoroalkyle, 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 can 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 cycles 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 n 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 relative 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) when Ri and R ₂ have the meanings defined in point v), the groups R1 and R2 form a heterocycle different from piperazines and diazacycloheptanes.

- And at least one second oxidation base chosen from heterocyclic oxidation bases, double bases, substituted paraaminophenols, orthoaminophenols, paraphenylenediamine derivatives of formula (II) below, and their addition salts with an acid :

in which :

- R ₅ represents a hydrogen atom, an alkyl radical in dC, monohydroxyalkyle in CC, polyhydroxyalkyle in C ₂ -C ₄ , alkoxy (Cι-

C _4. alkyl (Cι-C ₄ ), dC alkyl substituted by a nitrogen group, phenyl or 4'-aminophenyl;

- Rβ represents a hydrogen atom, a C1-C4 alkyl, monohydroxyalkyl in CC ₄ , polyhydroxyalkyl in C ₂ -C ₄ , alkoxy (d- C ₄ ) alkyl (Cι-C ₄ ) or alkyl in C1-C4 substituted by a nitrogen group;

- R ₇ represents a hydrogen atom, a halogen atom such as a chlorine, bromine, iodine or fluorine atom, a C1-C4 alkyl radical, C ₁ -C ₄ monohydroxyalkyl, hydroxyalkoxy in Cι-C ₄ , acetylaminoalkoxy in C1-C4, mesylaminoalkoxy in C1-C4 or carbamoylaminoalkoxy in C-1-C4, - Rs represents a hydrogen atom, halogen or an alkyl radical in it being understood that when R5, Rβ and Rs simultaneously represent a hydrogen atom, then R ₇ denotes neither a hydrogen atom, nor a chlorine atom, nor a methyl radical.

