CA2373099A1 - Oxidation dyeing composition for keratinous fibres and dyeing method using same - Google Patents

Abstract

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

Description

WO 01/6607

2 PCT / FRO1 / 00663 KERATIN FIBER OXIDATION DYE COMPOSITION
AND DYEING METHOD USING THE SAME
COMPOSITION
The subject of the invention is a composition for the oxidation dyeing of fibers s keratin, 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 certain substituted derivatives of the paraphenylenediamine and their addition salts with an acid and at least one second selected oxidation base, as well as the dyeing process 1o using this composition.
It is known to dye keratin fibers and in particular the hair humans with dye compositions containing precursors of oxidation dye, in particular ortho or paraphenylenediamines, is ortho or paraaminophenols, heterocyclic bases, generally called oxidation bases. Oxidation dye precursors, or bases oxidation, are colorless or weakly colored compounds which, associated with oxidizing products, can give birth by a process of oxidative condensation with colored and coloring compounds.
We also know that we can vary the nuances obtained with these oxidation bases by associating them with couplers or modifiers of coloring, the latter being chosen in particular from metadiamines aromatics, metaaminophenols, metadiphenols and certain compounds 2s heterocyclic.
The variety of molecules involved in the oxidation bases and couplers, allows obtaining a rich palette of colors.
3o The so-called "permanent" coloration obtained using these oxidation dyes, must moreover satisfy a certain number of requirements. So, she must to permit to obtain nuances in the desired intensity and to show good hold facing external agents (light, bad weather, washing, rippling permanent, sweating, rubbing).
The dyes should also cover white hair, and Finally, be the least selective possible, that is to say allow to obtain deviations lowest possible coloring throughout a single fiber keratin, which can indeed be sensitized differently (ie damaged) between its tip and its root.
1o II has already been proposed, in particular in patent applications JP-11158046, JP-11158047 and JP-11158048, compositions for oxidation dyeing keratin fibers containing, as dye precursors oxidation, certain substituted derivatives of paraphenylenediamine. However, the colorings obtained using these compositions are not 1 ~ always quite powerful, chromatic or resistant to different assaults on the hair.
However, the Applicant has now discovered that it is possible to obtain new dyes, capable of leading to color tints 2o varied, chromatic, powerful, aesthetic, not very selective and resistant well to the various aggressions that fibers can undergo, by associating at least a first oxidation base chosen from certain derivatives of ~ a paraphenylenediamine of formula (I) defined below and their addition salts with an acid and at least a second oxidation base suitably 2s selected.
This discovery is the basis of the present invention.
The first object of the invention is therefore a composition for dyeing.
3o of oxidation of keratin fibers and in particular of fibers keratin human like hair, characterized by the fact that it includes, in a suitable medium for dyeing WO 01/66072

3 PCT / FRO1 / 00663 - at least one first oxidation base chosen from substituted derivatives of paraphenylenediamine of formula (I) below, and their addition salts with an acid R2WNiR ~
(Rs) ~ (I) s in which - R, and R2 can take one of the following meanings i) to v) i) R, and R2 simultaneously represent a radical - (CH2) 2CHOHCH20H; or 1o ü) R ~ represents a radical -CH2 (CHOH) 4CH20H and R2 represents an atom hydrogen, an alkyl, aryl radical or a heterocycle; or üi) R, represents an alkyl, aryl or heterocycle radical and R2 represents a alkylene radical - (CH2) m- in which m is an integer equal to 2 or 3, said alkylene radical forming a ring together with the nitrogen atom, ~ s 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, being understood that when R, is an alkyl or aryl radical, then either R ~, or said alkylene radical is substituted by a radical containing at least one atom nitrogen, oxygen or sulfur;
2o iv) R ~ represents a radical - (CH2CH20) PR4 in which p is a number whole between 2 and 8 inclusive, Ra and R2, identical or different, represent a hydrogen atom, an alkyl or aryl radical or a heterocycle;
v) R ~ and R2 form, together with the nitrogen atom on which they are 2s fixed, a saturated heterocycle with 5, 6 or 7 links, said heterocycle being substituted by at least one radical containing at least one atom of carbon, nitrogen, sulfur oxygen;

WO 01/66072

4 PCT / FRO1 / 00663 - R3 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 radical, sulfo, alkoxy, aryloxy, cyanoamino, amino, anilino, ureido, sulfamylamino, mono-s or di-alkylsulfamylamino, alkylthio, arylthio, alkoxycarbonylamino, sulfonamido, carbamyl, mono- or di-alkylcarbamylsulfamyl, sulfonyl, alkoxycarbonyl, azo, acyloxy, carbamyloxy, mono- or di-alkylcarbamyloxy, silyl, silyloxy, aryloxycarbonylamino, imido, sulfinyl, phosphonyl, aryloxycarbonyl, acyl or mercapto;
io 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 radical, alkoxyalkyl, aminoalkyl optionally substituted on the nitrogen atom, is carboxyalkyle, alkylcarboxyalkyle, thioalkyle, alkyithioalkyle, cyanoalkyl, trifluoroalkyl, sulfoalkyl, phosphoalkyl, or haloalkyl;
said alkoxy radicals containing from 1 to 25 carbon atoms and capable of be linear, branched or cyclic;
said aryl radicals containing from 6 to 26 carbon atoms and capable of 2o be substituted by one or more radicals chosen from the radicals alkyl, substituted alkyl or alkoxy;
the heterocycles being mono or polycyclic, each cycle comprising 3, 4, or 6 links and may contain one or more heteroatoms, being understood that in the case of polycyclic heterocycles, at least one of 2s 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 East greater than 1, then the radicals R3 can be identical or different and form between them a saturated or unsaturated cycle with 3, 4, 5, or 6 links;
provided that 1) when R ~ and R2 have the meanings defined in point v), then the compounds of formula (I) do not contain more than 3 hydroxyl radicals;

