FR3014687A1 - PROCESS FOR COLORING KERATINIC MATERIALS FROM OLIGOMERS AND / OR COLOR POLYMERS FROM COUPLERS, COMPOSITION AND COLORING AGENT - Google Patents

Abstract

The subject of the invention is a) a process for dyeing keratin materials from a coloring agent chosen from oligomers and colored polymers obtained from the polycondensation of i) coupler in the presence of at least one ii) selected ingredient among the radical initiators and the chemical oxidizing agents, b) a composition comprising one or more colored oligomers and / or one or more colored polymers as defined above, c) a coloring agent, oligomer or colored polymer, obtained by reaction between i) and ii) as defined above and the use of the oligomer or colored polymer for dyeing the keratin materials. The dyeing method and the composition according to the invention makes it possible in particular to obtain a long-lasting coloration on the fibers. keratinous, intense, chromatic, and / or homogeneous.

Description

The invention relates to a) a process for the dyeing of keratin materials, especially keratinous fibers, preferably human fibers. such as hair, from a coloring agent chosen from oligomers and colored polymers obtained from the polycondensation of i) couplers in the presence of one or more ii) ingredients chosen from radical initiators and / or agents chemical oxidants, b) a composition comprising one or more colored oligomers and / or one or more colored polymers as defined above, c) a coloring agent, oligomer or colored polymer, obtained by reaction between i) and ii) as defined previously and the use of the one or more oligomers or colored polymers for dyeing keratin materials. It is known to dye the fibers keratinous, by direct staining or semi-permanent staining. Direct staining or semi-permanent staining involves bringing color through a colored molecule that adsorbs on the surface of the hair or penetrates the hair. Thus, the method conventionally used in direct dyeing consists in applying to the keratin fibers direct dyes which are colored and dyestuff molecules having an affinity for the fibers, to leave the fibers in contact with the coloring molecules and then possibly rinsing the fibers. Generally, this technology leads to chromatic colorations. To date, the main direct dyes used in hair dyeing are low molecular weight dyes. They generally present, because of their size, a good affinity for the hair fiber. But because of their solubility in water and their size, they have low tenacity to shampoos. In addition, natural and fundamental colors are generally difficult to achieve. It has also been described the synthesis of high molecular weight direct dyes (WO 2011/006946, WO 2011/113676, and WO 2011/113675). A priori, these colored polymers do not penetrate into the hair fiber. They tend to be deposited around keratinous fibers which causes particular problems of touch and / or tenacity to shampoos. There is therefore a real need to find new direct dyes that are able to mount well on the hair fiber, to have excellent tenacity including shampoo, to present a very good touch and to achieve natural colors and fundamental and / or which provides a coloration of the keratin fibers which are not very selective (ie whose color difference along the same keratin fiber between its tip and its root is weak, or homogeneous from one fiber to another. achieved with the present invention which firstly relates to a staining process using at least one coloring agent, obtained from the polycondensation of i) couplers reacting with each other in the presence of one or more ingredients ii) selected from among radical initiators and or chemical oxidizing agents. Another object is a coloring agent obtained from the polycondensation of i) couplers reacting with each other in the presence of ii) at least one radical initiator and / or at least one chemical oxidizing agent, it being understood that the couplers are different from 2,5-dimethoxyaniline, 2-methyl-5-methoxyaniline, 2-methoxy-5-methylaniline, 3-aminophenol. Another subject of the invention is a composition comprising at least one coloring agent as defined above; preferably not comprising an oxidation base and / or hydrogen peroxide. Another