FR2805738A1 - Composition for oxidation dyeing of keratinic fibers, especially human hair, comprises a substituted p-phenylenediamine developer and another developer - Google Patents

Abstract

Composition for oxidation dyeing of keratinic fibers comprises a first developer selected from p-phenylenediamine derivatives (I) and a second developer selected from heterocyclic developers, bifunctional developers, substituted p-aminophenols, o-aminophenols and p-phenylenediamine derivatives (II). Composition for oxidation dyeing of keratinic fibers comprises a first developer selected from p-phenylenediamine derivatives of formula (I); R1 = CH2(CHOH)4CH2OH or (CH2CH2O)pR4: R2, R4 = H, alkyl, aryl or heterocyclyl; p = 2-8; R3 = halogen, alkyl, aryl, heterocyclyl, heterocyclyloxy, heterocyclylthio, CN, NO2, OF, COOH, SO3H, alkoxy, aryloxy, cyanoamino, amino, anilino, ureido, sulfamoylamino, mono- or dialkylsulfamoylamino, alkylthio, arylthio, alkoxycarbonylamino, sulfonamido, carbamoyl, mono- or dialkylcarbamoyl, silyl, silyloxy, aryloxycarbonylamino, imido, sulfinyl, phosphonyl, aryloxycarbonyl, acyl or SH, or multiple R3 groups can form a 3- to 6-membered ring; alkyl = optionally substituted 1-25C linear, branched or cyclic alkyl; alkoxy = 1-25C linear, branched or cyclic alkoxy; aryl = 6-26C aryl optionally substituted by alkyl, substituted alkyl or alkoxy; heterocyclyl = mono- or polycyclic heterocyclyl in which each ring has 3-6 members and can contain one or more heteroatoms; n = 0-4; R1 and R2 = (CH2)2CHOHCH2OH; or R1 = alkyl, aryl or heterocyclyl and R2 = a (CH2)2 or (CH2)3 group (Q) that is attached to a C atom ortho to the NR1R2 group, provided that R1 or Q is substituted with a N-, O- or S-containing group when R1 is alkyl or aryl; or NR1R2 is a 5- to 7-membered ring substituted with at least one N-, O- or S-containing group; provided that: (1) the compound contains no more than 3 OH groups when NR1R2 is a ring; (2) when NR1R2 is 2-carbamoyl-1-pyrrolidinyl, then n is nonzero or the pyrrolidine ring has at least 2 substituents; (3) when NR1R2 is 2-hydroxymethyl-1-pyrrolidinyl and n = 0 or 1, then the pyrrolidine ring either has at least 2 additional substituents or has one additional substituent other than 4-OH, or when NR1R2 is 2-hydroxymethyl-1-pyrrolidinyl and n = 1, then R3 is not alkyl, hydroxyalkyl or polyhydroxyalkyl; (4) when R2 is Q, then either: (i) the ring formed by Q has a substituent in addition to R1; (ii) n is more than 1; (iii) R3 is aryl or heterocyclyl when n = 1; or (iv) R1 is aryl, heterocyclyl or substituted alkyl other than monohydroxyalkyl when n = 0 or 1. and a second developer selected from heterocyclic developers, bifunctional developers, substituted p-aminophenols, o-aminophenols and p-phenylenediamine derivatives of formula (II): R5 = H, 1-4C alkyl, 1-4C hydroxyalkyl, 2-4C polyhydroxyalkyl, (1-4C)alkoxy(1-4C)alkyl, 1-4C alkyl substituted with a N-containing group, phenyl or 4-aminophenyl; R6 = H, 1-4C alkyl, 1-4C hydroxyalkyl, 2-4C polyhydroxyalkyl, (1-4C)alkoxy(1-4C)alkyl or 1-4C alkyl substituted with a N-containing group; R7 = H, halogen, 1-4C hydroxyalkyl, 1-4C hydroxyalkoxy, acetylamino(1-4C)alkoxy, mesylamino(1-4C)alkoxy or carbamoylamino(1-4C)alkoxy; R8 = H, halogen or 1-4C alkyl; provided that R7 is not H, Cl or Me when R5, R6 and R8 are H.

Description

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The subject of the invention is a composition for the oxidation dyeing of keratin fibers, and in particular human keratinous fibers such as the hair comprising, in a medium suitable for dyeing, at least a first oxidation base chosen from certain substituted para-phenylenediamine derivatives 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 para-phenylenediamines, ortho or para-aminophenols, heterocyclic bases, generally known as oxidation bases. The oxidation dye precursors, or oxidation bases, are colorless or weakly colored compounds which, combined with oxidizing products, can give rise, by a process of oxidative condensation, 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 meta-diamines, meta-aminophenols, meta-diphenols and certain heterocyclic compounds.

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

The so-called "permanent" coloration obtained with these oxidation dyes must also meet a certain number of requirements. Thus, it must allow to obtain shades in the desired intensity and have a good resistance to external agents (light, bad weather, washing, permanent waving, perspiration, friction).

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The dyes must also make it possible to cover the white hair, and finally be the least selective possible, that is to say allow to obtain the smallest color differences possible throughout a single keratin fiber, which can be in effect differently sensitized (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 precursors of oxidation dyes, certain substituted derivatives. of para-phenylenediamine. However, the colorations obtained by using these compositions are not always powerful enough, chromatic or resistant to the various attacks that can suffer hair.

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 resistant to the various attacks that can suffer the fibers, associating at least a first oxidation base selected from certain paraphenylenediamine derivatives of formula (I) defined below and their addition salts with an acid and at least a second oxidation base suitably selected.

This discovery is the basis of the present invention.

The invention therefore firstly relates to a composition for the oxidation dyeing of keratin fibers and in particular human keratinous fibers such as the hair, characterized in that it comprises, in a medium suitable for dyeing: at least one first oxidation base chosen from the substituted paraphenylenediamine derivatives of formula (1) below, and their addition salts with an acid:

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dans laquelle : -R1 et R2 peuvent prendre l'une des significations i) à v) suivantes : i) Ri et R2 représentent simultanément un radical -(CH2)2CHOHCH20H ; ou ii) Ri représente un radical -CH2(CHOH)4CH20H et R2 représente un atome d'hydrogène, un radical alkyle, aryle ou un hétérocycle ; ou iii)R1 représente un radical alkyle, aryle ou un hétérocycle et R2 représente un radical alkylène -(CH2)m- dans lequel m est un entier égal à 2 ou à 3, ledit radical alkylène formant un cycle conjointement avec l'atome d'azote, l'atome de carbone du cycle benzénique portant l'atome d'azote et l'un des deux atomes de carbone du cycle benzénique qui lui sont adjacents, étant entendu que lorsque R1 est un radical alkyle ou aryle, alors soit R1, soit ledit radical alkylène est substitué par un radical contenant au moins un atome d'azote, d'oxygène ou de soufre ; iv)R1 représente un radical -(CH2CH20)pR4 dans lequel p est un nombre entier compris entre 2 et 8 inclusivement, R4 et R2, identiques ou différents, représentent un atome d'hydrogène, un radical alkyle, aryle ou un hétérocycle ; v) Ri et R2 forment, conjointement avec l'atome d'azote sur lequel ils sont fixés, un hétérocycle saturé à 5,6 ou 7 chaînons, ledit hétérocycle étant substitué par au moins un radical contenant au moins un atome de carbone, d'azote, d'oxygène de soufre ; - R3 représente un atome d'halogène, un radical alkyle ou aryle, un hétérocycle, un hétérocycle relié au cycle benzénique de la formule (I) par une liaison éther ou thio, un radical cyano, nitro, hydroxyle, carboxyle, sulfo,

in which: R 1 and R 2 can take on one of the following meanings i) to v): i) R 1 and R 2 simultaneously represent a - (CH 2) 2 CHOHCH 2 OH radical; or ii) R 1 is -CH 2 (CHOH) 4 CH 2 OH and R 2 is hydrogen, alkyl, aryl or heterocycle; or iii) R1 represents an alkyl, aryl or heterocycle radical and R2 represents an alkylene radical - (CH2) m- in which m is an integer equal to 2 or 3, said alkylene radical forming a ring together with the atom of nitrogen, 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 R1 is an alkyl or aryl radical, then either R1 either said alkylene radical is substituted with a radical containing at least one nitrogen, oxygen or sulfur atom; iv) R1 represents a radical - (CH2CH2O) pR4 in which p is an integer between 2 and 8 inclusive, R4 and R2, identical or different, represent a hydrogen atom, an alkyl radical, an aryl radical or a heterocycle; v) R 1 and R 2 form, together with the nitrogen atom to which they are attached, a saturated 5- or 7-membered heterocycle, said heterocycle being substituted with at least one radical containing at least one carbon atom, d. nitrogen, sulfur oxygen; 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 or sulpho radical;

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alkoxy, aryloxy, cyanoamino, amino, anilino, ureido, sulfamylamino, mono- or di-alkylsulfamylamino, alkylthio, arylthio, alkoxycarbonylamino, sulfonamido, carbamoyl, 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 having from 1 to 25 carbon atoms and which may be linear, branched or cyclic and may be substituted by one or more radicals and then represent a mono or polyhydroxyalkyl, alkoxyalkyl, aminoalkyl radical optionally substituted on the nitrogen atom, carboxyalkyl alkylcarboxyalkyl, thioalkyl, alkylthioalkyl, cyanoalkyl, trifluoroalkyl, sulfoalkyl, phosphoalkyl, or haloalkyl; said alkoxy radicals having from 1 to 25 carbon atoms and which may be linear, branched or cyclic; said aryl radicals having from 6 to 26 carbon atoms and being capable of being 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 may contain one or more heteroatoms, it being understood that in the case of polycyclic heterocycles, at least one ring contains at least one heteroatom such as N, O or S; n is an integer from 0 to 4; understood that when n is greater than 1, then the radicals R3 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 R 1 and R 2 have the meanings defined in item v), then the compounds of formula (I) contain not more than 3 hydroxyl radicals; 2) when R 1 and R 2 have the meanings defined in point v) and R 1 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

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 is different from 0; the pyrrolidine ring bears at least two substituents; 3) when R 1 and R 2 have the meanings defined in point v) and R 1 and R 2 form a pyrrolidine ring substituted by a hydroxymethyl radical on the carbon located in alpha position with respect to the nitrogen atom to which they are attached, and that n = 0 or 1, then either said ring carries at least two additional substituents, or said ring has only a second substituent different from a hydroxyl radical on the carbon located in the ss position relative to the atom. nitrogen and with respect to the carbon bearing said hydroxymethyl substituent; or when R 1 and R 2 have the meanings defined in item v) and R 1 and R 2 form a pyrrolidine ring substituted by a hydroxymethyl radical on the carbon located in alpha position relative to the nitrogen atom to which they are attached, 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 fulfill at least one of the following four conditions: a) whatever the value of n, the alkylene ring formed by the radical R2 comprises a substituent in addition to the radical R1; or b) n is greater than 1; c) when n is 1, then R3 represents an aryl radical or a heterocycle; or d) when n is zero or 1, then R 1 represents an aryl radical, a heterocycle or a substituted alkyl radical other than a monohydroxyalkyl radical; and at least one second oxidation base chosen from heterocyclic oxidation bases, double bases, substituted para-aminophenols, ortho-aminophenols, paraphenylenediamine derivatives of formula (II) below, and their addition salts with an acid :