WO 01/66072

5 PCT / FRO1 / 00663 2) when R, and R2 have the meanings defined in point v) and that R, and form a pyrrolidine ring substituted by a carbamoyl radical on the carbon in the alpha position of the nitrogen atom on which they are attached, then not is different from 0; or the pyrrolidine cycle carries at least two s substituents;
3) when R, and R2 have the meanings defined in point v) and that R, and form a pyrrolidine ring substituted by a hydroxymethyl radical on the carbon located in alpha position relative to the nitrogen atom on which they are fixed, and that n = 0 or 1, then either said cycle carries at least two to additional substituents, that is to say said cycle comprises only one second different substituent of a hydroxyl radical on the carbon located in position ~ i with respect to the nitrogen atom and with respect to the carbon carrying said hydroxymethyl substituent; or when R, and R2 have the meanings defined in point v) and that R, and R2 form a substituted pyrrolidine ring is by a hydroxymethyl radical on the carbon located in the alpha position by relation to the nitrogen atom on which they are fixed, and that n = 1, then R3 East different from an alkyl, mono- or polyhydroxyalkyl radical;
4) when R, and R2 have the meanings defined in point iii) the compounds of Form (I) must meet at least one of the following four conditions 2o a) whatever the value of n, the alkylene ring formed by the radical has a substituent in addition to the radical R,; or b) n is greater than 1; or c) when n is equal to 1, then R3 represents an aryl radical or a heterocycle; or 2s d) when n is equal to zero or to 1, then R represents an aryl radical, a heterocycle or a substituted alkyl radical different from a radical monohydroxyalkyl;
5) when R, and R2 have the meanings defined in point v), the groups and R2 form a heterocycle different from piperazines and 3o diazacycloheptanes.
- And at least one second oxidation base chosen from the bases heterocyclic oxidation, double bases, paraaminophenols WO 01/66072 Ö PCT / FRO1 / 00663 substituted, orthoaminophenols, paraphenylenediamine derivatives of following formula (II), and their addition salts with an acid R ~
R $ / (II) in which - R5 represents a hydrogen atom, a C ~ -C4 alkyl radical, C ~ -C4 monohydroxyalkyl, C2-C4 polyhydroxyalkyl, alkoxy (C ~ -C4) (C, -Ca) alkyl, C, -Ca alkyl substituted by a nitrogen group, phenyl or 4'-aminophenyl;
1o - R6 represents a hydrogen atom, a C ~ -C4 alkyl radical, C ~ -C4 monohydroxyalkyl, C2-C4 polyhydroxyalkyl, alkoxy (C ~ -C4) (C ~ -Ca) alkyl or C, -Ca alkyl substituted by a nitrogen group;
- R ~ represents a hydrogen atom, a halogen atom such as an atom chlorine, bromine, iodine or fluorine, a C 1 -C 4 alkyl radical, is C ~ -C4 monohydroxyalkyl, C, -C4 hydroxyalkoxy, acetylaminoalkoxy C, -C4, C, -Ca mesylaminoalkoxy or C, -C4 carbamoylaminoalkoxy, - R8 represents a hydrogen atom, a halogen atom or an alkyl radical in C ~ -Ca;
2o it being understood that when R5, R6 and R8 simultaneously represent an atom of hydrogen, then R ~ denotes neither a hydrogen atom, nor an atom of chlorine, nor a methyl radical.
The dye composition according to the invention leads to colorings in 2s of varied, chromatic, powerful, aesthetic nuances, presenting a low selectivity and excellent resistance properties both against live atmospheric agents such as light and bad weather and the sweating and various treatments that the hair can undergo.

According to a particular embodiment, the oxidation base is chosen among substituted para-phenylenediamine derivatives of formula (I) below, and their addition salts with an acid R2WN ~ Ri (R3) n (I) s in which - R, and RZ can take one of the following meanings i) to v) i) R, and R ~ simultaneously represent a radical - (CH2) 2CHOHCH20H; or 1o ii) R ~ represents a radical -CH2 (CHOH) 4CH20H and R2 represents an atom hydrogen, an alkyl radical; or iv) R, represents a radical - (CH2CH20) pR. ~ in which p is an integer between 2 and 8 inclusive, R4 and R2, identical or different, represent a hydrogen atom, an alkyl radical;
~ sv) R ~ and R ~ form, together with the nitrogen atom on which they are fixed, a 5, 6 or 7-membered saturated 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 atom heterocycle nitrogen;
20 - R3 represents a halogen atom, an alkyl or aryl radical, a heterocycle, n is an integer equal to 0, 1 or 2;
According to one embodiment of the invention, the groups R1 and R2 form a 2s heterocycle comprising a single heteroatom, nitrogen, for example a pyrolidine heterocycle.

WO 01/66072 $ PCT / FRO1 / 00663 Among the substituted paraphenylenediamine derivatives of formula (I) above, Mention may very particularly be made 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 s 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 to 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-ts methylthio paraphenylenediamine, 1-N, N-bis- (3 ', 4'-dihydroxybutyl) -3-ethylthio paraphenylenediamine, 1-N, N-bis- (3 ', 4'-dihydroxybutyl) -3-mercapto para-phenylenediamine 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 2o paraphenylenediamine, 1-N, N-bis- (3 ', 4'-dihydroxybutyl) -3-mercaptoethyl thioparaphenylenediamine, 1-N, N-bis- (3 ', 4'-dihydroxybutyl) -3- -hydrox y ethyl 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 2s 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, the 1-N- (2 ', 3', 4 ', 5', 6'-pentahydroxyhexyl) -3-methyl thioparaphenylenediamine, the 1-N- (2 ', 3', 4 ', 5', 6'-pentahydroxyhexyl) -3-mercapto paraphenylenediamine, la 1-N- (hexyl) -1-N- (2 ', 3', 4 ', 5', 6'-pentahydroxyhexyl) -3-isopropyl paraphenylene-diamine, 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, the s 1-N- (methyl) -1-N- (2 ', 3', 4 ', 5', 6'-pentahydroxyhexyl) -3-hydroxyethyloxy para-phenylenediamine, 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-lo methylpiperidyl) -1-N- (2 ', 3', 4 ', 5', 6'-pentahydroxyhexyl) -3-ethyloxy para-phenylenediamine, 4-N- (methyl) -4-N- (2 ', 3', 4 ', 5', 6'-pentahydroxyhexyl) -amino-7-amino-1-methylindole, 1-N- (hydroxyethyloxyethyl) -1-N- (2 ', 3', 4 ', 5', 6'-penta-hydroxyhexyl) -3-ethyl paraphenylenediamine, and their addition salts with a acid.
1s 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 2o 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'-2s 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) 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-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-s 3-methyl-5-aminoindoline, 1-ureidoethyl-6-methoxy-5-aminoindoline, 1- (2 ', 3', 4 ', 5', 6'-pentahydroxy-hexyl) -5-aminoindoline, 1-N- (2'-mercaptoethyl) -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-io 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-(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-ts trimethyl-1,2,3,4-tetrahydroquinoline, 6-amino-1- (ethyl-bis-(hydroxyethyloxy-ethyloxyethyloxyethyl)) - 2,2,3,7-tetramethyl-1,2,3,4-tetrahydroquinoline, the 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, the