subject relates to the use of a coloring agent as defined above for dyeing keratin materials, especially keratinous fibers, in particular human fibers such as the hair. The colorations obtained with the coloring process, the composition, or from the coloring agent (s) of the invention are aesthetic, intense, chromatic, and / or very stubborn with respect to common aggressions such as the sun, perspiration, sebum, and other hair treatments such as shampoos, while respecting keratin fibers. The intensity obtained is particularly remarkable. It is the same for the homogeneity of the color of keratin fibers i.e. of low selectivity from root to tip. For the purposes of the present invention, and unless a different indication is given: "Coloring agent" means an oligomer and / or polymer resulting from a covalent assembly, linear or otherwise, of a greater number or equal to 2 repeating units or monomeric units, resulting from the polycondensation of couplers with each other only, ie the oligomeric and / or polymeric chain does not comprise a monomeric unit originating from oxidation base for example; said coloring agent has a high molecular weight, particularly greater than or equal to 230 g / mol, preferably greater than 300 g / mol; By "oligomer" is meant a compound comprising from 2 to 4 monomeric units derived from the polycondensation of couplers between them only i.e. free in the oligomeric chain of monomeric unit derived from oxidation base; "Polymer" means a compound comprising at least 5 monomeric units and preferably between 5 and 100 monomeric units derived from the polycondensation of couplers between them only i.e. free in the monomeric unit polymer chain derived from oxidation base; the "aryl" or "heteroaryl" radicals or the aryl or heteroaryl part of a radical may be substituted by at least one substituent borne by a carbon atom, chosen from: a C 1 -C 8 alkyl radical, optionally substituted by one or more radicals chosen from hydroxyl, C 1 -C 4 alkoxy, (PolY) -hydroxyalkoxy C 2 -C 4, acylamino, amino radicals substituted by two identical or different C 1 -C 4 alkyl radicals, optionally carrying at least a hydroxyl group or both radicals which can form with the nitrogen atom to which they are attached, a 5- to 7-membered, preferably 5 or 6-membered, optionally substituted saturated or unsaturated heterocycle optionally comprising another identical heteroatom; or different from nitrogen; a halogen atom; a hydroxyl group; a C1-C4 alkoxy radical; a (poly) -hydroxyalkoxy radical at 02-04; an amino radical; an amino radical substituted with one or two identical or different C 1 -C 6 alkyl radicals optionally carrying at least: i) a hydroxyl group, ii) an amino group optionally substituted with one or two C 1 -C 3 alkyl radicals optionally substituted, iii) a quaternary ammonium group -N + R'R "R" ', M- for which R', R ", which may be identical or different, represent a hydrogen atom or a C 1 -C 4 alkyl group, and M - represents the anionic counterion, - an acylamino radical (-NR-C (O) -R ') in which the radical R is a hydrogen atom or a C1-C4 alkyl radical optionally carrying at least a hydroxyl group and the radical R 'is a C1-C4 alkyl radical; a carbamoyl radical ((R) 2N-C (O) -) in which the radicals R, which may be identical or different, represent a hydrogen atom, a C1-C4 alkyl radical optionally bearing at least one hydroxyl group; -an alkylsulfonylamino radical (R'-S (O) 2 -N (R) -) in which the radical R represents a hydrogen, a C1-C4 alkyl radical optionally bearing at least one hydroxyl group and the radical R 'represents a C1-C4 alkyl radical or a phenyl radical; an aminosulphonyl radical ((R) 2 N -S (O) 2 -) in which the R radicals, which may be identical or different, represent a hydrogen atom or a C 1 -C 4 alkyl radical optionally bearing at least one hydroxyl group; a carboxylic radical in acid or salified form (preferably with an alkali metal or an ammonium, substituted or unsubstituted); a cyano group; a nitro or nitroso group; a polyhaloalkyl group, preferentially trifluoromethyl; the cyclic or heterocyclic portion of a non-aromatic radical may be substituted by at least one substituent selected from: hydroxyl groups; - C1-C4 