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dans laquelle : - R5 représente un atome d'hydrogène, un radical alkyle en C1-C4, monohydroxyalkyle en Ci-C4, polyhydroxyalkyle en C2-C4, alcoxy(C1-
C4)alkyle(C1-C4), alkyle en C1-C4 substitué par un groupement azoté, phényle ou 4'-aminophényle ; - R6 représente un atome d'hydrogène, un radical alkyle en C1-C4, monohydroxyalkyle en C1-C4, polyhydroxyalkyle en C2-C4, alcoxy(C1-
C4)alkyle(C1-C4) ou alkyle en C1-C4 substitué par un groupement azoté ; - R7 représente un atome d'hydrogène, un atome d'halogène tel qu'un atome de chlore, de brome, d'iode ou de fluor, un radical alkyle en C1-C4, monohydroxyalkyle en C1-C4, hydroxyalcoxy en C1-C4, acétylaminoalcoxy en C1-C4, mésylaminoalcoxy en C1-C4 ou carbamoylaminoalcoxy en C1-C4, - R8 représente un atome d'hydrogène, d'halogène ou un radical alkyle en C1-C4 ; étant entendu que lorsque R5, R6 et R8 représentent simultanément un atome d'hydrogène, alors R7 ne désigne ni un atome d'hydrogène, ni un atome de chlore, ni un radical méthyle.

in which: R5 represents a hydrogen atom, a C1-C4 alkyl radical, a C1-C4 monohydroxyalkyl radical, a C2-C4 polyhydroxyalkyl radical or a C1-C4 alkoxy radical;
C4) (C1-C4) alkyl, C1-C4 alkyl substituted by nitrogen, phenyl or 4'-aminophenyl; R6 represents a hydrogen atom, a C1-C4 alkyl radical, a C1-C4 monohydroxyalkyl radical, a C2-C4 polyhydroxyalkyl radical or a C1-C4 alkoxy radical;
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 atom, a C1-C4 alkyl radical, a C1-C4 monohydroxyalkyl radical or a C1-C4 hydroxyalkoxy radical; C4, C1-C4 acetylaminoalkoxy, C1-C4 mesylaminoalkoxy or C1-C4 carbamoylaminoalkoxy; R8 represents hydrogen, halogen or C1-C4 alkyl; it being understood that when R5, R6 and R8 simultaneously represent a hydrogen atom, then R7 denotes neither a hydrogen atom, nor a chlorine atom, nor a methyl radical.

The dyeing composition according to the invention leads to colorations in various shades, chromatic, powerful, aesthetic, with a low selectivity and excellent properties of resistance both against atmospheric agents such as light and bad weather and with respect to perspiration and the different treatments that hair can undergo.

Among the substituted paraphenylenediamine derivatives of formula (I) above, mention may be made of 1-N, N-bis- (3 ', 4'-dihydroxybutyl) paraphenylenediamine, 1-N, N-bis- ( 3 ', 4'-Dihydroxybutyl) -3-methyl

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paraphénylènediamine la 1-N,N-bis-{3',4'-dihydroxybutyl)-3-n.butylthio paraphénylènediamine, la 1-N,N-bis-(3',4'-dihydroxybutyl)-3-n.octylthio paraphénylènediamine, la 1-N,N-bis-(3',4'-dihydroxybutyl)-3-mercaptoéthyl paraphénylènediamine, la 1-N,N-bis-(3',4'-dihydroxybutyl)-3-mercaptoéthyl

thioparaphénylènediamine, la 1-N,N-bis-(3',4'-dihydroxybutyl)-3-i-hydroxyéthyl thioparaphénylènediamine, la 1 -N-(2',3',4',5',6'-pentahydroxyhexyl) paraphénylènediamine, la 1 -N-(2',3',4',5',6'-pentahydroxyhexyl)-3-méthyl paraphénylènediamine, la 1-N-(2',3',4',5',6'-pentahydroxyhexyl)-3-isopropyl paraphénylènediamine, la 1 -N-(2',3',4',5',6'-pentahydroxyhexyl)-3-méthoxy paraphénylènediamine, la 1-N-(2',3',4',5',6'-pentahydroxyhexyl)-1-N-(4"N"méthylpipéridyl)-3-éthoxy paraphénylènediamine, la 1-N-(2',3',4',5',6'pentahydroxyhexyl)-3-isopropyloxy paraphénylènediamine, la 1-N-(2',3',4',5',6'pentahydroxyhexyl)-3-diméthylamino paraphénylènediamine, la 1-N-(2',3',4',5',6'-pentahydroxyhexyl)-3-méthyl thioparaphénylènediamine, la 1-N-(2',3',4',5',6'-pentahydroxyhexyl)-3-mercapto paraphénylènediamine, la 1-N-(hexyl)-1-N-(2',3',4',5',6'-pentahydroxyhexyl)-3-isopropyl paraphénylène-

diamine, la 1-N-(méthyl)-1-N-(2' ,3',4' ,5' ,6'-pentahydroxyhexyl)-3-isooctyloxy paraphénylènediamine, la 1-N-(méthyl)-1-N-(2',3',4',5',6'-pentahydroxyhexyl)-3- isopropyloxy paraphénylènediamine, la 1-N-(méthyl)-1-N-(2',3',4',5',6'pentahydroxyhexyl)-3-méthyl paraphénylène-diamine, la 1-N-(méthyl)-1-N- para-phenylenediamine, 1-N, N-bis- (3 ', 4'-dihydroxybutyl) -3-ethyl-para-phenylenediamine, 1-N, N-bis- (3', 4'-dihydroxybutyl) -3-propyl para-phenylenediamine, 1-N, N-bis- (3 ', 4'-dihydroxybutyl) -3-methoxy-para-phenylenediamine, 1-N, N-bis- (3', 4'-dihydroxybutyl) -3-ethoxy para-phenylenediamine, 1 N, N-bis- (3 ', 4'-dihydroxybutyl) -3-propyloxy-para-phenylenediamine, 1-N, N-bis- (3', 4'-dihydroxybutyl) -3-hexyloxy para-phenylenediamine, 1-N N-bis- (3 ', 4'-dihydroxybutyl) -3- (1 "-N-3", 5 "dimethylpyrazolyl para-phenylenediamine, 1-N, N-bis- (3', 4'-dihydroxybutyl) 3-ureido-para-phenylenediamine, 1-N, N-bis- (3 ', 4'-dihydroxybutyl) -3-trimethyl-1 ", 3", 3 "-ureido-para-phenylenediamine, 1-N, 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-para-phenylenediamine, 1-N, N-bis (3 ', 4'-dihydroxybutyl) -3-mercapto

1-N, N-bis- (3 ', 4'-dihydroxybutyl) -3-n-butylthio-para-phenylenediamine, para-phenylenediamine, 1-N, N-bis- (3', 4'-dihydroxybutyl) -3-n. octylthio paraphenylenediamine, 1-N, N-bis- (3 ', 4'-dihydroxybutyl) -3-mercaptoethyl para-phenylenediamine, 1-N, N-bis (3', 4'-dihydroxybutyl) -3-mercaptoethyl

thioparaphenylenediamine, 1-N, N-bis- (3 ', 4'-dihydroxybutyl) -3-i-hydroxyethyl thioparaphenylenediamine, 1-N- (2', 3 ', 4', 5 ', 6'-pentahydroxyhexyl) ) para-phenylenediamine, 1-N- (2 ', 3', 4 ', 5', 6'-pentahydroxyhexyl) -3-methyl para-phenylenediamine, 1-N- (2 ', 3', 4 ', 5', 6'-pentahydroxyhexyl) -3-isopropyl paraphenylenediamine, 1-N- (2 ', 3', 4 ', 5', 6'-pentahydroxyhexyl) -3-methoxy para-phenylenediamine, 1-N- (2 ', 3 ', 4', 5 ', 6'-Pentahydroxyhexyl) -1-N- (4 "N" methylpiperidyl) -3-ethoxy-para-phenylenediamine, 1-N- (2', 3 ', 4', 5 ', 6 pentahydroxyhexyl) -3-isopropyloxy-para-phenylenediamine, 1-N- (2 ', 3', 4 ', 5', 6'-pentahydroxyhexyl) -3-dimethylamino-para-phenylenediamine, 1-N- (2 ', 3', 4) ', 5', 6'-pentahydroxyhexyl) -3-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 paraphenylene

diamine, 1-N- (methyl) -1-N- (2 ', 3', 4 ', 5', 6'-pentahydroxyhexyl) -3-isooctyloxy para-phenylenediamine, 1-N- (methyl) -1- N- (2 ', 3', 4 ', 5', 6'-pentahydroxyhexyl) -3-isopropyloxy para-phenylenediamine, 1-N- (methyl) -1-N- (2 ', 3', 4 ') 6'-pentahydroxyhexyl) -3-methyl-para-phenylenediamine, 1-N- (methyl) -1-N-

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phénylènediamine, la 1-N-(méthyl)-1-N-(2',3',4',5',6'-pentahydroxyhexyl)-3- mercaptoéthyloxy paraphénylènediamine, la 1-N-(méthyl)-1-N-(2',3',4',5',6'pentahydroxyhexyl) paraphénylènediamine, la 1-N-(phényl)-1-N-(2',3',4',5',6'pentahydroxyhexyl)-3-éthyloxy paraphénylènediamine, la 1-N-(4"-Nméthylpiperidyl)-1-N-(2',3',4',5',6'-pentahydroxyhexyl)-3-éthyloxy paraphénylènediamine, le 4-N-(méthyl)-4-N-(2',3',4',5',6'-pentahydroxyhexyl)-amino-

7-amino-1-méthylindole, la 1-N-(hydroxyéthyloxyéthyl)-1-N-(2' ,3',4' ,5' ,6'-penta- hydroxyhexyl)-3-éthyl paraphénylènediamine, et leurs sels d'addition avec un acide. (2 ', 3', 4 ', 5', 6'-pentahydroxyhexyl) -3-ethyl-para-phenylenediamine, 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 para-phenylenediamine, 1-N- (methyl) -1- N- (2 ', 3', 4 ', 5', 6'-pentahydroxyhexyl) para-phenylenediamine, 1-N- (phenyl) -1-N- (2 ', 3', 4 ', 5', 6'-pentahydroxyhexyl) ) -3-ethyloxy-para-phenylenediamine, 1-N- (4 "-N-methylpiperidyl) -1-N- (2 ', 3', 4 ', 5', 6'-pentahydroxyhexyl) -3-ethyloxy para-phenylenediamine, 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-para-phenylenediamine, and salts thereof addition with an acid.