6-amino-1- (hydroxyethyloxyethyloxyethyl) -2,2,3-trimethyl-7-isopropyl-1,2,3,4-2o tetrahydroquinoline, 6-amino-1- (hydroxyethyloxyethyloxyethyloxyethyloxy-ethyloxyethyloxyethyloxyethyl) -2,2,3-trimethyl-7-isopropyl-1,2,3,4-tetrahydro-quinoline, 6-amino-1- (hydroxyethyloxyethyloxyethyloxyethyloxyethyloxy-ethyloxyethyloxyethyl) -2,2,3-trimethyl-1,2,3,4-tetrahydroquinoline, 6-amino-(mercaptoethyl) -1,2,3,4-tetrahydroquinoline, 6-amino-1- (3 ', 4'-dihydroxybutyl) -2s 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, the 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-3o ethyloxyethyloxyethyloxyethyloxyethyloxyethyloxyethyloxyethyl) -2,2-dimethyl-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- (hydroxy-ethyloxyethyloxyethytoxyethyloxyethyloxyethyl) -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-s 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- (hydroxy-lo ethyloxyethyloxyethyloxyethyl) -4- (hydroxyethyloxyethyloxyethyloxyethyl) -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'-is dihydroxypropyloxy) -1,2,3,4-tetrahydro-quinoline, 6-amino-1- (3 ', 4'-dihydroxybutyl) -2,2,7-trimethyl-3-mercaptomethyl-1,2,3,4-tetrahydroquinoline, the 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-propylsulfonic, the 6-amino-1- (4'-pyridinyl) -2,2,7-trimethyl-1,2,3,4-tetrahydroquinoline, 6-amino-20 1- (3 ', 4'-dihydroxybutyl) -2,2,4,7-tetramethyl-1,2,3,4-tetrahydroquinoline, the 6-amino-1,7-düsopropyl-2,2-dimethyl-4-trimethylsilanyloxy-1,2,3,4-tetrahydro-quinoline, 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-tetrahydro-quinoline, and their acid addition salts.
2s Mention may also be made most particularly of 1- (4'-amino-3'-isopropyloxyphenyl) -2,6-dimethyl pyrrolidine, 1- (4'-amino-3'-methylphenyl) -3-hydroxyethyloxy pyrrotidine, 1- (4'-amino-3'-methylphenyl) -4-hydroxy-2-methyl pyrrolidine, the 1- (4'-amino-3'-methylphenyl) -3-methylsulfonamido pyrrolidine, 1- (4'-amino-3'-3o phenoxyphenyl) -3-methylsulfonamido pyrrolidine, 3-n.butyl acid pyrrolidine 1- (4'-amino-3'-phenylsulfonic), 1- (4'-amino-3'-acetylaminophenyl) -3-hydroxymethyl pyrrolidine, 7-amino-4- (2'-methyl) -pyrrolydinyl-benzofuran, the 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, the 1- (4'-amino-3'-isopropyloxyphenyl) -2,6-dimethyl piperidine, la 1- (4'-amino-3'-isopropylphenyl) -2-hydroxymethyl piperidine, 1- (4'-amino-3'-isopropyl-s oxyphenyl) -2-hydroxymethyl piperidine, 1- (4'-amino-3'-aminophenyl) -2-hydroxymethyl piperidine, 1- (4'-amino-3'-dimethylfaminophenyl) -2-mercaptoethyloxyethyl piperidine, 1- (4'-amino-3 '(- 2 "', 4"'- dichloro) anilinophenyl) -4-methyl piperidine, 1- (4'-aminophenyl) -4-methyl piperidine, the 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 para-phenylenediamine, 1-N-methyl-1-N- (hydroxyethyloxyethyloxy-ts ethyl) paraphenylene diamine, 1-N-phenyl-1-N- (hydroxyethyloxyethyl) paraphenylenediamine, 1-N-benzyl-1-N- (hydroxyethyloxyethyloxyethyloxy-ethyloxyethyl) -3-trimethylsilyl paraphenylenediamine, 1-N-methyl-1-N-(hydroxyethyloxyethyloxyethyloxyethyloxyethyloxyethyloxyethyloxyethyl) -3-trimethylsilyloxy paraphenylenediamine, 1-N-ethyl-1-N- (methoxyethyloxy 2o ethyloxyethyloxyethyloxyethyl) -3-phenoxycarbonylamino paraphenylene diamine, 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 2s 1-N- (hydroxyethyloxyethyl) -3-phenoxycarbonyl paraphenylenediamine, la 1-N, N-bis- (hydroxyethyloxyethyloxyethyloxyethyl) paraphenylenediamine, the 1-N, N-bis- (methoxyethyloxyethyloxyethyloxyethyl) -3-isopropyloxy para-phenylenediamine, 1-N, N-bis- (hydroxyethyloxyethyloxyethyl) -3-isopropyloxy paraphenylenediamine, 1-N, N-bis- (hydroxyethyloxyethyloxyethyloxyethyl) -3-3o isopropyl paraphenylene diamine, 1-N, N-bis- (hydroxyethyloxyethyloxy-ethyloxyethyl) -3-isopropyl paraphenylenediamine, 1-N, N-bis- (methoxy-ethyloxyethyloxyethyloxyethyloxyethyloxyethyloxyethyl) -3-methoxy para-phenylenediamine, 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, s 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-to methylsuifonamido 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'-ts methylphenyl) -2-methyl azacycloheptane, 1- (4'-amino-3'-ureidophenyl) -3-hydroxy azacycloheptane, 1-N-4'-hydroxybutyl-1-N-(hydroxyethyloxyethyloxyethyl) -3-isopropy1 paraphenylenediamine, 1-N-methyl-1-N- (hydroxyethyloxyethyloxy-ethyl) paraphenylene diamine, 1-N, N-bis-(hydroxyethyloxy-ethyloxyethyloxyethyl) paraphenylenediamine, 1-N, N-bis-20 (hydroxyethyloxyethyloxyethyloxyethyl) -3-isopropyl paraphenyiene-diamine, the 1-N, N-bis- (hydroxyethyloxyethyloxyethyloxyethyl) -3-isopropyl paraphenylenediamine, 1-N, N-bis-(hydroxyethyloxyethyloxyethyloxyethyloxyethyfoxyethyloxyethyloxyethyl) -3-methyl paraphenylenediamine, 1-N, N-bis- (benzyloxyethyioxy-ethyloxyethyl) -3-2s 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 3o preferably from 0.001 to 15% by weight and even more preferably of 0.01 to 10% by weight relative to the total weight of the composition.
Among the para-phenylenediamines of formula (11) which can be used as second oxidation base in the dye composition according to the invention, can WO 01/66072 ~ 4 PCT / FRO1 / 00663 more particularly, quote 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, s 4-amino N, N-diethyl 3-methyl aniline, N, N-bis- (~ -hydroxyethyl) paraphenylenediamine, 4-N, N-bis- (~ i-hydroxyethyl) amino 2-methyl aniline, 4-N, N-bis- (~ -hydroxyethyl) amino 2-chloro aniline, la 2- ~ -hydroxyethyl paraphenylenediamine, 2-fluoro paraphenylenediamine, 2-isopropyl paraphenylenediamine, N- (~ i-hydroxypropyl) 1o paraphenylenediamine, 2-hydroxymethyl paraphenylenediamine, N, N-dimethyl 3-methyl paraphenylenediamine, N, N- (ethyl, a-hydroxyethyl) paraphenylenediamine, N- (~ i, y-dihydroxypropyl) paraphenylenediamine, N- (4'-aminophenyl) paraphenylenediamine, N-phenyl paraphenylenediamine, 2- ~ -hydroxyethyloxy paraphenylenediamine, 2- ~ i-acetylaminoethyloxy ts paraphenylenediamine, N- (~ -methoxyethyl) paraphenylenediamine, and their addition salts with an acid.
Among the paraphenylenediamines of formula (II) above, all are preferred particularly 2-isopropyl paraphenylenediamine, 2- ~ -hydroxyethyl 2o para-phenylenediamine, 2- ~ 3-hydroxyethyloxy para-phenylenediamine, 2,6-dimethyl paraphenylenediamine, 2,6-diethyl paraphenylenediamine, 2,3-dimethyl paraphenylenediamine, N, N-bis- (~ i-hydroxyethyl) para-phenylenediamine, 2- ~ i-acetylaminoethyloxy para-phenylenediamine, and their addition salts with an acid.
2s Even more preferably, among the paraphenylenediamines of formula (II) above, 2- ~ i-hydroxyethyl paraphenylenediamine, N, N-bis-(~ -hydroxyethyl) paraphenylenediamine, and their addition salts with an acid.
3o According to the invention, by double bases is meant the compounds comprising at at least two aromatic nuclei on which are carried groups amino and / or hydroxyl.