alkoxy, (poly) hydroxyalkoxy at 02-04; C1-C4 alkyl; alkylcarbonylamino (RC (O) -NR'-) in which the radical R 'is a hydrogen atom, a C1-C4 alkyl radical optionally bearing at least one hydroxyl group and the radical R is an alkyl radical; C1-C2, amino optionally substituted with one or two identical or different C1-C4 alkyl groups, themselves optionally bearing at least one hydroxyl group; alkylcarbonyloxy (RC (O) -O-) in which the radical R is a C 1 -C 4 alkyl radical, an amino group optionally substituted by one or two identical or different C 1 -C 4 alkyl groups, themselves optionally bearing minus one hydroxyl group; alkoxycarbonyl or aminocarbonyl (RGC (O) -) in which the radical R is a C 1 -C 4 alkoxy radical, G is an oxygen atom, or an amino group optionally substituted by a C 1 -C 4 alkyl group itself optionally carrying at least one hydroxyl group; a cyclic, heterocyclic, or nonaromatic portion of an aryl or heteroaryl radical may also be substituted by one or more oxo groups; an "aryl" radical represents a carbon group, mono- or polycyclic, condensed or not, comprising from 6 to 22 carbon atoms, and of which at least one ring is aromatic; preferably the aryl radical is phenyl, biphenyl, naphthyl, indenyl, anthracenyl, or tetrahydronaphthyl, more preferably phenyl; a "heteroaryl radical" represents a mono or polycyclic group, condensed or not, optionally cationic, comprising from 5 to 22 members, from 1 to 6 heteroatoms chosen from nitrogen, oxygen, sulfur and selenium; (preferably selected from N, O and S) and wherein at least one ring is aromatic; preferably heteroaryl is selected from acridinyl, benzimidazolyl, benzobistriazolyl, benzopyrazolyl, benzopyridazinyle, benzoquinolyl, benzothiazolyl, benzotriazolyl, benzoxazolyl, pyridinyl, tetrazolyl, dihydrothiazolyl, imidazopyridinyl, imidazolyl, indolyl, isoquinolyl, naphthoimidazolyle, naphthooxazolyle, naphthopyrazolyle, oxadiazolyl, oxazolyl, oxazolopyridyl phenazinyl, phenoxazolyl, pyrazinyl, pyrazolyl, pyrilyl, pyrazoyltriazyl, pyridyl, pyridinoimidazolyl, pyrrolyl, quinolyl, tetrazolyl, thiadiazolyl, thiazolyl, thiazolopyridinyl, thiazoylimidazolyl, thiopyrylyl, triazolyl, xanthylyl and its ammonium salt; - A "cationic heteroaryl radical" is a heteroaryl group as defined above which comprises an endocyclic or exocyclic quaternized cationic group, o when the cationic charge is endocyclic, it is taken in the electronic delocalization by mesomere effect, for example it is of pyridinium, imidazolium or indolinium group: with R and R 'being a heterorayl substituent as defined above and particularly a (hydroxy) (C 1 -C 8) alkyl group such as methyl; when the cationic charge is exocyclic, for example it is a substituent R + ammonium, phosphonium, such as trimethylammonium, being outside heteroaryl such as pyridinyl, indolyl, imidazolyl, or naphthalimidyl in question: with R a heteroaryl substituent as defined above and R + an ammonium group RaRbR, N + -, phosphonium RaRbR, P + - or ammonium RaRbR, N + - (Ci-C6) alkylamino with Ra, Rb and R, which are identical or different, represent an atom of hydrogen or a group (C1-C8) alkyl such as methyl; a "heterocyclic radical" or is a radical which may contain one or two unsaturations but not aromatic, mono or polycyclic, condensed or not, containing from 5 to 22 members, comprising from 1 to 6 heteroatoms selected from nitrogen, oxygen, sulfur and selenium (preferably selected from N, RN 1, R 1 and R 2), a "heterocycloalkyl radical" is a heterocyclic radical comprising the ego In a saturated ring: an "alkyl radical" is a linear or branched C 1 -C 20 hydrocarbon radical, preferably a C 1 -C 8 hydrocarbon radical; the expression "optionally substituted" assigned to the alkyl radical implies that said alkyl radical may be substituted by one or more radicals chosen from the radicals i) hydroxyl, ii) alkoxy C1-06, iii) acylamino, iv) amino optionally substituted with one or two identical or different C 1 -C 4 alkyl radicals, said alkyl radicals being capable of forming, with the nitrogen atom carrying them, a 5- to 7-membered heterocyl, optionally comprising another heteroatom which may or may not be different nitrogen; v) or a quaternary ammonium group -N + R'R "R" ', M- for which R', R ", which may be identical or different, represent a hydrogen atom, or a C1-C4 alkyl group, or else - N + R'R "R" 'forms a heteroaryl such as imidazolium optionally substituted by a C1-C4 alkyl group, and M- represents the anionic counterion; an "alkoxy radical" is an alkyl-oxy radical for which the alkyl radical is a hydrocarbon radical, linear or branched, C1-C10 preferably C1-C8; - "alkylthio radical" is an alkyl-S- radical for which the alkyl radical is a hydrocarbon radical, linear or branched, in Cl C.sub.1 -C.sub.10 preferably, when the alkoxy or alkylthio group is optionally substituted, this implies that the alkyl group is optionally substituted as defined above, - "organic or inorganic acid salt" is more particularly understood to mean salts selected from a salt derived from i) hydrochloric acid HCI, ii) hydrobromic acid HBr, iii) sulfuric acid H2504, iv) alkylsulphonic acids: Alk-S (O) 20H such as methylsulfonic acid and ethylsulfonic acid; v) arylsulfonic acids: Ar-S (O) 20H such as benzene sulfonic acid and toluene sulfonic acid; (vi) citric acid; vii) succinic acid; viii) tartaric acid; ix) lactic acid, x) alkoxysulfinic acids: Alk-O-S (O) OH such as methoxysulfinic acid and ethoxysulfinic acid; xi) aryloxysulfinic acids such as tolueneoxysulfinic acid and phenoxysulfinic acid; xii) phosphoric acid H3PO4; xiii) acetic acid CH3C (O) OH; xiv) triflic acid CF3SO3H and xv) tetrafluoroboric acid HBF4; the term "anionic counterion" means an anion or an anionic group derived from organic or inorganic acid salt counterbalancing the cationic charge of the dye; more particularly the anionic counterion is selected from i) halides such as chloride, bromide; ii) nitrates; iii) sulfonates, including C1-C6 alkylsulfonates: Alk-S (O) 20- such as methylsulfonate or mesylate and ethylsulfonate; iv) arylsulfonates: Ar-S (O) 20- such as benzenesulphonate and toluenesulphonate or tosylate; v) citrate; vi) succinate; (vii) tartrate; viii) lactate; ix) alkyl sulphates: Alk-O-S (O) O- such as methysulphate and ethylsulphate; x) arylsulfates: Ar-O-S (O) O- such as benzenesulphate and toluenesulphate; xi) alkoxysulfates: Alk-O-S (O) 20- such as methoxy sulfate and ethoxysulfate; xii) aryloxysulfates: Ar-OS (O) 20-, xiii) the phosphates O = P (01-1) 2-0-, O = P (O-) 2-01-1 0 = P (O-) 3, HO-P (O) (O-) 1w-P (O) (O-) 2 with w being an integer; (xiv) acetate; xv) triflate; and xvi) borates such as tetrafluoroborate, xvii) (0 =) 2S (O-) 2 or SO42- disulfate and HSO4- monosulfate; the anionic counterion, derived from organic or inorganic acid salt, ensures the electroneutrality of the molecule so it is understood that when the anion comprises several anionic charges then the same anion can be used for the electroneutrality of several cationic groups in the same molecule or else can be used for the electroneutrality of several molecules; for example a dislufure dye of formula (I) which contains two cationic chromophores may contain either two "monocharged" anionic ions or contains an anionic counterion "bicharged" such that (0 =) 2S (O-) 2 or 0 = P (0-) 2-01-1; Moreover, the addition salts that can be used in the context of the invention are chosen from among the addition salts with a cosmetically acceptable base, such as the alkaline agents as defined below, such as alkali metal hydroxides such as sodium hydroxide. potash, ammonia, amines or alkanolamines; ^ the expression "at least one" is equivalent to "one or more"; and "inclusively" for a concentration range means that the range terminals fall within the defined range. i) Couplers The process for preparing the coloring agent (s) of the invention uses one or more couplers, which are identical or different, preferably identical to one another. By "coupler" is meant a colorless or weakly colored compound, known to those skilled in the art, which can not stain in the presence of oxygen in the air, which is coupled with an oxidation base to generate the color keratinous fibers in the conventional oxidation dyeing process (see, for example, Kirk-Othmer Encyclopedia of Chemical Technology, "Hair Preparation", 4th Ed., Vol 12, 1994, 904; Ullmann's Encyclopedia of Industrial Chemistry, "Hair