1 -(carboxyméthyl)-2,2,3,7-tétraméthyl-1,2,3,4-tétrahydro-quinoline, la 1-N- (3 ', 4'-dihydroxybutyl) -5-aminoindoline, 1- (2'-hydroxyethyl) -2-methyl-5-aminoindoline, 1-methyl-2-hydroxymethyl-5-aminoindoline are also particularly suitable. 6-methyl-2-hydroxyethyl-5-aminoindoline, 2-hydroxyethyloxyethyl-5-aminoindoline, 2-hydroxyethyloxyethyloxyethyloxyethyl-5-aminoindoline, 2-hydroxyethyloxyethyloxyethyloxyethyloxyethyloxyethyl-6-isopropyl-5-aminoindoline, 2-hydroxyethyl-3-methyl-5-aminoindoline, 2-hydroxyethyloxyethyloxyethyl-5-aminoindoline, 1-carboxymethyl-2,3,3-trimethyl-5-aminoindoline, 1-methylsulfonamidoethyl-3-methyl-5-aminoindoline, 1-ureidoethyl-6-methoxy-5-aminoindoline, 1- (2 ', 3', 4 ', 5', 6'-pentahydroxyhexyl) -5-aminoindoline, 1-N- (2'-2 ', mercaptoethyl) -5 aminoindoline, phosphonic acid 6-amino-1-methyl-1,2,3,4-tetrahydro-furo- [2,3, h] -quinoline 4-methyl ester; 1,2,2-amino-trimethyl-4-trimethylsilanyloxy-1,2,3,4-tetrahydroquinolin e, 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-tetrahydroquinoline 3,4-Tetrahydroquinoline, 6-amino-1- (hydroxyethyloxyethyloxyethyloxyethyl) -2,2,3-trimethyl-1,2,3,4-tetrahydroquinoline, 6-amino-1- (hydroxyethyloxyethyl) -2,2,3-trimethyl-1 2,3,4-tetrahydroquinoline, 6-amino-1- (ethyl-bis (hydroxyethyloxyethyloxyethyloxyethyl) -2,2,3,7-tetramethyl-1,2,3,4-tetrahydroquinoline,

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

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2,2,3-triméthyl-7-isopropyl-1,2,3,4-tétrahydro-quinoline, la 6-amino-1-(3',4'- dihydroxybutyl)-2,2,7-triméthyl-4-hydroxyméthyl-1,2,3,4-tétrahydroquinoline, la 6-amino-1-(3',4'-dihydroxybutyl)-2,2-diméthyl-4-hydroxyméthyl-7-isopropyl- 1,2,3,4-tétrahydroquinoline, la 6-amino-1-(3-hydroxypropyl)-2,2-diméthyl-4-

hydroxyméthyl-7-isopropyl-1,2,3,4-tétrahydro-quinoline, la 6-amino-1-(hydroxy- éthyloxyéthyloxyéthyloxyéthyloxyéthyloxyéthyfoxyéthyloxyéthyl)-2,2-diméthyl-4- hydroxyméthyl-7-isopropyl-1,2,3,4-tétrahydroquinoline, la 6-amino-1-(hydroxy- éthyloxyéthyloxyéthyloxyéthyl)-2,2-diméthyl-4-hydroxyméthyl-7isopropyl- 1,2,3,4-tétrahydroquinoline, la 6-amino-1-(hydroxyéthyloxyéthyloxyéthyloxy- éthyloxyéthyl)-2,2-diméthyl-7-isopropyl-1,2,3,4-tétrahydroquinoline, la 6-amino-

1 -( hyd roxy-éthyloxyéthyloxyéthyloxyéthyloxyéthyloxyéthy) )-2,2-d i méthyl-7- isopropyl-1,2,3,4-tétrahydroquinoline, la 6-amino-1-(hydroxyéthyloxyéthyl)-2,2diméthyl-1,2,3,4-tétrahydroquinoline, la 6-amino-1,2,2,4,7-pentaméthyl-3hydroxy-1,2,3,4-tétrahydroquinoline, la 6-amino-1-(3'-hydroxypropyl)-4- (hydroxyéthyloxyéthyloxyéthyloxyéthyl)-2,2-diméthyl-7-isopropyl-1,2,3,4-tétrahydroquinoline, la 6-amino-1-(hydroxyéthyloxyéthyloxyéthyloxyéthyl)-4,4- diméthyl-1,2,3,4-tétra-hydroquinoline, la 6-amino-1-(3',4'-dihydroxybutyl)-2,2diméthyl-7-isopropyl-1,2,3,4-tétrahydroquinoline, la 6-amino-1-(hydroxy- éthyloxyéthyloxyéthyloxyéthyl)-4-(hydroxyéthyloxyéthyloxyéthyloxyéthyl)-2,2,7triméthyl-1,2,3,4-tétrahydro-quinoline, la 6-amino-1-(hydroxyéthyloxyéthyloxy- éthyloxyéthyl)-2,2-diméthyl-7-isopropyl-1,2,3,4-tétra-hydroquinoline, la 6-amino- 1-(2',3',4',5',6'-pentahydroxy-hexyl)-2,2,4-triméthyl-7-isopropyl-1,2,3,4-tétrahydroquinoline, la 6-amino-1 -(mercaptoéthyl)-2,2,4-triméthyl-7-(2',3'- dihydroxypropyloxy)-1,2,3,4-tétrahydro-quinoline, la 6-amino-1-(3',4'dihydroxybutyl)-2,2,7-triméthyl-3-mercaptométhyl-1,2,3,4-tétrahydroquinoline, la

6-amino-1 -(uréidoéthyl)-2,2,4-triméthyl-1,2,3,4-tétrahydroquinoline, l'acide 1 - (Hydroxypropyl) -2,2,3-trimethyl-7-methoxy-1,2,3,4-tetrahydroquinoline, 6-amino-1- (hydroxyethyloxyethyloxyethyl) -2,2,3-trimethyl-7 isopropyl-1,2,3,4-tetrahydroquinoline, 6-amino-1- (hydroxyethyloxyethyloxyethyloxyethyloxyethyloxyethyloxyethyloxyethyl) -2,2,3-trimethyl-7-isopropyl-1,2,3,4-tetrahydroquinoline, 6-amino 1- (hydroxyethyloxyethyloxyethyloxyethyloxyethyloxyethyloxyethyloxyethyl) -2,2,3-trimethyl-1,2,3,4-tetrahydroquinoline, 6-amino-1- (mercaptoethyl) -1,2,3,4-tetrahydroquinoline, -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 1,2-dihydroxymethyl-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- (hydroxyethyloxyethyloxyethyloxyethyloxyethyloxyethyloxyethyloxyethyl) -2,2-dimethyl-4-hydroxymethyl-7-isopropyl-1,2,3 4-Tetrahydroquinoline, 6-amino-1- (hydroxyethyloxyethyloxyethyloxyethyl) -2,2-dimethyl-4-hydroxymethyl-7-isopropyl-1,2,3,4-tetrahydroquinoline, 6-amino-1- (hydroxyethyloxyethyloxyethyloxy) -2- ethyloxyethyl) -2,2-dimethyl-7-isopropyl-1,2,3,4-tetrahydroquinoline, 6-amino

1 - (Roxy-ethyloxyethyloxyethyloxyethyloxyethyloxyethyl) -2,2-di-methyl-7-isopropyl-1,2,3,4-tetrahydroquinoline, 6-amino-1- (hydroxyethyloxyethyl) -2,2-dimethyl-1,2, 3,4-tetrahydroquinoline, 6-amino-1,2,2,4,7-pentamethyl-3-hydroxy-1,2,3,4-tetrahydroquinoline, 6-amino-1- (3'-hydroxypropyl) -4 - (Hydroxyethyloxyethyloxyethyloxyethyl) -2,2-dimethyl-7-isopropyl-1,2,3,4-tetrahydroquinoline, 6-amino-1- (hydroxyethyloxyethyloxyethyloxyethyl) -4,4-dimethyl-1,2,3,4- tetrahydroquinoline, 6-amino-1- (3 ', 4'-dihydroxybutyl) -2,2-dimethyl-7-isopropyl-1,2,3,4-tetrahydroquinoline, 6-amino-1- (hydroxyethyloxyethyloxyethyloxyethyl) ) -4- (Hydroxyethyloxyethyloxyethyloxyethyl) -2,2,7-trimethyl-1,2,3,4-tetrahydroquinoline, 6-amino-1- (hydroxyethyloxyethyloxyethyloxyethyl) -2,2-dimethyl-7-isopropyl-1 2,3,4-tetrahydroquinoline, 6-amino-1- (2 ', 3', 4 ', 5', 6'-pentahydroxyhexyl) -2,2,4-trimethyl-7-isopropyl 1,2,3,4-tetrahydroquinoline, 6-amino-1 - (mercapto) aptoethyl) -2,2,4-trimethyl-7- (2 ', 3'-dihydroxypropyloxy) -1,2,3,4-tetrahydroquinoline, 6-amino-1- (3', 4'-dihydroxybutyl) 2,2,7-trimethyl-3-mercaptomethyl-1,2,3,4-tetrahydroquinoline, the

6-Amino-1- (ureidoethyl) -2,2,4-trimethyl-1,2,3,4-tetrahydroquinoline, the acid

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6-amino-2,2-diméthyl-7-chloro-1,2,3,4-tétrahydroquinoline-1-propylsulfonique, la 6-amino-1-(4'-pyridinyl)-2,2,7-triméthyl-1,2,3,4-tétrahydroquinoline, la 6-amino- 1-(3',4'-dihydroxybutyl)-2,2,4,7-tétraméthyl-1,2,3,4-tétrahydroquinoline, la 6-ami no- 1,7-d iiso pro pyl-2,2-d i méthyl-4-tri méthylsilanyloxy- 1,2,3,4-tétrahyd ro- quinoline, la 6-amino-1,2,2,4-tétraméthyl-3-hydroxy-1,2,3,4-tétrahydroquinoline, la 6-amino-1-bromo-2,2-diméthyl-4-mercapto-7-isopropyloxy-1,2,3,4-tétrahydro- quinoline, et leurs sels d'addition avec un acide.

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, the 6- No. 1,7-disopropyl-2,2-di-methyl-4-tri-methylsilanyloxy-1,2,3,4-tetrahydroquinoline, 6-amino-1,2,2,4- 3-amino-1-bromo-2,2-dimethyl-4-mercapto-7-isopropyloxy-1,2,3,4-tetrahydroquinoline and their addition salts with an acid.