Among the double bases 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 the following formula (III), and their addition salts with an acid Z ~ Z2 R ~~ Ri2 Rs YI Rio (III) NR ~ 3R, a NR ~ sR ~ s s in which - Z ~ and Z2, identical or different, represent a hydroxyl radical or -which may be substituted by a C 1 -C 4 alkyl radical or by an arm of bond Y;
1o - 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, sulfur or nitrogen atoms, and optionally substituted by one or more hydroxyl or alkoxy radicals 1s in C ~ -C6;
- Rs and Rio represent a hydrogen or halogen atom, an alkyl radical in C, -C4, monohydroxyalkyl in C ~ -C4, polyhydroxyalkyl in C2-C4, C 1-4 aminoalkyl or a linker Y;
R, ~, R, 2, R ~ 3, R, 4, R ~ 5 and R ~ 6, identical or different, represent a atom 2o of hydrogen, a linker Y or a C 1 -C 4 alkyl radical;
it being understood that the compounds of formula (III) have only one arm bond Y per molecule.
2s Among the nitrogenous groups of formula (III) above, there may be mentioned in particular the amino, monoalkyl (C, -C4) amino, dialkyl (C ~ -C4) amino radicals, trialkyl (C, -C4) amino, monohydroxyalkyl (C, -C4) amino, imidazolinium and ammonium.

Among the double bases of formula (III) above, one can more particularly mention N, N'-bis- (~ -hydroxyethyl) N, N'-bis- (4'-aminophenyl) 1,3-diamino propanol, N, N'-bis- (~ i-hydroxyethyl) N, N'-bis- (4'-aminophenyl) s ethylenediamine, N, N'-bis- (4-aminophenyl) tetramethylenediamine, N, N'-bis- (~ -hydroxyethyl) N, N'-bis- (4-aminophenyl) tetramethylenediamine, the 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.
io Among these double bases of formula (III), N, N'-bis- (~ i-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.
1s Among the substituted para-aminophenols which can be used as a second base oxidation in the dye composition according to the invention, it is possible to in particular mention the compounds of formula (IV) below, and their salts addition with an acid OH
R ~~
(IV) Shea in which - R, ~ represents a hydrogen or halogen atom, an alkyl radical in C ~ -C4, C ~ -C4 monohydroxyalkyl, (C, -C4) alkoxy (C, -C4) alkyl, aminoalkyl 2s in C, -C4 or hydroxyalkyl (C ~ -C4) aminoalkyl in C, -C4, - R ~ $ represents a hydrogen or halogen atom, an alkyl radical in C ~ -C4, C ~ -C4 monohydroxyalkyl, C2-C4 polyhydroxyalkyl, aminoalkyl in C ~ -C4, cyanoalkyl in C ~ -C4 OR aICOXy (C ~ -C4) alkyl (C ~ -C4), it being understood that at least one of the radicals R "or Ri $ is different from an atom 3o of hydrogen.

Among the para-aminophenols of formula (IV) above, one can more particularly mention para-aminophenol, 4-amino 3-methyl phenol, 4-amino 3-fluoro phenol, 4-amino 3-hydroxymethyl phenol, 4-amino s 2-methyl phenol, 4-amino 2-hydroxymethyl phenol, 4-amino 2-methoxymethyl phenol, 4-amino 2-aminomethyl phenol, 4-amino 2- (~ i-hydroxyethyl aminomethyl) phenol, 4-amino 2-fluoro phenol, and their salts addition with an acid.
to Among the orthoaminophenols which can be used as oxidation bases in the dye compositions according to the invention, more can be particularly quote 2-amino phenol, 2-amino 5-methyl phenol, 2-amino 6-methyl phenol, 5-acetamido 2-amino phenol, and their acid addition salts.
Is Among the heterocyclic bases which can be used as oxidation bases in the dye compositions according to the invention, more can be particularly quote pyridine derivatives, pyrimidine derivatives, derivatives pyrazoles, and their addition salts with an acid.
2. Among the pyridine derivatives, there may be mentioned more particularly the compounds described for example in patents GB 1,026,978 and GB 1,153,196, as the 2,5-diamino pyridine, 2- (4-methoxyphenyl) amino 3-amino pyridine, 2,3-diamino 6-methoxy pyridine, 2- (~ i-methoxyethyl) amino 3-amino 6-methoxy pyridine, 3,4-diamino pyridine, and their addition salts with a 2s acid.
Among the pyrimidine derivatives, mention may be made more particularly of 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 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 derivatives pyrazolo-pyrimidiniques 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; the 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; the 3-amino s 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, the 2 - [(3-amino-pyrazolo [1,5-a] pyrimidin-7-yl) - (2-hydroxy-ethyl) -amino] -ethanol, the 2 - [(7-amino-pyrazolo [1,5-a] pyrimidin-3-yl) - (2-hydroxy-ethyl) -amino] -ethanol, the 5,6-dimethyl pyrazolo- [1,5-a] -pyrimidine-3,7-diamine, 2,6-dimethyl pyrazolo-io [1,5-a] -pyrimidine-3,7-diamine, la 2, 5, N 7, N 7-tetramethyl pyrazolo- [1,5-at]-pyrimidine-3,7-diamine, 3-amino-5-methyl-7-imidazolylpropylamino pyrazolo-[1,5-a] -pyrimidine, their addition salts with an acid, and their forms tautomers, when there is a tautomeric equilibrium.
ts Among the pyrazole derivatives, mention may more particularly be made of compounds described in patents DE 3,843,892, DE 4,133,957 and 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, 20 4,5-diamino 1 - ([i-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, the 4,5-diamino 1 - ([i-hydroxyethyl) 3-methyl pyrazole, 4,5-diamino 1-ethyl 2s 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, 30 1-methyl 3,4,5-triamino pyrazole, 3,5-diamino 1-methyl 4-methylamino pyrazole, 3,5-diamino 4 - ([i-hydroxyethyl) amino 1-methyl pyrazole, and their addition salts with an acid.

The oxidation base (s) used as the 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%
in weight about that weight.
s According to a preferred embodiment of the invention, the composition dye contains at least one coupler.
These couplers can in particular be chosen from 1o metaphenylenediamines, meta-aminophenols, metadiphenols and heterocyclic couplers such as, for example, indole derivatives, indolinic derivatives, benzimidazole derivatives, derivatives of benzomorpholine, sesamol derivatives, pyridine derivatives, pyrimidinics and pyrazolics, and their acid addition salts.
is These couplers are more particularly chosen from 2-methyl 5-amino phenol, 5-N- (~ i-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 1- (~ -hydroxyethyloxy) benzene, 20 2-amino 4- (~ -hydroxyethylamino) 1-methoxy benzene, 1,3-diamino benzene, 1,3-bis- (2,4-diaminophenoxy) propane, sesamol, 1-amino 2-methoxy 4,5-methylenedioxy benzene, a-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 2s 3-methyl pyrazole 5-one, and their addition salts with an acid.
When they are present, the coupler (s) preferably represent 0.0001 to 15% by weight approximately relative to the total weight of the composition.
3o The dye composition in accordance with the invention may, in addition, contain a or several additional oxidation bases different from the bases oxidation described above and / or one or more direct dyes.