preparation" 2002 DOI: 10.1002 / 14356007.a12-571). The couplers according to the invention comprise at least one (hetero) aryl group substituted with an electron-donor group by the mesomeric (+ M) effect, preferably hydroxy or amino, and preferably comprises a second mesomeric electron-donor group (+ M) positioned in meta of said electron-donor group on r (hetero) aryl, more preferably the electron-donor group or groups are chosen from hydroxy, amino, (di) (C1-C10) (alkyl) amino with alkyl groups optionally substituted in particular with one or more hydroxyl groups. More preferably, the couplers of the invention are of formulas (I) to (IV) below: ## STR2 ## 3 6 4 - 8 7 y 9 1 IIY 6 4 Z 3 5 - 7 1 \\ 2 zz 6 5 3 (IV) X (R 1) r, X (R 1) r, (II) (III) X (R 1) r, as well as their salts of acids or mineral or organic bases, their optical isomers, geometrical, their tautomers, and / or their solvates such as hydrates; formulas (I) to (IV) in which: X represents a radical bonded to the remainder of the molecule covalently to a carbon atom, said radical a group chosen from: i) hydroxyl, ii) amino, iii) (di ) (01- 06) alkylamino wherein the one or both alkyl groups are optionally substituted by one or more radicals selected from hydroxyl, (C1-C6) alkoxy, (di) (C1-C6) (alkyl) amino, carboxy (-0 (0) -OH), sulfonic (-SO3H), amino, sulfate-OSO3H; - R1 represents a radical bonded to the remainder of the molecule covalently to a carbon atom, said radical R1 is chosen from: i) halogen; ii) hydroxyl OH; iii) SH thiol; iv) amino; y) (di) (C1-C12) alkylamino wherein the one or both alkyl groups of the amino are optionally substituted by one or more atoms or radicals selected from: 1) hydroxyl, 2) (C1-C6) alkoxy, (3) amide or aminocarbonyl (-C (O) -NH2), 4) (di) (C1C6) alkylamino, 5) carboxy (-O (O) _OH), 6) sulfonic (-SO3H), 7) heterocycloalkyl comprising from 5 to 7 monocyclic linkers such as pyrrolidinyl, N- (O-C6) alkylpyrrolidinyl, piperidinyl, morpholinyl, N- (O-C6) alkylpiperazinyl; 8) 5- to 7-membered heteroaryl, monocyclic such as pyridinyl, tetrahydrofuranyl or imidazolyl; 9) aryl such as phenyl; 10) halogen; 11) nitrile; 12) cationic heterocycloalkyl comprising from 5 to 7 chain members, monocyclic such as N, N-di (01-06) alkylpiperazinium, N- (01-06) alkyl, AP- (01-06) alkylpiperazinium, N- (O-C6) ) alkylpiperidinium, N- (O-C6) alkylmorpholinium, N- (O-C6) alkylpyrrolidinium; 13) 5- to 7-membered cationic heteroaryl, monocyclic such as N- (O-C6) alkylpyridinium, N- (O-C6) alkylimidazolium; 14) tri- (O-C6) alkylammonium; 15) (di) (01-06) alkylaminocarbonyl or (di) (01-06) alkylacetamido; 16) H-C (O) -N (C1-C6) (alkyl) amino or (01-06) (alkyl) carbonyl (01-06) (alkyl) amino such as acetamido CH3-C (O) -NH-; 17) -NH-S (O) 2-R2, 18) C1-C6 alkylcarbonyl; and 19) urea (-NH-C (O) -NH 2) and 20) halo; vi) (C1-C6) alkyl optionally substituted with one or more atoms or groups selected from 1) to 20) as defined above for v); vii) (C1-C6) alkoxy optionally substituted with one or more atoms or groups selected from 1) to 20) as defined above for v); the alkyl chain of the alkoxy which can be interrupted by one or more oxygen atoms, preferably 1 oxygen atom; viii) (C1-C6) alkylthio optionally substituted with one or more atoms or groups selected from 1) to 20) as defined previously for vi); the alkyl chain of the alkylthio may be interrupted by one or more sulfur atoms, preferably 1 sulfur atom; ix) (hetero) aryl (C1-C6) (alkyl) amino such as phenylamino Ph-N (H) -; x) (hetero) (C1-C6) cycloalkyl (alkyl) amino such as cyclohexylamino; xi) (hetero) aryloxy such as phenoxy Ph-O-; xii) (hetero) arylthio such as phenylthio Ph-S-; xiii) R2-C (W) -W'- with R2 representing a hydrogen atom or a group selected from (C1-C12) alkyl, aryl such as phenyl and aryl (C1-C6) alkyl such as benzyl, W representing an oxygen atom, a sulfur atom or an N (R 3) amino group, preferably oxygen, and W 'representing an oxygen, sulfur atom or N (R 4) group with R 3 and R 4, which may be identical or different representing a hydrogen atom or a (C 1 -C 4) alkyl group, preferably a hydrogen atom; xiv) R2- (W) p-C (VV) - with R2, and W, and W 'as previously defined and p is 0 or 1; xv) R2-W'-C (W) -W "- with R2 