hydroxy azacycloheptane, le 1-(4' -amino-3' -sulfamoylaminophényl)-2, 7 -diméthyl azacycloheptane, le 1-(4'-amino-3'-méthylthiophényl)-2,7-diméthyl azacycloheptane, la 1-N-4'-hydroxybutyl-1-N-(hydroxyéthyloxyéthyloxyéthyl)-3- isopropyl paraphénylènediamine, la 1-N-méthyl-1-N-(hydroxyéthyloxyéthyloxy- éthyl) paraphénylène-diamine, la 1-N-phényl-1-N-(hydroxyéthyloxyéthyl) paraphénylènediamine, la 1-N-benzyl-1-N-(hydroxyéthyloxyéthyloxyéthyloxy- éthyloxyéthyl)-3-triméthylsilyl paraphénylènediamine, la 1-N-méthyl-1-N- 1- (4'-Amino-3'-isopropyloxyphenyl) -6,6-dimethylpyrrolidine, 1- (4'-amino-3'-methylphenyl) -3-hydroxyethyloxy pyrrolidine, may be mentioned in particular. - (4'-amino-3'-methylphenyl) -4-hydroxy-2-methylpyrrolidine, 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'-aminophenyl) -2- (4" -aminophenoxymethyl) piperidine, amino-3'-acetylphenyl) -4-hydroxypiperidine, 1- (4'-aminophenyl) -2- (hydroxyethyl) piperidine, 1- (4'-amino-3'-methoxyphenyl) -2,6-dihydroxymethylpiperidine 1- (4'-amino-3'-isopropyloxyphenyl) -2,6-dimethylpiperidine, 1- (4'-amino-3'isopropylphenyl) -2-hydroxymethylpiperidine, 1- (4'-amino) -3'-isopropyloxyphenyl) -2-hydroxymethyl pi peridine, 1- (4'-amino-3'-aminophenyl) -2-hydroxymethylpiperidine, 1- (4'-amino-3'-dimethylaminophenyl) -2mercaptoethyloxyethylpiperidine, 1- (4'-amino-3 ', -2 "', 4"' - (dichloro) anilinophenyl) -4-methylpiperidine, 1- (4'-aminophenyl) -4-methylpiperidine, 1- (4'-aminophenyl) -2,7-dimethylazacycloheptane 1- (4'-amino-3'-methylphenyl) -2-methylazacycloheptane, 1- (4'-amino-3'-ureidophenyl) -3-

hydroxy azacycloheptane, 1- (4'-amino-3'-sulfamoylaminophenyl) -2,7-dimethylazacycloheptane, 1- (4'-amino-3'-methylthiophenyl) -2,7-dimethylazacycloheptane, 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- (hydroxyethyloxyethyloxyethyloxyethyloxyethyl) -3-trimethylsilyl para-phenylenediamine, 1-N-methyl-1-N-

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 (1-N-ethyl-1-N- (methoxyethyloxyethyloxyethyloxyethyloxyethyl) -3-phenoxycarbonylamino) para-phenylenediamine, 1-N-methyl-1-N- (methoxyethyloxyethyloxyethyl) -3- (2 '), 5'-dioxopyrrolidinyl) paraphenylenediamine, 1-N-ethyl-1-N- (hydroxyethyloxyethyloxyethyl) -3-4'pyridinylthio para-phenylenediamine, 1-N-propyl-1-N- (hydroxyethyloxyethyloxyethyl) -3- sulfinyl paraphenylenediamine, 1-N-methyl-1-N- (hydroxyethyloxyethyl) -3-phenoxycarbonyl para-phenylenediamine, 1-N, N-bis (hydroxyethyloxyethyloxyethyloxyethyl) paraphenylenediamine, 1-N, N-bis (methoxyethyloxyethyloxyethyloxyethyl) - 3-isopropyloxyprophenylenediamine, 1-N, N-bis (hydroxyethyloxyethyloxyethyl) -3-isopropyloxy para-phenylenediamine, 1-N, N-bis (hydroxyethyloxyethyloxyethyloxyethyl) -3-isopropyl paraphenylene diamine, 1-N, N-bis - (hydro xyethyloxyethyloxyethyloxyethyl) -3-isopropyl paraphenylenediamine, 1-N, N-bis (methoxyethyloxyethyloxyethyloxyethyloxyethyloxyethyloxyethyl) -3-methoxy-para-phenylenediamine, 1-N, N-bis (hydroxyethyloxyethyloxyethyloxyethyloxyethyloxyethyloxyethyloxyethyl) -3-methyl-para-phenylenediamine, 1-N, N-bis (hydroxyethyloxyethyloxyethyloxyethyl) -3-isopropyloxy para-phenylenediamine, 1-N, N-bis (hydroxyethyloxyethyl) -3-mercaptoethyl para-phenylenediamine, 1-N, N-bis (benzyloxyethyloxyethyloxyethyl) -3 isopropyl paraphenylenediamine, and their addition salts with an acid.

The paraphenylenediamine 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, more preferably from 0.001 to 15% by weight. 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) that can be used as the second oxidation base in the dye composition in accordance with the invention, there may be mentioned more particularly 2,3-dimethyl paraphenylenediamine, 2,6-dimethyl paraphenylenediamine, 2 6-diethyl paraphenylenediamine, 2,5-dimethyl paraphenylenediamine, N, N-dimethyl paraphenylenediamine,

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paraphénylènediamine, la 4-N,N-bis-((i-hydroxyéthyl)amino 2-méthyl aniline, la 4-N,N-bis-(P-hydroxyéthyl) amino 2-chloro aniline, la 2-p-hydroxyéthyl paraphénylènediamine, la 2-fluoro paraphénylènediamine, la 2-isopropyl paraphénylènediamine, la N-(-hydroxypropyl) paraphénylènediamine, la 2-hydroxyméthyl paraphénylènediamine, la N,N-diméthyl 3-méthyl paraphénylènediamine, la N,N-(éthyl, ss-hydroxyéthyl)

paraphénylènediamine, la N-(P,y-dihydroxypropyl) paraphénylènediamine, la N-(4'-aminophényl) paraphénylènediamine, la N-phényl paraphénylènediamine,

la 2-p-hydroxyéthyloxy paraphénylènediamine, la 2-5-acétylaminoéthyloxy paraphénylènediamine, la N-(ss-méthoxyéthyl) paraphénylènediamine, et leurs sels d'addition avec un acide. N, N-diethyl paraphenylenediamine, N, N-dipropyl paraphenylenediamine, 4-amino N, N-diethyl-3-methylaniline, N, N-bis (hydroxyethyl)

paraphenylenediamine, 4-N, N-bis - ((i-hydroxyethyl) amino-2-methylaniline, 4-N, N-bis- (P-hydroxyethyl) amino 2-chloroaniline, 2-p-hydroxyethyl paraphenylenediamine , 2-fluoro-para-phenylenediamine, 2-isopropyl-para-phenylenediamine, N - (- hydroxypropyl) para-phenylenediamine, 2-hydroxymethyl-para-phenylenediamine, N, N-dimethyl-3-methyl-para-phenylenediamine, N, N- (ethyl, ss-hydroxyethyl) )

paraphenylenediamine, N- (P, y-dihydroxypropyl) paraphenylenediamine, N- (4'-aminophenyl) paraphenylenediamine, N-phenyl paraphenylenediamine,

2-p-hydroxyethyloxy para-phenylenediamine, 2-5-acetylaminoethyloxy para-phenylenediamine, N- (ss-methoxyethyl) paraphenylenediamine, and their acid addition salts.

Of the paraphenylenediamines of formula (II) above, 2-isopropyl paraphenylenediamine, 2-ss-hydroxyethyl paraphenylenediamine, 2-p-hydroxyethyloxy paraphenylenediamine, 2,6-dimethyl paraphenylenediamine, 2,6 ethyl paraphenylenediamine, 2,3-dimethyl paraphenylenediamine, N, N-bis- (ss-hydroxyethyl para-phenylenediamine, 2-p-acetylaminoethyloxy para-phenylenediamine, and their addition salts with an acid.

Even more preferably, among the paraphenylenediamines of formula (II) above, 2-p-hydroxyethyl paraphenylenediamine, N, N-bis (s-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 bearing amino and / or hydroxyl groups.

Among the double bases that can be used as the second oxidation base in the dyeing 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:

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dans laquelle : - Z1 et Z2, identiques ou différents, représentent un radical hydroxyle ou-NH2 pouvant être substitué par un radical alkyle en C1-C4 ou par un bras de liaison
Y; - le bras de liaison Y représente une chaîne alkylène comportant de 1 à 14 atomes de carbone, linéaire ou ramifiée pouvant être interrompue ou terminée par un ou plusieurs groupements azotés et/ou par un ou plusieurs hétéroatomes tels que des atomes d'oxygène, de soufre ou d'azote, et éventuellement substituée par un ou plusieurs radicaux hydroxyle ou alcoxy en Ci-Ce ; - Rg et R10 représentent un atome d'hydrogène ou d'halogène, un radical alkyle en C1-C4, monohydroxyalkyle en C1-C4, polyhydroxyalkyle en C2-C4, aminoalkyle en C1-C4 ou un bras de liaison Y ; - R11, R12, R13, R14, R15 et R16, identiques ou différents, représentent un atome d'hydrogène, un bras de liaison Y ou un radical alkyle en C1-C4; étant entendu que les composés de formule (III) ne comportent qu'un seul bras de liaison Y par molécule.

in which: Z1 and Z2, which are identical or different, represent a hydroxyl or -NH2 radical which may be substituted by a C1-C4 alkyl radical or by a linker arm
Y; the linking 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 atoms, sulfur or nitrogen, and optionally substituted by one or more hydroxyl or alkoxy radicals Ci-Ce; - Rg and R10 represent a hydrogen or halogen atom, a C1-C4 alkyl, C1-C4 monohydroxyalkyl, C2-C4 polyhydroxyalkyl, C1-C4 aminoalkyl or a Y linkage arm; - R11, R12, R13, R14, R15 and R16, identical or different, represent a hydrogen atom, a linker Y or a C1-C4 alkyl radical; it being understood that the compounds of formula (III) have only one Y linker per molecule.

trialkyl(Ci-C4)amino, monohydroxyalkyl(CI-C4)amino, imidazolinium et ammonium. Parmi les bases doubles de formule (III) ci-dessus, on peut plus

particulièrement citer le N,N'-bis-(i-hydroxyéthyl) N,N'-bis-(4'-aminophényl) Among the nitrogen groups of formula (III) above, mention may be made especially of amino, monoalkyl (C 1 -C 4) amino, dialkyl (C 1 -C 4) amino radicals,

tri (C 1 -C 4) alkylamino, monohydroxy (C 1 -C 4) alkylamino, imidazolinium and ammonium. Among the double bases of formula (III) above, it is possible

particularly mention N, N'-bis- (i-hydroxyethyl) N, N'-bis- (4'-aminophenyl)

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1,3-diamino propanol, la N,N'-bis-((3-hydroxyéthyl) N,N'-bis-(4'-aminophényl) éthylènediamine, la N,N'-bis-(4-aminophényl) tétraméthylènediamine, la

N,N'-bis-((3-hydroxyéthyl) N,N'-bis-(4-aminophényl) tétraméthylènediamine, la N,N'-bis-(4-méthyl-aminophényl) tétraméthylènediamine, la N,N'-bis-(éthyl) N,N'-bis-(4'-amino, 3'-méthylphényl) éthylènediamine, le 1,8-bis-(2,5diaminophénoxy) -3,5-dioxaoctane, et leurs sels d'addition avec un acide.