WO 01/66072 2 ~ PCT / FR01 / 00663 Among the additional oxidation bases which can be used according to the invention, can mention the paraphenylenediamines other than those of formula (I) and (II) defined above, such as for example paraphenylenediamine, paratoluylenediamine, 2-chloro paraphenylenediamine, and s paraaminophenols other than those of formula (IV) defined above, such as the 4-amino phenol, and their addition salts with an acid.
When present, the additional oxidation base (s) preferably represent from 0.0001 to 15% by weight approximately relative to the to total weight of the composition.
In general, the acid addition salts usable in the framework of the dye compositions of the invention are in particular chosen among hydrochlorides, hydrobromides, sulfates, tartrates, lactates and the is acetates.
The medium suitable for dyeing (or support) generally consists through water or a mixture of water and at least one organic solvent to solubilize compounds which are not sufficiently soluble in water.
2o As organic solvent, mention may, for example, be made of alkanols lower in C ~ -C4, such as ethanol and isopropanol; glycerol, glycols and ethers of glycols such as 2-butoxyethanol, propylene glycol, monomethyl ether propylene glycol, monoethyl ether and monomethyl ether of diethylene glycol, as well as aromatic alcohols such as benzyl alcohol or 2s phenoxyethanol, analogues and their mixtures.
The solvents can be present in proportions preferably 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 3o weight approximately.
The pH of the dye composition in accordance with the invention is generally between 3 and 12. It can be adjusted to the desired value using agents acidifiers or alkalinizers usually used in fiber dyeing keratinous.
Among the acidifying agents, there may be mentioned, by way of example, the acids minerals or organic like hydrochloric acid, acid s orthophosphoric, carboxylic acids such as tartaric acid, acid citric, lactic acid, sulfonic acids.
Among the basifying agents, there may be mentioned, by way of example, ammonia, the alkaline carbonates, alkanolamines such as mono-, di- and 1o triethanolamines as well as their derivatives, hydroxyalkylamines and oxyethylenated and / or oxypropylenated ethylenediamines, the hydroxides of sodium or potassium and the compounds of formula (V) below Rio N-R_N R22 (V) R ~ ~ R2 ~
IS

in which R is a propylene residue optionally substituted by a hydroxyl group or a C 1 -C 4 alkyl radical; Ris, R2o, R2 ~ and R22, identical or different, represent a hydrogen atom, an alkyl radical C ~ -C4 or hydroxyalkyl C ~ -C4.
Acidifying agents are conventionally, for example, acids minerals or organic like hydrochloric acid, acid orthophosphoric, carboxylic acids like tartaric acid, acid citric, lactic acid, or sulfonic acids.
The dye composition according to the invention may also contain various adjuvants conventionally used in dyeing compositions hair, such as anionic, cationic, non-surface active agents ionic, amphoteric, zwitterionic or mixtures thereof, polymers 3o anionic, cationic, nonionic, amphoteric, zwitterionic or their mixtures, mineral or organic thickening agents, agents reducing agents or antioxidants, penetration agents, agents sequestering agents, perfumes, buffers, dispersing agents, agents conditioning agents such as, for example, silicones, film-forming agents, preservatives, opacifiers, silicone UV filters or s non-silicone, vitamins or provitamins.
The reducing or antioxidant agents can be chosen in particular among sodium sulfite, thioglycolic acid, thiolactic acid, bisulfite sodium, dehydroascorbic acid, hydroquinone, 2-methyl-hydroquinone, io ter-butyl-hydroquinone and homogentisic acid, and they are then generally present in amounts which can vary between 0.05 and 1.5% in weight approximately relative to the total weight of the composition.
Preferably, the dye composition in accordance with the invention contains the 1s minus a nonionic surfactant in a proportion varying from preferably between 0.1 and 20% by weight approximately relative to the total weight of the composition, and at least one cationic or amphoteric substantive polymer in a proportion preferably varying between 0.05 and 10% by weight relative to at total weight of the composition.
Preferably, the dye composition in accordance with the invention contains the at least one thickening polymer comprising at least one hydrophilic unit and at least minus a fatty chain in a proportion preferably varying between 0.05 and 10% by weight relative to the total weight of the composition.
2s Of course, those skilled in the art will take care to choose the possible compound (s) above mentioned, so that the properties advantageous intrinsically attached to the dye composition according to the invention is not, or is not substantially, altered by the 3o additions envisaged.
The dye composition in accordance with the invention may be presented in various forms, such as in the form of liquids, creams, gels, or under any other suitable form for dyeing the fibers keratin, including human hair.
Another object of the invention is a process for dyeing oxidation of fibers keratin and in particular human keratin fibers such as s hair using the dye composition as defined previously.
According to this process, at least one composition is applied to the fibers dye as defined above, the color being revealed at pH
acid, io neutral or alkaline using an oxidizing agent which is added just to the time of use in the dye composition or which is present in a composition oxidant applied simultaneously or sequentially separately.
According to a particularly preferred form of implementation of the Is a dye according to the invention, the mixture is mixed, at the time of use, composition dye as defined above with an oxidizing composition containing, in an environment suitable for dyeing, at least one oxidizing agent present in sufficient amount to develop coloration. The mixture obtained is then applied to the keratin fibers and left to stand for 3 at 20 to 50 minutes approximately, preferably 5 to 30 minutes approximately, after which rinse, washed with shampoo, rinsed again and dried.
The oxidizing agent can be chosen from conventionally oxidizing agents used for oxidation dyeing of keratin fibers, and among which one 2s can cite hydrogen peroxide, urea peroxide, bromates of metals alkalis, persalts such as perborates and persulfates, and enzymes such as peroxidases, laccases, tyrosynases and oxidoreductases among which we can in particular mention the pyranose oxidases, glucose oxidases, glycerol oxidases, lactates 30 oxidases, pyruvate oxidases, and uricases, said enzymes being possibly 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 keratin fibers varies from preference between 3 and 12 approximately and even more preferably between 5 and 11. It is s adjusted to the desired value using acidifying or basifying agents usually used in dyeing keratin fibers and such as defined previously.
The oxidizing composition as defined above can also contain 1o various adjuvants conventionally used in compositions for the dyeing hair and as defined above.
The composition which is finally applied to the keratin fibers can is present in various forms, such as in the form of liquids, is creams, gels, or in any other suitable form to achieve a dyeing of keratin fibers, and in particular human hair.
Another object of the invention is a device with several compartments or "kit"
multi-compartment dye or any other system of 2 packaging with several compartments including 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 for delivering to the hair the desired mixture, such as the devices described in the patent 2s FR-2 586 913 in the name of the plaintiff.
The following examples are intended to illustrate the invention.