2. Composition according to Claim 1, in which the oxidation base is 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 ) ₂ CHOHCH ₂ OH; or ii) Ri represents a radical -CH2 (CHOH) ₄ CH ₂ OH and R ₂ represents a hydrogen atom, an alkyl radical; or iv) Rι represents a radical - (CH ₂ CH2θ) pR ₄ in which p is an integer between 2 and 8 inclusive, R ₄ 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 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 the substituted derivatives 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-propyloxy paraphenylenediamine, 1-N, N-bis - (3 ', 4'-dihydroxybutyl) -3-hexyloxy paraphenylene- diamine, 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'-dihydro xybutyl) -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- -hyd roxyethylthioparaphenylenediamine, 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, 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-7-amino- 1-methylindole, 1-N- (hydroxyethylethyloxyethyl) -1-N- (2 ', 3', 4 ', 5', 6'-pentahydroxyhexyi) -3-ethyl paraphenylenediamine, 1-N- (3 ', 4'-dihydroxybutyl) -5-aminoindoline, 1- (2'-hydroxyethyl) - 2methyl-5-aminoindoline, 1-me thyl-2-hydroxymethyl-5-aminoindoline, 6-methyl-2-hydroxyethyl-5-aminoindoline, 2-hydroxyethyloxyethyl-5-aminoindoline, 2-hydroxyethyloxyethyloxyethyloxy-ethyl-5-aminoindoline, 2-hydroxyethyloxy-ethyloxyethyloxyethyloxyethyloxyethyl- 6-isopropyl-5-aminoindoline, 2-hydroxy-ethyl-3-methyl-5-aminoindoline, 2-hydroxyethylo-xyethyloxyethyl) -5-amino indoline, 1-carboxymethyl-2,3,3-trimethyl -5- aminoindoline, 1-methyl-sulfonamidoethyl-3-methyl-5-aminoindoline, 1-ureaidoethyl-6-methoxy-5-amino indoline, 1- (2 ', 3', 4 ', 5', 6'-pentahydroxy-hexyl) - 5-aminoindoline, 1-N- (2'-mercaptoethyl) -5-amino indoline, dimethyl ester 6-amino-1-methyl-1, 2,3,4-tetrahydro- furo- [2,3, h] -quinoline 4-phosphoric acid methylester, 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- tetrahydroquinoin, 6-amino-1- (3 ', 4'-dihydroxybutyl) -2,2,3 -trim thyl-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- tetrahydroquinoin, 6-amino-1- (ethyl-bis- (hydroxy-ethyloxyethyloxy-ethyloxyethyl)) - 2,2,3,7-tetramethyl-1,2,3,4- tetrahydroquinoline, 1- (carboxy-methyl) -2,2,3,7-tetramethyl-1,2,3,4-tetrahydro-quinoline, 1- (hydroxypropyl) - 2,2,3-trimethyl-7- 1, 2,3,4-tetrahydro-quinoline, 6-amino-1- (hydroxy- ethyloxyethyloxyethyl) -2,2,3-trimethyl-7-isopropyl-1,2,3,4-tetrahydro-quinoline, 6-amino-1- (hydroxyethyloxyethyloxyethyloxyethyloxyethyloxyethyloxyethyloxyethyl) -2,2,3-trimethyl-7- isopropyl-1,2,3,4-tetra-hydroquinoline, 6-amino-1- (hydroxyethyloxyethyloxyethyloxyethyloxyethyloxyethyloxyethyloxy-ethyl) -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-tetrahydro-quinoline, 6-amino-1- (3-hydroxypropyl) - 2,2-dimethyl-4-hydroxymethyl-7-isopropyl-1,2,3,4-tetrahydroquinoline, 6-amino-1 - (hydroxy-ethyloxyethyloxyethyloxyethyloxyethyloxy-ethyloxyethyloxyethyl) -2,2-dimethyl-4-hydroxymethyl -7-isoprop yl-1,2,3,4-tetra-hydroquinoline, 6-amino-1 - (hydroxyethyloxyethyloxy-ethyloxyethyl) -2,2-dimethyl-4-hydroxymethyl-7isopropyl-1, 2,3,4-tetrahydro-quinoline , 6-amino-1- (hydroxyethyloxyethyloxyethyloxyethyloxyethyl) -2,2-dimethyl-7-isopropyl-1, 2,3,4-tetrahydroquinoline, 6-amino-1 - (hydroxyethyloxyethyloxyethyloxyethyloxy-ethyloxyethyl) -2,2-dimethyl -7-isopropyl-1,2,3,4-tetra-hydroquinoline, 6-amino-1- (hydroxyethyloxyethyl) -2,2-dimethyl-1,2,3,4-tetra-hydroquinoline, 6-amino - 1,2,2,4,7-pentamethyl-3-hydroxy-1,2,3,4-tetra-hydroquinoline, 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-hydro- quinoline, 6-amino-1- (3 ', 4'- dihydroxybutyl) -2,2-dimethyl-7-isopropyl-1, 2,3,4-tetrahydroquinoline, 6-amino- 1- (hydroxyethyloxyethyloxyethyloxyethyl) - 4- (hydroxyethyl loxyethyloxyethyloxyethyl) -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-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-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, 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'-am inophenyl) -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-mercapto-ethyloxyethyl 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) paraphenylenediamine, 1-N-phenyl-1-N- (hydroxyethyloxyethyl) paraphenylenediamine, 1-N-benzyl-1-N- (hydroxyethyloxyethylyioxyethyloxyethyloxyethyl) -3- trimethylsilyl paraphenylenediamine, 1-N-methyl-1-N- (hydroxy-ethyloxyethyloxyethyloxyethyloxyethyloxyethyloxyethyloxyethyl) -3-trimethylsilyloxy paraphenylenediamine, 1-N-ethyl-1-N- (methoxyethyloxyethyloxyethyloxy-ethyloxyethyl) -3-phenoxycarbonyleniamine -methyl-1- N- (methoxyethyloxyethyloxyethyl) -3- (2 ', 5'-dioxopyrrolidinyl) paraphenylene- diamine, 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- (hydroxyethyloxyethyloxyethyl) -3-isopropyloxy paraphenylenediamine, 1-N, N-bis- (hydroxyethyloxyethyloxyethyloxyethyl) -3-isopropyl paraphenylenediamine, 1-N, N-bis- (hydroxyethyloxyethyloxyethyloxyethyl) -3 -isopropyl para-phenylenediamine, 1-N, N-bis- (methoxyethyloxyethyloxyethyloxyethyloxy-ethyloxyethyloxyethyl) -3-methoxy paraphenylenediamine, 1-N, N-bis- (hydroxy-ethyloxyethyloxyethyloxyethyloxyethyloxyethyloxyethyloxyethyl) -3-methyl paraphenylenediamine , N-bis- (hydroxy ethyloxyethyloxyethyloxyethyl) -3- isopropyloxy paraphenylenediamine, 1-N, N-bis- (hydroxyethyloxyethyl) -3- mercaptoethyl paraphenylenediamine, 1-N, N-bis- (benzyloxyethyloxy-ethyloxyethyl) -3-isopropyl paraphenylenediamine, and their salts 'addition with an acid.

4. Composition according to any one of the preceding claims, in which the oxidation base is 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-para-phenylenediamine, 1-N- (2 ', 3', 4 ', ^5', 6'-pentahydroxyhexyl) -3-isopropyl para-phenylenediamine, 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.