1,3-diamino propanol, N, N'-bis - ((3-hydroxyethyl) N, N'-bis- (4'-aminophenyl) ethylenediamine, N, N'-bis (4-aminophenyl) tetramethylenediamine , the

N, N'-bis - ((3-hydroxyethyl) N, N'-bis- (4-aminophenyl) tetramethylenediamine, N, N'-bis- (4-methylaminophenyl) tetramethylenediamine, N, N'- bis- (ethyl) N, N'-bis- (4'-amino, 3'-methylphenyl) ethylenediamine, 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- (i-hydroxyethyl) N, N'-bis- (4'-aminophenyl) 1,3-diamino propanol, 1,8-bis- (2,5-Diaminophenoxy) -3,5-dioxaoctane or an acid addition salt thereof are particularly preferred.

dans laquelle : -R17 représente un atome d'hydrogène ou d'halogène, un radical alkyle en C1-C4, monohydroxyalkyle en C1-C4, alcoxy(Ci-C4)alkyle(Ci-C4), aminoalkyle

en Ci-C4 ou hydroxyalkyl(C-C4)aminoalkyle en Ci-C4, - Ris représente un atome d'hydrogène ou d'halogène, un radical alkyle en C1-C4, monohydroxyalkyle en Ci-C4, polyhydroxyalkyle en C2-C4, aminoalkyle

en C1-C4, cyanoalkyle en C1-C4 ou alcoxy(CI-C4)alkyle(Ci-C4), étant entendu qu'au moins un des radicaux R17 ou R18 est différent d'un atome d'hydrogène. Among the substituted para-aminophenols which may be used as second oxidation bases 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:

in which: R 17 represents a hydrogen or halogen atom, a C 1 -C 4 alkyl, C 1 -C 4 monohydroxyalkyl, C 1 -C 4 alkoxy (C 1 -C 4) alkyl, aminoalkyl radical;

C1-C4 or C1-C4 hydroxyalkyl (C1-C4) aminoalkyl; - R6 represents a hydrogen or halogen atom, a C1-C4 alkyl radical, a C1-C4 monohydroxyalkyl radical or a C2-C4 polyhydroxyalkyl radical; aminoalkyl

C1-C4, C1-C4 cyanoalkyl or (C1-C4) alkoxy (C1-C4) alkyl, it being understood that at least one of the radicals R17 or R18 is different from a hydrogen atom.

Among the para-aminophenols of formula (IV) above, mention may be made more particularly of para-aminophenol, 4-amino-3-methylphenol,

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 4-amino-3-fluoro phenol, 4-amino-3-hydroxymethylphenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2- aminomethyl phenol, 4-amino 2- (ss-hydroxyethylaminomethyl) phenol, 4-amino-2-fluoro phenol, and their addition salts with an acid.

Among the ortho-aminophenols that can be used as oxidation bases in the dyeing compositions in accordance with the invention, mention may be made more particularly of 2-amino phenol, 2-amino-5-methylphenol and 2-amino-6-methylphenol. 5-acetamido-2-amino phenol, and their addition salts with an acid.

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

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

Among the pyrimidine derivatives, there may be mentioned more particularly the compounds described for example in DE 2,359,399; 88-169,571; JP 05 163 124; 0 770 375 or patent application WO 96/15765 such as 2,4,5,6-tetraaminopyrimidine, 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 pyrazolopyrimidine derivatives such as those mentioned in patent application FR-A- 2,750,048 and including 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] -

<Desc / Clms Page number 16>

 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-hydroxyethyl) amino] ethanol, 2 - [(7-amino-pyrazolo [1], 5-a] pyrimidin-3-yl) - (2-hydroxyethyl) amino] ethanol, 5,6-dimethyl pyrazolo [1,5-a] pyrimidine-3,7-diamine, 2 6-dimethylpyrazolo [1,5-a] pyrimidine-3,7-diamine, 2,5, 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 acid addition salts, and their tautomeric forms, when tautomeric equilibrium exists.

Among the pyrazole derivatives, mention may be made more particularly 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- (ss-hydroxyethyl) pyrazole, 4,5-diamino-3-methyl-1-phenyl pyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 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 1- (ss-hydroxyethyl) 3-methyl pyrazole, 4,5-diamino-1-ethyl-3-methyl pyrazole, 4,5-diamino-1-ethyl-3- 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 pyrazine ole, 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- (ss-hydroxyethyl) amino-1-methyl pyrazole, and their addition salts with a 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

<Desc / Clms Page number 17>

 the dye composition, and even more preferably from 0.005 to 6% by weight approximately of this weight.

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

These couplers may especially be chosen from meta-phenylenediamines, meta-aminophenols, meta-diphenols and heterocyclic couplers such as, for example, indole derivatives, indoline derivatives, benzimidazole derivatives, benzomorpholine derivatives, sesamol derivatives, derivatives thereof. pyridines, pyrimidines and pyrazoles, and their addition salts with an acid.

phénol, le 5-N-(p-hydroxyéthyl)amino 2-méthyl phénol, le 3-amino phénol, le 1,3-dihydroxy benzène, le 1,3-dihydroxy 2-méthyl benzène, le 4-chloro 1,3-dihydroxy benzène, le 2,4-diamino 1-(ss-hydroxyéthyloxy) benzène, le 2-amino 4-(-hydroxyéthylamino) 1-méthoxy benzène, le 1,3-diamino benzène, le 1,3-bis- (2,4-diaminophénoxy) le sésamol, le 1-amino 2-méthoxy 4,5-méthylènedioxy benzène, l'a-naphtol, le 2-méthyl-1-naphtol, le 6-hydroxy indole, le 4-hydroxy indole, le 4-hydroxy N-méthyl indole, la 6-hydroxy indoline, la 2,6-dihydroxy 4-méthyl pyridine, le 1-H 3-méthyl pyrazole 5-one, le 1-phényl 3-méthyl pyrazole 5-one, et leurs sels d'addition avec un acide. These couplers are more particularly chosen from 2-methyl-5-amino

phenol, 5-N- (p-hydroxyethyl) amino 2-methyl phenol, 3-amino phenol, 1,3-dihydroxy benzene, 1,3-dihydroxy-2-methyl benzene, 4-chloro-1,3 dihydroxybenzene, 2,4-diamino 1- (ss-hydroxyethyloxy) benzene, 2-amino-4 - (- hydroxyethylamino) 1-methoxybenzene, 1,3-diamino benzene, 1,3-bis- ( 2,4-diaminophenoxy) sesamol, 1-amino-2-methoxy-4,5-methylenedioxybenzene, α-naphthol, 2-methyl-1-naphthol, 6-hydroxyindole, 4-hydroxyindole, 4-hydroxy N-methylindole, 6-hydroxyindoline, 2,6-dihydroxy-4-methylpyridine, 1-H-3-methylpyrazole-5-one, 1-phenyl-3-methylpyrazole-5-one, and their addition salts with an acid.

When present, the coupler or couplers 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 that can be used according to the invention, mention may be made of para-phenylenediamines other than those of formula (1) and (II) defined

<Desc / Clms Page number 18>

 above, such as, for example, para-phenylenediamine, paratoluylenediamine, 2-chloro-para-phenylenediamine, and para-aminophenols other than those of formula (IV) defined above, such as 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 total weight of the composition.

In general, the addition salts with an acid that can be used in the context of the dyeing compositions of the invention are especially chosen from hydrochlorides, hydrobromides, sulphates, tartrates, lactates and acetates.

The medium suitable for dyeing (or support) is generally constituted by water or a mixture of water and at least one organic solvent to solubilize compounds that are not sufficiently soluble in water.

As organic solvent, there may be mentioned for example lower alkanols C1-C4, such as ethanol and isopropanol; glycerol, glycols and glycol ethers such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and monomethyl ether, as well as aromatic alcohols such as benzyl alcohol or phenoxyethanol, the like and their derivatives. 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 by means of acidifying or basifying agents usually used for dyeing keratinous fibers.

<Desc / Clms Page number 19>

Among the acidifying agents, mention may be made, for example, of mineral or organic acids such as hydrochloric acid, orthophosphoric acid, carboxylic acids such as tartaric acid, citric acid, lactic acid, sulfonic acids.

dans laquelle R est un reste propylène éventuellement substitué par un groupement hydroxyle ou un radical alkyle en C1-C4 ; R19, R2o, R21 et R22, identiques ou différents, représentent un atome d'hydrogène, un radical alkyle en C1-C4 ou hydroxyalkyle en C1-C4. Among the alkalinizing agents that may be mentioned, for example, ammonia, alkali carbonates, alkanolamines such as mono-, di- and triethanolamines and their derivatives, hydroxyalkylamines and ethylenediamines oxyethylenated and / or oxypropylenated, the hydroxides of sodium or potassium and the compounds of formula (V) below:

in which R is a propylene residue optionally substituted by a hydroxyl group or a C 1 -C 4 alkyl radical; R19, R2o, R21 and R22, which may be identical or different, represent a hydrogen atom, a C1-C4 alkyl radical or a C1-C4 hydroxyalkyl radical.

The acidifying agents are conventionally, for example, inorganic 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 hair, such as anionic, cationic, nonionic, amphoteric, zwitterionic surfactants or mixtures thereof, anionic, cationic polymers, nonionic, amphoteric, zwitterionic or mixtures thereof, inorganic or organic thickening agents, reducing or antioxidant agents, penetrating agents, sequestering agents, perfumes, buffers, dispersing agents, agents

<Desc / Clms Page number 20>

 for example, silicones, film-forming agents, preserving agents, opacifying agents, silicone or non-silicone UV filters, vitamins or provitamines.

The reducing agents or antioxidants may be chosen in particular from sodium sulphite, thioglycolic acid, thiolactic acid, sodium bisulfite, dehydroascorbic acid, hydroquinone, 2-methyl-hydroquinone, ter- butyl hydroquinone and the homogentisic acid, and they are then generally present in amounts ranging from about 0.05 to 1.5% by weight relative to the total weight of the composition.

Preferably, the dyeing composition according to 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 substantive cationic or amphoteric polymer in a proportion preferably ranging between 0.05 and 10% by weight relative to the total weight of the composition.

Preferably, the dyeing 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 ranging 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 additional compounds or compounds mentioned above, so that the advantageous properties intrinsically attached to the dye composition according to the invention are not, or not substantially impaired by the addition or additions envisaged.

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

<Desc / Clms Page number 21>

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

According to this method, 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 moment of use to 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 process 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 which is suitable for dyeing, at least one oxidizing agent present in an amount sufficient to develop a coloration. The resulting mixture is then applied to the keratin fibers and allowed to stand for about 3 to 50 minutes, preferably about 5 to 30 minutes, after which it is rinsed, washed with shampoo, rinsed again and dried.

The oxidizing agent may 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 oxidation enzymes such as peroxidases, laccases, tyrosynases and oxydo-reductases among which 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 dyeing composition, the pH of the resulting composition applied to the keratinous fibers preferably varies

<Desc / Clms Page number 22>

 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 alkalizing agents usually used in dyeing keratinous fibers and as defined above.

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

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

Another subject of the invention is a multi-compartment device or multi-compartment dyeing kit or any other multi-compartment packaging system of which a first compartment contains the dye composition as defined above and a second compartment contains the oxidizing composition as defined above.

These devices may be equipped with means for delivering the desired mixture onto 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.