The following dye compositions were prepared, in accordance with the invention 1- (4'-amino-3'-2.10'32.10'3) hydrochloride 2.10-32.10'3 2.10'3 methyl-phnyl) -4-hydroxy-2-methyl-mole mole mole mole mole pyrrolidine (driv substituted of paraphnylnediamine of formula (I) according to the invention) 2-methyl 5-amino phnol 3.10-33.10'3 3.10-33.10-3 3.10-3 (coupler) mole mole mole mole mole 4-amino 3-methyl phnol 10-3 - - - -(second oxidation base) mole N, N-bis- (~ -hydroxy-- 10 3 - - - sulfate thyl) paraphnyl-diamine mole (second oxidation base) N, N'-bis tetrachloride - ((i-- - 10 - -hydroxythyl) N, N'-bis- (4'-amino- mole phnyl) 1,3-diamino propanol (second oxidation base) 4,5-diamino dihydrochloride - - - 10 3 -methyl pyrazole (second base mole oxidation) Orthoaminophnol (second - - - - 10 base 3 oxidation) mole Common dye support (*) (*) (*) (*) (*) Demineralized water qs 100 100 100 100 100 ggggg (*) Common dye support - Alkyl Cs-C ~ o polyglucoside in 60% aqueous solution, sold under the name ORAMIX CG 110 ~ by the company SEPPIC 5.4 g io - 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 DISSOLUIN D-40 ~ by AKZO 1.08 g s - Sodium metabisulfite 0.205 g - 20.5% NH3 ammonia 10.0 g At the time of use, the compositions were mixed weight for weight dye described above with 20% hydrogen peroxide solution io volumes (6% by weight).
The mixtures thus produced were applied for 30 minutes to locks of natural gray hair permed with 90% white. Highlights were then rinsed, washed with a standard shampoo, rinsed with 1s new then dried.
The hair was dyed in the following shades Examples Shades obtained 1 Deep red purple 2 Deep purple 3 Deep purple 4 Deep red Deep red brown

Claims (26)

1. Composition for the oxidation dyeing of keratin fibers and in in particular human keratin fibers such as the hair, characterized by the fact that it comprises, in a suitable medium for dyeing:

- at least one first oxidation base chosen from substituted derivatives of para-phenylenediamine of formula (I) below, and their addition salts with an acid:
in which:
- R1 and R2 can take one of the following meanings i) to v):

i) R1 and R2 simultaneously represent a -(CH2)2CHOHCH2OH radical; Where ii) R1 represents a -CH2(CHOH)4CH2OH radical and R2 represents an atom hydrogen, an alkyl or aryl radical or a heterocycle; Where iii) R1 represents an alkyl or aryl radical or a heterocycle and R2 represents a alkylene radical -(CH2)m- in which m is an integer equal to 2 or 3, said alkylene radical forming a ring together with the nitrogen atom, the carbon atom of the benzene ring bearing the nitrogen atom and one of two carbon atoms of the benzene ring which are adjacent to it, being understood that when R1 is an alkyl or aryl radical, then either R1 or said alkylene radical is substituted by a radical containing at least one atom nitrogen, oxygen or sulphur;
iv) R1 represents a -(CH2CH2O)PR4 radical in which p is an integer between 2 and 8 inclusive, R4 and R2, identical or different, represent a hydrogen atom, an alkyl or aryl radical or a heterocycle;
v) R1 and R2 form, together with the nitrogen atom on 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 atom of carbon, nitrogen, oxygen, sulfur;
- R3 represents a halogen atom, an alkyl or aryl radical, a heterocycle, a heterocycle connected to the benzene ring of formula (I) by an ether or thio bond, a cyano, nitro, hydroxyl, carboxyl radical, sulpho, alkoxy, aryloxy, cyanoamino, amino, anilino, ureido, sulfamylamino, mono-or di-alkylsulfamylamino, alkylthio, arylthio, alkoxycarbonylamino, sulfonamido, carbamyl, mono- or di-alkylcarbamylsulfamyl, sulfonyl, alkoxycarbonyl, azo, acyloxy, carbamyloxy, mono- or di-alkylcarbamyloxy, silyl, silyloxy, aryloxycarbonylamino, imido, sulphinyl, phosphonyl, aryloxycarbonyl, acyl or mercapto;
said alkyl radicals comprising from 1 to 25 carbon atoms and possibly be linear, branched or cyclic and be substituted by one or more radicals and then represent a mono or polyhydroxyalkyl radical, alkoxyalkyl, aminoalkyl optionally substituted on the nitrogen atom, carboxyalkyl, alkylcarboxyalkyl, thioalkyl, alkylthioalkyl, cyanoalkyl, trifluoroalkyl, sulfoalkyl, phosphoalkyl, or haloalkyl;
said alkoxy radicals comprising from 1 to 25 carbon atoms and possibly be linear, branched or cyclic;
said aryl radicals comprising from 6 to 26 carbon atoms and possibly be substituted by one or more radicals chosen from alkyl radicals, substituted alkyl or alkoxy;
the heterocycles being mono or polycyclic, each cycle comprising 3, 4, or 6 membered and may contain one or more heteroatoms, 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 R3 can be identical or different and form between them a saturated or unsaturated ring with 3, 4, 5, or 6 members;
provided that 1) when R1 and R2 have the meanings defined in point v), then the compounds of formula (I) do not contain more than 3 hydroxyl radicals;
2) when R1 and R2 have the meanings defined in point v) and when R1 and 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 bears at least two substituents;
3) when R1 and R2 have the meanings defined in point v) and when R1 and form a pyrrolidine ring substituted by a hydroxymethyl radical on the carbon located in the alpha position with respect to the nitrogen atom on which they are fixed, and that n = 0 or 1, then either said cycle carries at least two additional substituents, or said ring comprises only a second substituent different from a hydroxyl radical on the carbon located in position .beta.
with respect to the nitrogen atom and with respect to the carbon bearing said hydroxymethyl substituent; or when R1 and R2 have the meanings defined in point v) and that R1 and R2 form a substituted pyrrolidine ring by a hydroxymethyl radical on the carbon located in position alpha by relative to the nitrogen atom on which they are fixed, and that n = 1, then R3 is different from an alkyl, mono- or polyhydroxyalkyl radical;
4) when R1 and R2 have the meanings defined in point iii) the compounds of formula (I) must meet at least one of the following four conditions a) whatever the value of n, the alkylene ring formed by the radical R2 has a substituent in addition to the radical R1; Where b) n is greater than 1; Where c) when n is equal to 1, then R3 represents an aryl radical or a heterocycle; Where d) when n is equal to zero or 1, then R1 represents an aryl radical, a heterocycle or a substituted alkyl radical other than a radical monohydroxyalkyl;
5) when R, and R2 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 the bases heterocyclic oxidation agents, double bases, paraaminophenols substituted orthoaminophenols, paraphenylenediamine derivatives of following formula (II), and their addition salts with an acid in which - R5 represents a hydrogen atom, a C1-C4 alkyl radical, monohydroxy C1-C4 alkyl, polyhydroxy C2-C4 alkyl, alkoxy(C1-C4)alkyl (C1-C4), C1-C4 alkyl substituted by a nitrogen group, phenyl or 4'-aminophenyl;
- R6 represents a hydrogen atom, a C1-C4 alkyl radical, monohydroxy C1-C4 alkyl, polyhydroxy C2-C4 alkyl, alkoxy(C1-C4) (C1-C4) alkyl or C1-C4 alkyl substituted with a nitrogen group;
- R7 represents a hydrogen atom, a halogen atom such as a chlorine, bromine, iodine or fluorine, a C1-C4 alkyl radical, C1-C4 monohydroxyalkyl, C1-C4 hydroxyalkoxy, C1-C4 acetylaminoalkoxy C1-C4, mesylaminoalkoxy C1-C4 or carbamoylaminoalkoxy C1-C4, - R8 represents a hydrogen or halogen atom or an alkyl radical in C1-C4;