5. Composition according to any one of claims 1 to 3 in which the oxidation base is 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-1 -N- (hydroxyethyloxyethyloxy-ethyl) paraphenylene diamine, 1-N, N-bis- (hydroxyethyl loxy-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- (benzyloxyethyloxy-ethyloxyethyl) - 3-isopropyl paraphenylenediamines addition with an acid.

6. Composition according to any one of the preceding claims, characterized in that the paraphenylenediamine derivative (s) of formula (I) represent from 0.0001 to 20% by weight of the total weight of the composition.

7. Composition according to claim 1 or 2, characterized in that the groups R1 and R2 form a pyrrolidine heterocycle.

8. Composition according to any one of the preceding claims, characterized in that the paraphenylenediamines of formula (II) are chosen from 2,3-dimethyl paraphenylenediamine, 2,6-dimethyl paraphenylenediamine, 2,6-diethyl paraphenylenediamine , 2,5-dimethyl paraphenylenediamine, N, N-dimethyl paraphenylenediamine, N, N-diethyl paraphenylenediamine, N, N-dipropyl paraphenylenediamine, 4-amino N, N-diethyl 3-methyl aniline, N, N-bis- (β- hydroxyethyl) paraphenylenediamine, 4-N, N-bis- (β-hydroxyethyl) amino 2-methyl aniline, 4-N, N-bis- (β-hydroxyethyl) amino 2-chloro aniline, 2-β -hydroxyethyl paraphenylene diamine, 2-fluoro paraphenylenediamine, 2-isopropyl paraphenylenediamine, N- (β-hydroxypropyl) paraphenylenediamine, 2-hydroxymethyl paraphenylenediamine, N, N-dimethyl 3-methyl paraphenylenediamine, (ethyl, β-hydroxyethyl) paraphenylenediamine, N- (β, γ-dihydroxypropyl) paraphenylenediamine, N- (4'-aminophenyl) paraphenylenediamine, N-phenyl paraphenylenediamine, 2-β-hydroxyethyloxy paraphenylenediamine -acetylaminoethyloxy paraphenylenediamine, N- (β-methoxyethyl) paraphenylenediamine, and their addition salts with a acid.

9. Composition according to Claim 8, characterized in that the paraphenylenediamines of formula (II) are chosen from 2-isopropyl paraphenylenediamine, 2-β-hydroxyethyl paraphenylenediamine, 2-β-hydroxyethyloxy paraphenylenediamine, 2,6- dimethyl paraphenylenediamine, 2,6-diethyl paraphenylenediamine, 2,3-dimethyl paraphenylenediamine, N, N-bis- (β-hydroxyethyl) paraphenylenediamine, 2-β-acetylaminoethyloxy paraphenylenediamine, and their addition salts with an acid .

10. Composition according to Claim 9, characterized in that the paraphenylenediamines of formula (II) are chosen from 2-β-hydroxyethyl paraphenylenediamine, NN-bis- (β-hydroxyethyl) paraphenylenediamine, and their addition salts with an acid.

11. Composition according to any one of claims 1 to 7, characterized in that the double bases are chosen from the compounds of formula (III) below, and their addition salts with an acid:

in which :

- Zi and Z ₂ , identical or different, represent a hydroxyl radical or -NH _{2 which} can be substituted by a C1-C4 alkyl radical or by a linking arm

Y;

- the link arm Y represents an alkylene chain comprising from 1 to 14 carbon atoms, linear or branched which can be interrupted or terminated by one or more nitrogen groups and / or by one or more heteroatoms such as oxygen atoms, sulfur or nitrogen, and optionally substituted by one or more hydroxyl or alkoxy radicals

- R ₉ and R ₁₀ represent a hydrogen or halogen atom, an alkyl radical in CC ₄ , monohydroxyalkyl in CrC ₄ , polyhydroxyalkyl in C ₂ -C, aminoalkyl in C ₁ -C4 or a link arm Y;

- R11, R12, R13, Ru, R15 and R16, identical or different, represent a hydrogen atom, a link arm Y or a Cι-C alkyl radical;

12. Composition according to Claim 11, characterized in that the double bases of formula (III) are chosen from N, N'-bis- (β-hydroxyethyl) N, N'-bis- (4'-aminophenyl) 1, 3-diamino propanol, N, N'-bis- (β-hydroxyethyl) N, N'-bis- (4'-aminophenyl) ethylenediamine, N, N'-bis- (4-aminophenyl) tetramethylenediamine, N, N'-bis- (β-hydroxyethyl) N, N'-bis- (4-aminophenyl) tetramethylenediamine, N, N'-bis- (4-methyl-aminophenyl) tetramethylenediamine, N, N'- bis- (ethyl) N, N'-bis- (4'-amino, 3'-methylphenyl) ethylenediamine, 1,8-bis- (2,5-diaminophenoxy) -3,5-dioxaoctane, and their addition salts with an acid.