<Desc / Clms Page number 23>

EXAMPLES 1 TO 5 DYEING The dyeing compositions according to the invention were prepared as follows:

<Tb>
<tb> EXAMPLES <SEP> 1 <SEP> 2 <SEP> 3 <SEP> 4 <SEP> 5
<Tb>

Dichlorhydrate de1-(4'-amino-3'- 2.10'3 2.10-3 2.10-3 2.10-3 2.10'3

1- (4'-amino-3'-2.10'3) dihydrochloride 2.10-3 2.10-3 2.10-3 2.10'3

<Tb>
<tb> methylphenyl) -4-hydroxy-2-methyl <SEP> mole <SEP> mole <SEP> mole <SEP> mole <SEP> mole
<tb> pyrrolidine <SEP> (derived <SEP> substituted <SEP> from
<tb> para <SEP> phenylenediamine <SEP> of <SEP> formula
<tb> (I) <SEP> compliant <SEP> to <SEP> the invention)
<tb> 2-methyl <SEP> 5-amino <SEP> phenol <SEP> 3.10-3 <SEP> 3.10-3 <SEP> 3.10-3 <SEP> 3.10-3 <SEP> 3.10-3
<tb> (coupler) <SEP> mole <SEP> mole <SEP> mole <SEP> mole <SEP> mole
<tb> 4-amino <SEP> 3-methyl <SEP> phenol <SEP> 10-3 <SEP> -
<tb> (second <SEP> base <SEP> oxidation) <SEP> mole
<tb> Sulfate <SEP> of <SEP> N, N-bis- (ss-hydroxy- <SEP> - <SEP> 10-3 <SEP> -
<tb> ethyl) <SEP> paraphenylene diamine <SEP> mole
<tb> (second <SEP> base <SEP> oxidation)
<tb> tetrahydrochloride <SEP> of <SEP> N, N-bis- (ss- <SEP> - <SEP> - <SEP> 10-3
<tb> hydroxyethyl) <SEP> N, N'-bis- <SEP>(4'-amino-<SEP> mole
<tb> phenyl) <SEP> 1,3-diamino <SEP> propanol
<tb> (second <SEP> base <SEP> oxidation)
<tb> Dihydrochloride <SEP> of <SEP> 4,5-diamino <SEP> 1- <SEP> - <SEP> - <SEP> - <SEP> 10-3 <SEP> methyl <SEP> pyrazole <SEP> (second <SEP> base <SEP> mole
<tb> oxidation)
<tb> Orthoaminophenol <SEP> (second <SEP> base- <SEP> - <SEP> - <SEP> - <SEP> 10-3
<tb> oxidation) <SEP> mole
<tb> Support <SEP> of <SEP> tincture <SEP> common <SEP> (*) <SEP> (*) <SEP> (*) <SEP> (*) <SEP> (*)
<tb> Demineralized <SEP> water <SEP> qsp <SEP> 100 <SEP> g <SEP> 100 <SEP> g <SEP> 100 <SEP> g <SEP> 100 <SEP> g <SEP> 100 <SEP > g
<Tb>
(*) Common dye support: - Alkyl C8-C18 polyglucoside in aqueous solution at 60%, sold

<Tb>
<tb> under <SEP> the <SEP> name <SEP> ORAMIX <SEP> CG <SEP> 110 <SEP>#<SEP> by <SEP> the <SEP> company <SEP> SEPPIC <SEP> 5.4 <SEP> g
<tb> - <SEP> Ethanol <SEP> 18.0 <SEP> g
<tb> -Alcohol <SEP> Benzyl <SEP> 1.8 <SEP> g
<Tb>

<Desc / Clms Page number 24>

<Tb>
<tb> - <SEP> Polyethylene <SEP> Glycol <SEP> 400 <SEP> 2.7 <SEP> g
<tb> - <SEP><SEP> pentasodium salt <SEP> of <SEP><SEP> diethylene <SEP> triamine <SEP> pentacetic acid <SEP> in
<tb> aqueous <SEP> solution <SEP> to <SEP> 40%, <SEP> sold <SEP> under <SEP> the <SEP> denomination
<tb> DISSOLUINE <SEP> D-40 <SEP>#<SEP> by <SEP> the <SEP> company <SEP> AKZO <SEP> 1,08 <SEP> g
<tb> - <SEP> Metabisulfite <SEP> of <SEP> sodium <SEP> 0.205 <SEP> g
<tb> - <SEP> Ammonia <SEP> to <SEP> 20.5% <SEP> of <SEP> NH3 <SEP> 10.0 <SEP> g
<Tb>
At the time of use, the weight and weight of the dye compositions described above were mixed with a solution of hydrogen peroxide at 20 volumes (6% by weight).

The mixtures thus produced were applied for 30 minutes on strands of natural gray hair permed with 90% of whites. The locks were then rinsed, washed with standard shampoo, rinsed again and dried.

The hair has been dyed in the following shades:

<Tb>
<tb> Examples <SEP> Shades <SEP> obtained
<tb> 1 <SEP> Purple <SEP> red <SEP> supported
<tb> 2 <SEP> Purple <SEP> supported
<tb> 3 <SEP> Purple <SEP> supported
<tb> 4 <SEP> Red <SEP> supported
<tb> 5 <SEP> Brown <SEP> red <SEP> supported
<Tb>

Claims (1)

1. A composition for the oxidation dyeing of keratinous fibers and in particular human keratinous fibers such as the hair, characterized in that it comprises, in a medium suitable for dyeing: at least a first base of oxidation chosen from substituted paraphenylenediamine derivatives of formula (I) below, and their addition salts with an acid: in which: R 1 and R 2 may take on one of the following meanings i) to v): i) Ri and R2 simultaneously represent a radical - (CH2) 2CHOHCH20H; or ii) R 1 is -CH 2 (CHOH) 4 CH 2 OH and R 2 is hydrogen, alkyl, aryl or heterocycle; or iii) R1 represents an alkyl, aryl or heterocycle radical and R2 represents an alkylene radical - (CH2) m- in which m is an integer equal to 2 or 3, said alkylene radical forming a ring together with the atom of nitrogen, the carbon atom of the benzene ring bearing the nitrogen atom and one of the two carbon atoms of the benzene ring which are adjacent to it, it being understood that when R 1 is an alkyl or aryl radical, then either R 1 either said alkylene radical is substituted with a radical containing at least one nitrogen, oxygen or sulfur atom; iv) R 1 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, which are identical or different, represent a hydrogen atom, a radical alkyl, aryl or a heterocycle; v) R1 and R2 form, together with the nitrogen atom to which they are attached, a saturated 5- or 7-membered heterocycle, said heterocycle being substituted by at least one radical containing at least one carbon atom, d. nitrogen, sulfur oxygen; - 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, sulfo, alkoxy radical; aryloxy, cyanoamino, amino, anilino, ureido, sulfamylamino, mono- or di-alkylsulfamylamino, alkylthio, arylthio, alkoxycarbonylamino, sulfonamido, carbamoyl, mono- or di-alkylcarbamylsulfamyl, sulphonyl, alkoxycarbonyl, azo, acyloxy, carbamyloxy, mono- 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 may be substituted by one or more radicals and then represent a mono or polyhydroxyalkyl, alkoxyalkyl, aminoalkyl radical optionally substituted on the nitrogen atom, carboxyalkyl alkylcarboxyalkyl, thioalkyl, alkylthioalkyl, cyanoalkyl, trifluoroalkyl, sulfoalkyl, phosphoalkyl, or haloalkyl; said alkoxy radicals having from 1 to 25 carbon atoms and which may be linear, branched or cyclic; said aryl radicals having from 6 to 26 carbon atoms and being capable of being 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 may contain one or more heteroatoms, it being understood that in the case of polycyclic heterocycles, at least one ring contains at least one heteroatom such as N, O or S; <Desc / Clms Page number 27>  n is an integer from 0 to 4; understood that when n is greater than 1, then the radicals R3 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 R 1 and R 2 have the meanings defined in item v), then the compounds of formula (I) contain not more than 3 hydroxyl radicals; 2) when R 1 and R 2 have the meanings defined in point v) and R 1 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; the pyrrolidine ring bears at least two substituents; 3) when R 1 and R 2 have the meanings defined in point v) and R 1 and R 2 form a pyrrolidine ring substituted by a hydroxymethyl radical on the carbon located in alpha position with respect to the nitrogen atom to which they are attached, and that n = 0 or 1, then either said ring carries at least two additional substituents, or said ring has only a second substituent different from a hydroxyl group on the carbon located in position 3 with respect to the nitrogen and with respect to the carbon bearing said hydroxymethyl substituent; or when R1 and R2 have the meanings defined in point v) and R1 and R2 form a pyrrolidine ring substituted by a hydroxymethyl radical on the carbon located in the alpha position relative to the nitrogen atom to which they are attached, 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 fulfill at least one of the following four conditions: a) whatever the value of n, the alkylene ring formed by the radical R2 comprises a substituent in addition to the radical R1; or b) n is greater than 1; c) when n is 1, then R3 represents an aryl radical or a heterocycle; or <Desc / Clms Page number 28>  d) when n is zero or 1, then R 1 represents an aryl radical, a heterocycle or a substituted alkyl radical other than a monohydroxyalkyl radical; and at least one second oxidation base chosen from heterocyclic oxidation bases, double bases, substituted para-aminophenols, ortho-aminophenols, paraphenylenediamine derivatives of formula (II) below, and their addition salts with an acid :

 in which: R5 represents a hydrogen atom, a C1-C4 alkyl radical, a C1-C4 monohydroxyalkyl radical, a C2-C4 polyhydroxyalkyl radical or a C1-C4 alkoxy radical; C4) (C1-C4) alkyl, C1-C4 alkyl substituted by nitrogen, phenyl or 4'-aminophenyl; R6 represents a hydrogen atom, a C1-C4 alkyl radical, a C1-C4 monohydroxyalkyl radical, a C2-C4 polyhydroxyalkyl radical or a C1-C4 alkoxy radical; 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 atom, a C1-C4 alkyl radical, a C1-C4 monohydroxyalkyl radical or a C1-C4 hydroxyalkoxy radical; C4, acetylaminoalkoxy C1-C4, mesylaminoalkoxy C1-C4 or carbamoylaminoalkoxy C1-C4; - R8 represents a hydrogen atom, halogen or a C1-C4 alkyl radical; it being understood that when R5, R6 and Rs simultaneously represent a hydrogen atom, then R7 denotes neither a hydrogen atom, nor a chlorine atom, nor a methyl radical. <Desc / Clms Page number 29> 2. Composition according to claim 1, characterized in that the substituted paraphenylenediamine derivatives of formula (1) are chosen from 1-N, N-bis- (3 ', 4'-dihydroxybutyl) para-phenylenediamine, 1-N. , N-bis- (3 ', 4'-dihydroxybutyl) -3-methyl-para-phenylenediamine, 1-N, N-bis- (3', 4'-dihydroxybutyl) -3-ethyl-para-phenylenediamine, 1-N, N-bis - (3 ', 4'-dihydroxybutyl) -3-propyl-para-phenylenediamine, 1-N, N-bis- (3', 4'-dihydroxybutyl) -3-methoxy-para-phenylenediamine, 1-N, N-bis- (3 ') , 4'-dihydroxybutyl) -3-ethoxy para-phenylenediamine, 1-N, N-bis- (3 ', 4'-dihydroxybutyl) -3-propyloxy para-phenylenediamine, 1-N, N-bis- (3') 4'-dihydroxybutyl) -3-hexyloxy-para-phenylenediamine, 1-N, N-bis- (3 ', 4'-dihydroxybutyl) -3- (1 "-N-3", 5 "-dimethylpyrazolyl para-phenylenediamine) , the

 1-N, N-bis- (3 ', 4'-dihydroxybutyl) -3-ureido para-phenylene-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 ') 4-Dihydroxybutyl) -3-methylthio-para-phenylenediamine, 1-N, N-bis (3 ', 4'-dihydroxybutyl) -3-ethylthio

 1-N, N-bis- (3 ', 4'-dihydroxybutyl) -3-mercapto-para-phenylenediamine, 1-N, N-bis- (3', 4'-dihydroxybutyl) -3-n-paraphenylenediamine. butylthio paraphenylenediamine, 1-N, N-bis- (3 ', 4'-dihydroxybutyl) -3-n-octylthio