it being understood that when R5, R6 and R8 simultaneously represent an atom of hydrogen, then R7 denotes neither a hydrogen atom nor a chlorine, nor a methyl radical. 2. Composition according to claim 1, in which the oxidation base is chosen from substituted para-phenylenediamine derivatives of formula (I) following, and their addition salts with an acid in which - R1 and R2 can take one of the following meanings i) to v) i) R1 and R2 simultaneously represent a -(CH2)2CHOHCH2OH radical; Where ii) R1 represents a -CH2(CHOH)4CH2OH radical and R2 represents an atom of hydrogen. an alkyl radical; Where iv) R1 represents a radical -(CH2CH2O)p R4 in which p is an integer between 2 and 8 inclusive, R4 and R2, identical or different, represent a hydrogen atom, an alkyl radical;
v) R1 and R2 form, together with the nitrogen atom on which they are fixed, a 5, 6 or 7 membered saturated 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 with respect to the atom heterocycle nitrogen;
- R3 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 para-phenylenediamine derivatives of formula (I) are chosen from the 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 para-phenylenediamine, 1-N,N-bis-(3',4'-dihydroxybutyl)-3-propyloxy para-phenylenediamine, 1-N,N-bis-(3',4'-dihydroxybutyl)-3-hexyloxy paraphenylene-diamine, 1-N,N-bis-(3',4'-dihydroxybutyl)-3-(1"-N-3",5"-dimethylpyrazolyl para-phenylenediamine, 1-N,N-bis-(3',4'-dihydroxybutyl)-3-ureido paraphenylene-diamine, 1-N,N-bis-(3',4'-dihydroxybutyl)-3-trimethyl 1",3",3"-ureido para-phenylenediamine, 1-N,N-bis-(3',4'-dihydroxybutyl)-3-dimethylamino para-phenylenediamine, 1-N,N-bis-(3',4'-dihydroxybutyl)-3-methylthio para-phenylenediamine, 1-N,N-bis-(3',4'-dihydroxybutyl)-3-ethylthio paraphenylene-diamine, 1-N,N-bis-(3',4'-dihydroxybutyl)-3-mercapto paraphenylenediamine the 1-N,N-bis-(3',4'-dihydroxybutyl)-3-n.butylthio paraphenylenediamine, the 1-N,N-bis-(3',4'-dihydroxybutyl)-3-n.octylthio paraphenylenediamine, the 1-N,N-bis-(3',4'-dihydroxybutyl)-3-mercaptoethyl paraphenylenediamine, the 1-N,N-bis-(3',4'-dihydroxybutyl)-3-mercaptoethyl thioparaphenylenediamine, la 1-N,N-bis-(3',4'-dihydroxybutyl)-3--hyd r oxyethylthioparaphenylenediamine , the 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, the 1-N-(2',3',4',5',6'-pentahydroxyhexyl)-3-dimethylamino paraphenylenediamine, the 1-N-(2',3',4',5',6'-pentahydroxyhexyl)-3-methyl thioparaphenylenediamine, la 1-N-(2',3',4',5',6'-pentahydroxyhexyl)-3-mercapto paraphenylenediamine, la 1-N-(hexyl)-1-N-(2',3',4',5',6'-pentahydroxyhexyl)-3-isopropyl paraphenylene-diamine, 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 paraphenylenediamine, 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 para-phenylenediamine, 1-N-(methyl)-1-N-(2',3',4',5',6'-pentahydroxyhexyl) paraphenylenediamine, 1-N-(phenyl)-1-N-(2',3',4',5',6'-pentahydroxyhexyl)-3-ethyloxy 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-(hydroxy-ethyloxyethyl)-1-N-(2',3',4',5',6'-pentahydroxyhexyl)-3-ethyl paraphenylene-diamine, 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-hydroxyethyloxy-ethyloxyethyloxyethyloxyethyloxyethyl-6-isopropyl-5-amino-indoline, 2-hydroxy-ethyl-3-methyl-5-aminoindoline, 2-hydroxyethylo-xylethyloxyethyl)-5-amino indoline, 1-carboxymethyl-2,3,3-trimethyl-5-aminoindoline, 1-methyl-sulfonamidoethyl-3-methyl-5-aminoindoline, 1-ureidoethyl-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-methyl ester acid phosphoric, 6-amino-1,2,2-trimethyl-4-trimethylsilanyloxy-1,2,3,4-tetrahydroquinoline, 6-amino-1-hexyl-2,2,7-trimethyl-4-mercaptomethyl-1,2,3,4-tetrahydroquinoline, 6-amino-1-(3',4'-dihydroxybutyl)-2,2,3-trimethyl-1,2,3,4-tetrahydroquinoline, 6-amino-1-(ethoxyethoxyethoxyethoxy-3',4'-dihydroxybutyl)-2,2,3,7-tetramethyl-1,2,3,4-tetrahydroquinoline, 6-amino-1-(hydroxyethyloxyethyloxyethyloxyethyl)-2,2,3-trimethyl-1,2,3,4-tetrahydro-quinoline, 6-amino-1-(hydroxyethyloxyethyl)-2,2,3-trimethyl-1,2,3,4-tetrahydroquinoline, 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-methoxy-1,2,3,4-tetrahydro-quinoline, 6-amino-1-(hydroxy-ethyloxyethyloxyethyl)-2,2,3-trimethyl-7-isopropyl-1,2,3,4-tetrahydro-quinoline, the 6-amino-1-(hydroxyethyloxyethyloxyethyloxyethyloxyethyloxyethyloxyethyloxy-ethyl)-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-(3-hydroxypropyl)-2,2-dimethyl-4-hydroxymethyl-7-isopropyl-1,2,3,4-tetrahydro-quinoline, 6-amino-1-(hydroxy-ethyloxyethyloxyethyloxyethyloxyethyloxy-ethyloxyethyloxyethyl)-2,2-dimethyl-4-hydroxymethyl-7-isopropyl-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-(hydroxyethyloxyethyloxyethyloxy-ethyl)-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, the 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, the 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-propylsulfonic, the 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, the 6-amino-1,2,2,4-tetramethyl-3-hydroxy-1,2,3,4-tetrahydroquinoline, 6-amino-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'-aminophenyl)-2-(hydroxyethyl) piperidine, 1-(4'-amino-3'-methoxyphenyl)-2,6-dihydroxymethyl piperidine, the 1-(4'-amino-3'-isopropyloxyphenyl)-2,6-dimethyl piperidine, 1-(4'-amino-3'-isopropylphenyl)-2-hydroxymethyl piperidine, 1-(4'-amino-3'-isopropyloxy-phenyl)-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, the 1-(4'-amino-3'-methylthiophenyl)-2,7-dimethyl azacycloheptane, the 1-N-4'-hydroxybutyl-1-N-(hydroxyethyloxyethyloxyethyl)-3-isopropyl para-phenylenediamine, 1-N-methyl-1-N-(hydroxyethyloxyethyloxyethyl) paraphenylenediamine, 1-N-phenyl-1-N-(hydroxyethyloxyethyl) paraphenylene-diamine, 1-N-benzyl-1-N-(hydroxyethyloxyethyloxyethyloxyethyloxyethyl)-3-trimethylsilyl paraphenylenediamine, 1-N-methyl-1-N-(hydroxy-ethyloxyethyloxyethyloxyethyloxyethyloxyethyloxyethyloxyethyl)-3-trimethylsilyloxy paraphenylenediamine, 1-N-ethyl-1-N-(methoxyethyloxyethyloxyethyloxy-ethyloxyethyl)-3-phenoxycarbonylamino paraphenylenediamine, 1-N-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, the 1-N,N-bis-(hydroxyethyloxyethyloxyethyloxyethyl)-3-isopropyl paraphenylene-diamine, 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 para-phenylenediamine, 1-N,N-bis-(hydroxyethyloxyethyloxyethyloxyethyl)-3-isopropyloxy paraphenylenediamine, 1-N,N-bis-(hydroxyethyloxyethyl)-3-mercaptoethyl paraphenylenediamine, 1-N,N-bis-(benzyloxyethyloxy-ethyloxyethyl)-3-isopropyl paraphenylenediamine, and their addition salts with a 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 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 paraphenylenediamine, 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) 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 selected 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, the 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) paraphenylenediamine, 1-N,N-bis-(hydroxyethyloxy-ethyloxyethyloxyethyl) paraphenylenediamine, 1-N,N-bis-(hydroxyethyloxyethyloxyethyloxyethyl)-3-isopropyl paraphenylenediamine, 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, and their addition salts with an acid. 6. Composition according to any one of the preceding claims, characterized in that the para-phenylenediamine 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 R1 and R2 groups form a pyrrolidine heterocycle. 