13. Composition according to any one of claims 1 to 7, characterized in that the substituted para-aminophenols are chosen from the compounds of formula (IV) below, and their addition salts with an acid:

OH

R 17

(IV)

R 18

NH ₂ wherein: - R ₁₇ represents a hydrogen or halogen atom, an alkyl radical in C1-C4 monohydroxyalkyl, C1-C4, alkoxy (Cι-C ₄₎ alkyl (Cι-C4) aminoalkyl in C ₁ -C ₄ or hydroxyalkyl (Cι-C ₄ ) C1-C4 aminoalkyl, - Ris represents a hydrogen or halogen atom, an alkyl radical in CC ₄ , monohydroxyalkyl in CC ₄ , polyhydroxyalkyl in C ₂ - C ₄ , Cι-C aminoalkyl, Cι-C ₄ cyanoalkyl or alkoxy (CrC ₄ ) alkyl (Cι-C4), it being understood that at least one of the radicals R17 or Ris is different from a hydrogen atom.

14. Composition according to claim 13, characterized in that the para-aminophenols of formula (IV) are chosen from para-aminophenol,

4-amino 3-methyl phenol, 4-amino 3-fluoro phenol, 4-amino 3-hydroxymethyl phenol, 4-amino 2-methyl phenol, 4-amino 2-hydroxymethyl phenol, 4-amino 2- methoxymethyl phenol, 4-amino 2-aminomethyl phenol, 4-amino 2- (β-hydroxyethyl aminomethyl) phenol, 4-amino 2-fluoro phenol, and their addition salts with an acid.

15. Composition according to any one of claims 1 to 7, characterized in that the orthoaminophenols are chosen from 2-amino phenol, 2-amino 5-methyl phenol, 2-amino 6-methyl phenol, 5 -acetamido 2-amino phenol, and their addition salts with an acid.

16. Composition according to any one of claims 1 to 7, characterized in that the heterocyclic bases are chosen from pyridine derivatives, pyrimidine derivatives, pyrazole derivatives, and their addition salts with an acid.

17. Composition according to any one of the preceding claims, characterized in that the oxidation base or bases used as second oxidation base represent from 0.0005 to 12% by weight of the total weight of the dye composition .

18. Composition according to Claim 17, characterized in that the oxidation base or bases used as second oxidation base represent from 0.005 to 6% by weight of the total weight of the dye composition.

19. Composition according to any one of the preceding claims, characterized in that it contains at least one coupler chosen from metaphenylenediamines, meta-aminophenols, metadiphenols and heterocyclic couplers, and their addition salts with an acid .

20. Composition according to Claim 19, characterized in that the couplers are chosen from 2-methyl 5-amino phenol, 5-N- (β-hydroxyethyl) amino 2-methyl phenol, 3-amino phenol, 1, 3-dihydroxy benzene, 1, 3-dihydroxy 2-methyl benzene, 4-chloro 1, 3-dihydroxy benzene, 2,4-diamino l- (β-hydroxyethyloxy) benzene, 2-amino 4- (β-hydroxyethylamino) 1-methoxy benzene, 1,3-diamino benzene, 1,3-bis- (2,4-diaminophenoxy) propane, sesamol, 1-amino 2-methoxy 4,5-methylenedioxy benzene , α-naphthol, 2-methyl-1-naphthol, 6-hydroxy indole, 4-hydroxy indole, 4-hydroxy N-methyl indole, 6-hydroxy indoline, 2,6-dihydroxy 4 -methyl pyridine, 1-H 3-methyl pyrazole 5-one, 1-phenyl 3-methyl pyrazole 5-one, and their addition salts with an acid.

21. Composition according to claim 19 or 20, characterized in that the coupler (s) represent from 0.0001 to 15% by weight relative to the total weight of the composition.

22. Composition according to any one of the preceding claims, characterized in that it contains one or more additional oxidation bases chosen from paraphenylenediamine, paratoluylenediamine, 2-chloro paraphenylenediamine, 4-amino phenol, and their addition salts with an acid.

23. 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.

24. Process for the oxidation dyeing of keratin fibers and in particular human keratin fibers such as the hair, characterized in that at least one dye composition as defined in any one of the claims is applied to said fibers 1 to 23, the color being revealed at acid, neutral or alkaline pH using an oxidizing agent which is added just at the time of use to the dye composition or which is present in an oxidizing composition applied simultaneously or sequentially separately.

25. The method of claim 24, characterized in that the oxidizing agent is chosen from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts and oxidizing enzymes.

26. Multi-compartment device, or “kit” for dyeing with several compartments, a first compartment of which contains a dye composition as defined in any one of claims 1 to 23 and a second compartment of which contains an oxidizing composition.