 1-N, N-bis- (3 ', 4'-dihydroxybutyl) -3-mercaptoethyl para-phenylenediamine, 1-N, N-bis- (3', 4'-dihydroxybutyl) -3-mercaptoethyl thioparaphenylenediamine, para-phenylenediamine; 1-N, N-bis- (3 ', 4'-dihydroxybutyl) -3-3-hydroxyethyl thioparaphenylenediamine, 1-N- (2', 3 ', 4', 5 ', 6'-pentahydroxyhexyl) para-phenylenediamine, 1-N- (2 ', 3', 4 ', 5', 6'-pentahydroxyhexyl) -3-methyl para-phenylenediamine, 1-N- (2 ', 3', 4 ', 5', 6 1-N- (2 ', 3', 4 ', 5', 6'-pentahydroxyhexyl) -3-methoxy-para-phenylenediamine, 1-N- (2 ', 3') -pentahydroxyhexyl) -3-isopropyl paraphenylenediamine; , 4 ', 5', 6'-pentahydroxyhexyl) -1-N- (4 "N" methylpiperidyl) -3-ethoxy para-phenylenediamine, 1-N- (2 ', 3', 4 ', 5', 6 ' pentahydroxyhexyl) -3-isopropyloxy-para-phenylenediamine, 1-N- (2 ', 3', 4 ', 5', 6'-pentahydroxyhexyl) -3-dimethylamino-para-phenylenediamine, 1-N- (2 ', 3', 4 ') , 5 ', 6'-pentahydroxyhexyl) -3-methyl thioparaphenylenediamine, the

 1-N- (2 ', 3', 4 ', 5', 6'-pentahydroxyhexyl) -3-mercapto-para-phenylenediamine, 1-N- (hexyl) -1-N- (2 ', 3', 4 ') 5 ', 6'-pentahydroxyhexyl) -3-isopropyl paraphenylene <Desc / Clms Page number 30>  diamine, 1-N- (methyl) -1-N- (2 ', 3', 4 ', 5', 6'-pentahydroxyhexyl) -3-isooctyloxy para-phenylenediamine, 1-N- (methyl) -1- N- (2 ', 3', 4 ', 5', 6'-pentahydroxyhexyl) -3-isopropyloxy para-phenylenediamine, 1-N- (methyl) -1-N- (2 ', 3', 4 ') 6-Pentahydroxyhexyl) -3-methyl-para-phenylenediamine, 1-N- (methyl) -1-N- (2 ', 3', 4 ', 5', 6'-pentahydroxyhexyl) -3-ethyl-para-phenylenediamine , the

 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 para-phenylenediamine, 1-N- (methyl) -1-N- (2 ', 3', 4 ', 5 ', 6'-pentahydroxyhexyl) paraphenylenediamine, 1-N- (phenyl) -1-N- (2', 3 ', 4', 5 ', 6'-pentahydroxyhexyl) -3-ethyloxy para-phenylenediamine, 1-N- (4 "-N-methylpiperidyl) -1-N- (2 ', 3', 4 ', 5', 6'-pentahydroxyhexyl) -3-ethyloxy para-phenylenediamine, 4-N- (methyl) -4-N- (2 ', 3', 4 ', 5', 6'-pentahydroxyhexyl) amino-

 7-Amino-1-methylindole, 1-N- (hydroxyethyloxyethyl) -1-N- (2 ', 3', 4 ', 5', 6'-pentahydroxyhexyl) -3-ethyl-para-phenylenediamine, 1-N- (3 ', 4'-dihydroxybutyl) -5-aminoindoline, 1- (2'-hydroxyethyl) -2-methyl-5-aminoindoline, 1-methyl-2-hydroxymethyl-5-aminoindoline, 6-methyl-2- hydroxyethyl-5-aminoindoline, 2-hydroxyethyloxyethyl-5-aminoindoline, 2-hydroxyethyloxyethyloxyethyloxy-ethyl-5-aminoindoline, 2-hydroxyethyloxyethyloxyethyloxyethyloxyethyloxyethyl-6-isopropyl-5-aminoindoline, 2-hydroxyethyl-3-methyl-2-hydroxyethyloxyethyloxyethyloxyethyloxyethyl 5-aminoindoline, 2-hydroxyethyloxyethyloxyethyl-5-aminoindoline, 1-carboxymethyl-2,3,3-trimethyl-5-aminoindoline, 1-methylsulfonamidoethyl-3-methyl-5-aminoindoline, ureidoethyl-6-methoxy-5-aminoindoline, 1- (2 ', 3', 4 ', 5', 6'-pentahydroxyhexyl) -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 of p-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- (hydroxyethyloxyethyloxyethyloxyethyl) -2,2,3-tetrahydroquinoline 1,2,3,4-tetrahydroquinoline, 6-amino-1- (hydroxyethyloxyethyl) -2,2,3-trimethyl-1,2,3,4-tetrahydroquinoline, 6-amino-1- ( ethyl-bis- (hydroxyethyloxyethyloxyethyloxyethyl) - 2,2,3,7-tetramethyl-1,2,3,4-tetrahydro- <Desc / Clms Page number 31>

 quinoline, 1- (carboxymethyl) -2,2,3,7-tetramethyl-1,2,3,4-tetrahydroquinoline, 1- (hydroxypropyl) -2,2,3-trimethyl-7-methoxy- 1,2,3,4-tetrahydroquinoline, 6-amino-1- (hydroxyethyloxyethyloxyethyl) -2,2,3-trimethyl-7-isopropyl-1,2,4,4-tetrahydroquinoline, amino-1- (hydroxyethyloxyethyloxyethyloxyethyloxyethyloxyethyloxyethyloxyethyl) -2,2,3-trimethyl-7-isopropyl-1,2,3,4-tetrahydroquinoline, 6-amino-1- (hydroxyethyloxyethyloxyethyloxyethyloxyethyloxyethyloxyethyloxyethyl) -2- 2,3-trimethyl-1,2,3,4-tetrahydroquinoline, 6-amino-1- (mercaptoethyl) -1,2,3,4-tetrahydroquinoline, 6-amino-1- (3 ', 4 dihydroxybutyl) -2,2,3-trimethyl-7-isopropyl-1,2,3,4-tetrahydroquinoline, 6-amino-1- (3 ', 4'-dihydroxybutyl) -2,2,7 -trimethyl-4-hydroxymethyl-1,2,3,4-tetra-

 hydroquinoline, 6-amino-1- (3 ', 4'-dihydroxybutyl) -2,2-dimethyl-4-hydroxymethyl-7-isopropyl-1,2,3,4-tetrahydroquinoline, 6-amino 1- (3-Hydroxypropyl) -2,2-dimethyl-4-hydroxymethyl-7-isopropyl-1,2,3,4-tetrahydroquinoline, 6-amino-1- (hydroxyethyloxyethyloxyethyloxyethyloxyethyloxyethyloxyethyloxyethyl) -2, 2-dimethyl-4-hydroxymethyl-7-isopropyl-1,2,3,4-tetrahydroquinoline, 6-amino-1- (hydroxyethyloxyethyloxyethyloxyethyl) -2,2-dimethyl-4-hydroxymethyl-7-isopropyl-1,2,3 4-Tetrahydroquinoline, 6-amino-1- (hydroxyethyloxyethyloxyethyloxyethyloxyethyl) -2,2-dimethyl-7-isopropyl-1,2,3,4-tetrahydroquinoline, 6-amino-1- (hydroxyethyloxyethyloxyethyloxyethyloxyethyloxyethyl) -

 2,2-dimethyl-7-isopropyl-1,2,3,4-tetrahydroquinoline, 6-amino-1- (hydroxyethyloxyethyl) -2,2-dimethyl-1,2,3,4-tetra -hydroquinoline, 6-amino-1,2,2,4,7-pentamethyl-3-hydroxy-1,2,3,4-tetrahydroquinoline, 6-amino-1- (3-hydroxypropyl) -4-hydroxypropyl - (Hydroxyethyloxyethyloxyethyloxyethyl) -2,2-dimethyl-7isopropyl-1,2,3,4-tetrahydroquinoline, 6-amino-1- (hydroxyethyloxyethyloxyethyloxyethyl) -4,4-dimethyl-1,2,3,4- tetrahydroquinoline, 6-amino-1- (3 ', 4'-dihydroxybutyl) -2,2-dimethyl-7-isopropyl-1,2,3,4-tetrahydroquinoline, 6-amino-1 - (hydroxyethyloxyethyloxyethyloxyethyl) -4- (hydroxyethyloxyethyloxyethyloxyethyl) -2,2,7-trimethyl-1,2,3,4-tetrahydroquinoline, 6-amino-1- (hydroxyethyloxyethyloxyethyloxyethyl) -2,2-dimethyl-7-one 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-tetrahydroquinoline, 6-amino 1- (3 ', 4'-dihydroxybutyl) -2,2,7-trimethyl-3-mercaptomethyl-1,2,3,4-tetrahydro- <Desc / Clms Page number 32>  quinoline, 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-6-amino 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-dimethylpyrrolidine, 1- (4'-amino-3'-methylphenyl) -3-hydroxyethyloxy pyrrolidine, 1- (4'-amino-3'-methylphenyl) -4-hydroxy-2-yl methyl pyrrolidine, 1- (4'-amino-3'-methylphenyl) -3-methylsulfonamido pyrrolidine, 1- (4'-amino-3'-phenoxyphenyl) -3-methylsulfonamido pyrrolidine, 3-n-acid 1- (4'-amino-3'-phenylsulfonic) butyl pyrrolidine, 1- (4'-amino-3'-acetylaminophenyl) -3-hydroxymethylpyrrolidine, 7-amino-4- (2'-met) pyrrolydinylbenzofuran, 1- (4'-aminophenyl) -2- (4 "-aminophenoxymethyl) piperidine, 1- (4'-amino-3'-acetylphenyl) -4-hydroxypiperidine, - (4'-aminophenyl) -2- (hydroxyethyl) piperidine, 1- (4'-amino-3'-methoxyphenyl) -2,6-dihydroxymethylpiperidine, 1- (4'-amino-3'isopropyloxyphenyl) - 2,6-dimethylpiperidine, 1- (4'-amino-3'-isopropylphenyl) -2-hydroxymethylpiperidine, 1- (4'-amino-3'-isopropyloxyphenyl) -2-hydroxymethylpiperidine, 1- (4'-amino-3'-aminophenyl) -2-hydroxymethylpiperidine, 1- (4'-amino-3'-dimethylaminophenyl) -2-mercapto-ethyloxyethylpiperidine, 1- (4'-amino) 3 '(2' ', 4' '- dichloro) anilinophenyl) -4-methylpiperidine, 1- (4'-aminophenyl) -4-methylpiperidine, 1- (4'-aminophenyl) -2,7 dimethyl azacycloheptane, 1- (4'-amino-3'-methylphenyl) -2-methylazacycloheptane, 1- (4'-amino-3'-ureidophenyl) -3-hydroxyazacycloheptane, 1- (4 ') 3-amino-3-sulfamoylaminophenyl) -2,7-dimethyl azacycloheptane, the 1- (4'- amino-3'-methylthiophenyl) -2,7-dimethylazacycloheptane, 1-N-4'-hydroxybutyl-1-N- (hydroxyethyloxyethyloxyethyl) -3-isopropyl para-phenylenediamine, 1-N-methyl-1-N- (hydroxyethyloxyethyloxyethyl) paraphenylenediamine, 1-N-phenyl-1-N- (hydroxyethyloxyethyl) paraphenylenediamine, 1-N-benzyl-1-N- (hydroxyethyloxyethyloxyethyloxyethyloxyethyl) -3-trimethylsilyl-para-phenylenediamine, 1-N-methyl-1-N- (hydroxy-éthyloxyéthyloxyéthyloxyéthyloxy- <Desc / Clms Page number 33>  ethyloxyethyloxyethyloxyethyl) -3-trimethylsilyloxy para-phenylenediamine, 1-N-ethyl-1-N- (methoxyethyloxyethyloxyethyloxyethyloxyethyl) -3-phenoxycarbonylamino para-phenylenediamine, 1-N-methyl-1-N- (methoxyethyloxyethyloxyethyl) -3- (2 ') 5'-dioxopyrrolidinyl) paraphenylenediamine, 1-N-ethyl-1N- (hydroxyethyloxyethyloxyethyl) -3-4'pyridinylthio-para-phenylenediamine, 1-N-propyl-1-N- (hydroxyethyloxyethyloxyethyl) -3-sulphinyl paraphenylenediamine, 1-N-methyl-1-N- (hydroxyethyloxyethyl) -3-phenoxycarbonyl para-phenylenediamine, 1-N, N-bis (hydroxyethyloxyethyloxyethyloxyethyl) para-phenylenediamine, 1-N, N-bis (methoxyethyloxyethyloxyethyloxyethyl) -3-isopropyloxy para-phenylenediamine, 1-N, N-bis (hydroxyethyloxyethyloxyethyl) -3-isopropyloxy para-phenylenediamine, 1-N, N-bis (hydroxyethyloxyethyloxyethyloxyethyl) -3-isopropyl paraphenylene diamine, 1-N, N-bis - (hydroxyethyloxyethyloxyethyloxyethyl) -3-isopropyl para-phenylenediamine, 1-N, Nbis (methoxyethyloxyethyloxyethyloxyethyloxyethyloxyethyloxyethyl) -3-methoxy-para-phenylenediamine, 1-N, N-bis (hydroxyethyloxyethyloxyethyloxyethyloxyethyloxyethyloxyethyloxyethyl) -3-methyl-para-phenylenediamine, 1-N N-bis- (hydroxyethyloxyethyloxyethyloxyethyl) -3-isopropyloxy-para-phenylenediamine, 1-N, N-bis (hydroxyethyloxyethyl) -3-mercaptoethyl-para-phenylenediamine, 1-N, N-bis (benzyloxyethyloxyethyloxyethyl) -3-isopropyl paraphenylenediamine, and their addition salts with an acid. 3. Composition according to claim 1 or 2, 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. 4. Composition according to claim 3, characterized in that the paraphénylènediamine derivative (s) of formula (I) represent from 0.01 to 15% by weight of the total weight of the composition. 5. 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 and 2,6-diethyl paraphenylenediamine. 2,5-dimethyl <Desc / Clms Page number 34>  paraphenylenediamine, N, N-dimethyl paraphenylenediamine, N, N-diethyl paraphenylenediamine, N, N-dipropyl paraphenylenediamine, 4-amino N, N-diethyl-3-methylaniline, N, N-bis- (P-) hydroxyethyl) paraphenylenediamine,