8. Composition according to any one of the preceding claims, characterized in that the para-phenylenediamines of formula (II) are chosen from 2,3-dimethyl para-phenylenediamine, 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-(.beta.-hydroxyethyl) paraphenylenediamine, 4-N,N-bis-(.beta.-hydroxyethyl)amino 2-methyl aniline, 4-N,N-bis-(.beta.-hydroxy-ethyl) amino 2-chloro aniline, 2-.beta.-hydroxyethyl paraphenylenediamine, the 2-fluoro paraphenylenediamine, 2-isopropyl paraphenylenediamine, N-(.beta.-hydroxypropyl)paraphenylenediamine, 2-hydroxymethyl paraphenylenediamine, N,N-dimethyl 3-methyl paraphenylenediamine, N,N-(ethyl, (.beta.-hydroxyethyl) paraphenylenediamine, N-(.beta.,.gamma.-dihydroxypropyl) paraphenylenediamine, N-(4'-aminophenyl) paraphenylenediamine, N-phenyl paraphenylenediamine, 2-.beta.hydroxyethyloxy paraphenylenediamine, 2-.beta.-acetylaminoethyloxy paraphenylenediamine, N-(.beta.-methoxyethyl) paraphenylenediamine, and their addition salts with a acid. 9. Composition according to claim 8, characterized in that the para-phenylenediamines of formula (II) are chosen from 2-isopropyl paraphenylenediamine, 2-(.beta.-hydroxyethyl paraphenylenediamine, 2-.beta.-hydroxyethyloxy paraphenylenediamine, 2,6-dimethyl paraphenylenediamine, 2,6-diethyl paraphenylenediamine, 2,3-dimethyl paraphenylenediamine, N,N-bis-(.beta.-hydroxyethyl) paraphenylenediamine, the 2-(.beta.-acetylaminoethyloxy paraphenylenediamine, and their addition salts with a acid. 10. Composition according to claim 9, characterized in that the para-phenylenediamines of formula (II) are chosen from 2-.beta.-hydroxyethyl paraphenylenediamine, N,N-bis-(.beta.-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) following, and their addition salts with an acid in which - Z1 and Z2, identical or different, represent a hydroxyl radical or -which may be substituted by a C1-C4 alkyl radical or by a connection Y;
- the connecting arm Y represents an alkylene chain comprising from 1 to 14 carbon atoms, linear or branched which may be interrupted or terminated by one or more nitrogenous groups and/or by one or more heteroatoms such as oxygen, sulfur or nitrogen atoms, and optionally substituted by one or more hydroxyl or alkoxy radicals in C1-C6;
- R9 and R10 represent a hydrogen or halogen atom, an alkyl radical C1-C4, monohydroxy C1-C4 alkyl, polyhydroxy C2-C4 alkyl, C1-C4 aminoalkyl or a Y linker;
- R11, R12, R13, R14, R15 and R16, identical or different, represent a atom hydrogen, a connecting arm Y or a C1-C4 alkyl radical;
it being understood that the compounds of formula (III) have only one arm of Y bonds per molecule. 12. Composition according to claim 11, characterized in that the basics doubles of formula (III) are chosen from N,N'-bis-(.beta.-hydroxyethyl) N,N'-bis-(4'-aminophenyl) 1,3-diamino propanol, N,N'-bis-(.beta.-hydroxyethyl) N,N'-bis-(4'-aminophenyl) ethylenediamine, N,N'-bis-(4-aminophenyl) tetramethylenediamine, N,N'-bis-(.beta.-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 salts addition with an acid. 13. Composition according to any one of claims 1 to 7, characterized in that the substituted para-aminophenols are chosen from compounds of the following formula (IV), and their addition salts with an acid:
in which - R17 represents a hydrogen or halogen atom, an alkyl radical in C1-C4, monohydroxy C1-C4 alkyl, alkoxy(C1-C4)alkyl(C1-C4), aminoalkyl C1-C4 or hydroxyalkyl (C1-C4)aminoalkyl C1-C4, - R18 represents a hydrogen or halogen atom, an alkyl radical in C1-C4, C1-C4 monohydroxyalkyl, C2-C4 polyhydroxyalkyl, aminoalkyl C1-C4, cyanoalkyl C1-C4 or alkoxy (C1-C4) alkyl (C1-C4), it being understood that at least one of the radicals R17 or R18 is different from an atom of hydrogen. 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-(.beta.-hydroxyethyl aminomethyl) phenol, the 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 derivatives pyridine derivatives, pyrimidine derivatives, pyrazole derivatives, and their salts addition 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 weight total dye composition. 18. Composition according to claim 17, characterized in that the or them oxidation bases used as second oxidation base represent of 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 them meta-phenylenediamines, meta-aminophenols, meta-diphenols 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-(.beta.-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 1-(.beta.-hydroxyethyloxy) benzene, 2-amino 4-(.beta.-hydroxyethylamino) 1-methoxy benzene, 1,3-diamino benzene, 1,3-bis-(2,4-diaminophenoxy) propane, sesamol, 1-amino 2-methoxy 4,5-methylenedioxy benzene, .alpha.-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 pyrazol 5-one, 1-phenyl 3-methyl pyrazole 5-one, and their acid addition salts. 21. Composition according to claim 19 or 20, characterized in that the or the couplers represent from 0.0001 to 15% by weight based on the weight composition total. 22. Composition according to any one of the preceding claims, characterized in that it contains one or more oxidation bases additional additives chosen from para-phenylenediamine, paratolylenediamine, 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 among hydrochlorides, hydrobromides, sulphates, tartrates, lactates and the acetates. 24. Oxidation dyeing process for keratin fibers and in particular of the human keratin fibers such as hair, characterized by the fact that at least one dye composition such as that defined in any one of claims 1 to 23, the color being developed at acidic, neutral or alkaline pH using an oxidizing agent which is added just to time of use to the dye composition or which is present in a oxidizing composition applied simultaneously or sequentially so separated. 25. Process according to claim 24, characterized in that the agent oxidant is chosen from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts and oxidizing enzymes. 26. Multi-compartment device, or multi-dye "kit"
compartments, of which a first compartment contains a composition dye as defined in any one of claims 1 to 23 and a second compartment contains an oxidizing composition.