 4-N, N-bis (i-hydroxyethyl) amino-2-methylaniline, 4-N, N-bis (2-hydroxyethyl) amino 2-chloroaniline, 2-p-hydroxyethyl paraphenylene diamine , 2-fluoro-para-phenylenediamine, 2-isopropyl-para-phenylenediamine, N - (- hydroxypropyl) para-phenylenediamine, 2-hydroxymethyl-para-phenylenediamine, N, N-dimethyl-3-methyl-para-phenylenediamine,

 N, N- (ethyl, p-hydroxyethyl) paraphenylenediamine, N- (i, dihydroxypropyl) paraphenylenediamine, N- (4'-aminophenyl) para-phenylenediamine, N-phenyl-para-phenylenediamine, 2-p-hydroxyethyloxy-para-phenylenediamine, 2-p-acetylaminoethyloxy para-phenylenediamine, N - (methoxyethyl) paraphenylenediamine, and their addition salts with an acid. 6. Composition according to Claim 5, characterized in that the para-phenylenediamines of formula (II) are chosen from 2-isopropyl paraphenylenediamine, 2-p-hydroxyethyl paraphenylenediamine, 2-p-hydroxyethyloxy paraphenylenediamine, 2,6 dimethyl paraphenylenediamine, 2,6-diethyl paraphenylenediamine, 2,3-dimethyl paraphenylenediamine, N, N-bis (ss-hydroxyethyl) paraphenylenediamine, 2-p-acetylaminoethyloxy para-phenylenediamine, and their addition salts with an acid . 7. Composition according to Claim 6, characterized in that the paraphenylenediamines of formula (II) are chosen from 2-ss-hydroxyethyl.

 paraphenylenediamine, N, N-bis (i-hydroxyethyl) paraphenylenediamine, and their addition salts with an acid. 8. Composition according to any one of claims 1 to 4, characterized in that the double bases are chosen from the compounds of formula (III) below, and their addition salts with an acid: <Desc / Clms Page number 35>

 in which: -Z1 and Z2, identical or different, represent a hydroxyl radical or -NH2 may be substituted by a C1-C4 alkyl radical or a linker arm Y; the linking 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 atoms, sulfur or nitrogen, and optionally substituted by one or more hydroxyl or alkoxy radicals Ci-Ce; - Rg and R10 represent a hydrogen or halogen atom, a C1-C4 alkyl, C1-C4 monohydroxyalkyl, C2-C4 polyhydroxyalkyl, C1-C4 aminoalkyl or a Y linkage arm; - R11, R12, R13, R14, R15 and R16, identical or different, represent a hydrogen atom, a linker Y or a C1-C4 alkyl radical; it being understood that the compounds of formula (III) have only one Y linker per molecule. 9. Composition according to Claim 8, characterized in that the double bases of formula (III) are chosen from N, N'-bis (hydroxyethyl) N, N'-bis (4'-aminophenyl) 1. 3-diaminopropanol, N, N-bis (ss-hydroxyethyl) N, N'-bis (4'-aminophenyl) ethylenediamine, N, N'-bis (4-aminophenyl)

 tetramethylenediamine, N, N'-bis- (3-hydroxyethyl) N, N'-bis (4-aminophenyl) tetramethylenediamine, N, N'-bis- (4-methylaminophenyl) tetramethylenediamine, N, N Bis (ethyl) N, N'-bis (4'-amino, 3'-methylphenyl) <Desc / Clms Page number 36>  ethylenediamine, 1,8-bis (2,5-diaminophenoxy) -3,5-dioxaoctane, and their addition salts with an acid. 10. Composition according to any one of claims 1 to 4, characterized in that the substituted para-aminophenols are chosen from the compounds of formula (IV) below, and their addition salts with an acid:

 in which: R 17 represents a hydrogen or halogen atom, an alkyl radical

 C1-C4, C1-C4 monohydroxyalkyl. (C1-C4) alkoxy (C1-C4) alkyl, (C1-C4) aminoalkyl or (C1-C4) hydroxyalkyl (C1-C4) aminoalkyl. R18 represents a hydrogen or halogen atom, a C1-C4 alkyl radical, a C1-C4 monohydroxyalkyl radical, a C2-C4 polyhydroxyalkyl radical or aminoalkyl radical;

 C1-C4, C1-C4 cyanoalkyl or (C1-C4) alkoxy (C1-C4) alkyl, it being understood that at least one of the radicals R17 or R18 is different from a hydrogen atom. 11. Composition according to Claim 10, characterized in that the para-aminophenols of formula (IV) are chosen from para-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluoro phenol and 4-amino. 3-hydroxymethyl phenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol, 4-amino-2- hydroxyethyl aminomethyl) phenol, 4-amino-2-fluoro phenol, and their addition salts with an acid. 12. Composition according to any one of claims 1 to 4, characterized in that the ortho-aminophenols are chosen from 2-amino phenol, 2-amino-5-methyl phenol, 2-amino-6-methyl phenol, -acetamido 2-amino phenol, and their addition salts with an acid. <Desc / Clms Page number 37> 13. Composition according to any one of claims 1 to 4, characterized in that the heterocyclic bases are chosen from pyridine derivatives, pyrimidine derivatives, pyrazole derivatives, and their addition salts with an acid. 14. Composition according to any one of the preceding claims, characterized in that the oxidation base or bases used as the second oxidation base represent from 0.0005 to 12% by weight of the total weight of the dye composition. . 15. Composition according to Claim 14, characterized in that the oxidation base (s) used as the second oxidation base represent from 0.005 to 6% by weight of the total weight of the dyeing composition. 16. Composition according to any one of the preceding claims, characterized in that it contains at least one coupler chosen from meta-phenylenediamines, meta-aminophenols, metadiphenols and heterocyclic couplers, and their addition salts with an acid. . 17. Composition according to claim 16, characterized in that the couplers are chosen from 2-methyl-5-amino phenol,

 5-N- (α-hydroxyethyl) amino-2-methylphenol, 3-amino phenol, 1,3-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene, 4-chloro-1,3-dihydroxybenzene 2,4-diamino-1- (ss-hydroxyethyloxy) benzene, 2-amino-4- (ss-hydroxyethylamino) -1-methoxybenzene, 1,3-diamino benzene, 1,3-bis- (2, 4-diaminophenoxy) sesamol, 1-amino-2-methoxy-4,5-methylenedioxybenzene, α-naphthol, 2-methyl-1-naphthol, 6-hydroxyindole, 4-hydroxyindole, 4-diaminophenoxy N-methyl-indole, 6-hydroxyindoline, 2,6-dihydroxy-4-methylpyridine, 1-H-3-methylpyrazole-5-one, 1-phenyl-3-methyl-pyrazole-5-one, and their addition salts with an acid. <Desc / Clms Page number 38> 18. Composition according to Claim 16 or 17, characterized in that the coupler or couplers represent from 0.0001 to 15% by weight relative to the total weight of the composition. 19. Composition according to any one of the preceding claims, characterized in that it contains one or more additional oxidation bases selected from para-phenylenediamine, paratoluylenediamine, 2-chloro-para-phenylenediamine, 4-amino phenol, and their addition salts with an acid. 20. Composition according to any one of the preceding claims, characterized in that the addition salts with an acid are chosen from hydrochlorides, hydrobromides, sulphates, tartrates, lactates and acetates. 21. A 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 20, the color being revealed at acidic, neutral or alkaline pH with the aid of an oxidizing agent which is added just at the moment of use to the dyeing composition or which is present in an oxidizing composition applied simultaneously or sequentially separately. 22. The method of claim 21, characterized in that the oxidizing agent is selected from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts and oxidation enzymes. 23. A multi-compartment device or "kit" containing several compartments, a first compartment contains a dye composition as defined in any one of claims 1 to 20 and a second compartment contains an oxidizing composition.