being as defined above, R3 and R4, identical or different, representing a hydrogen atom or a (C1-C4) alkyl group, preferably a a hydrogen atom, W being as defined above, preferably an oxygen atom and W 'being as defined for W, preferably representing a group N (R3) with R3 as defined above; xvi) R2-W - C (W) - with R2, W and W 'being as previously defined; xvii) R2-S (O) p- (N) q- with R2 and W as previously defined and p valant 1 or 2 and ## STR2 ## where R 2 and p are as defined above, xix) aryl such as phenyl, xx) cationic or non-cationic heteroaryl such as imidazolyl or N- (C1-C6) alkylimidazolium; xxi) 5 to 7-membered monocyclic heterocycloalkyl, cationic or non-cationic, preferably chosen from a) piperidino optionally substituted with one or more -C (O) NH2 or (hydroxy) (C1-C6) alkyl groups, N- (C1-C6) alkylimidazolium, b) pyrrolidino optionally substituted by one or more hydroxyl, (C1-C6) alkyl, (di) (C1-C6) (alkyl) amino, tri (C1-C6) alkyl ammonium radicals, N- (C1-C6) alkylimidazolium, c) piperazino may be functionalized with one or more (C1-C6) alkyl groups; d) N, N- (C1-C6) dialkylpiperazinium; e) (di) azepano; f) morpholino; xxii) a nitrile radical (-CN); n represents an integer between 0 and 6, preferably between 1 and 4; Y represents a carbon atom, a CH group or a nitrogen atom; Z represents i) a carbon atom, a CH group or a CRi group; ii) a heteroatom selected from oxygen or sulfur atom when Z is at position 3 of formula (III), or at position 3 or 5 of formula (IV); iii) a nitrogen atom when Z is in position 1 or 2 of formula (III) or in position 1, 2, 6 and 7 of formula (IV); iv) NR5 when Z is in the 3 position of the formula (III) or 3 and 5 of the formula (IV) with R5 representing a hydrogen atom or a (C1-C6) alkyl group optionally substituted by one or more radicals a) hydroxyl, b) (ClC6) alkoxy, c) (di) (C1-C6) (alkyl) amino, d) heterocycloalkyl or heterraryl with 5 or 6 chain members preferably cationic such as N, N '- (C1- C6) alkylpyperazinium, N- (C1-C6) alkylpyperidinium, N- (C1-C6) alkyl-morpholinium or N- (C1-C6) alkylimidazolum, e) carboxy, or f) sulfonic acid; it being understood that: when n is greater than or equal to two, the radicals R 1 are identical or different; when the compounds of formula (I) to (IV) comprise a cationic group, an anionic counterion is associated to reach the electroneutrality of the molecule, two adjacent radicals R 1 may together form a ring a fused heterocyclic ring such as morpholino ; for the formula (II), X or R 1 are bound on carbon atoms 1 to 4 or 6 to 9; for the formula (III), X or R 1 are bound on the carbon atoms 1, 2 to 5 or on a carbon or nitrogen atom 3; and for the formula (IV), X or R1 are bonded on one of the carbon atoms 1, 2, 6 and 7, or on a carbon or nitrogen atom 3 and 5. Preferably, R2 represents a carbon atom. hydrogen or a C1-C6 alkyl, phenyl or 4-methylphenyl group.

Preferably, the couplers of the invention are of formula (I) as defined above and more particularly benzene and include an amino group X, or (di) (C1-C6) alkylamino whose or both alkyl groups are optionally substituted by a or more radicals selected from hydroxyl, (C1-C6) alkoxy, (di) (C1-C6) (alkyl) amino, carboxy (-O (O) -OH), sulfonic (-SO3H). According to a particular embodiment of the invention, the coupler (s) are chosen from metabenzenic couplers of formula (Ib): ## STR1 ## as well as their salts of inorganic or organic acids or bases, and their optical isomers , geometric, their tautomers, and / or their solvates such as hydrates; Formula (lb) wherein: L represents i) a halogen atom; or a group selected from: ii) R8-G- and iii) R2- (VV ') pC (VV) - (VV ") q- such as carboxy or (C1-C6) alkylcarbonyl with p, q = 0 or 1 , R2 representing a hydrogen atom or a group selected from (C1-C6) alkyl, W representing an oxygen atom, sulfur or an amino group N (R3), preferably an oxygen atom and W 'and W "representing an oxygen atom, sulfur atom or a group N (R4) with R3, and R4, identical or different, representing a hydrogen atom or a (C1-C4) alkyl group, preferably a hydrogen atom; ; preferably L is R8-0-; G represents a bond, an oxygen or sulfur atom, preferably oxygen; R6 and R7, which may be identical or different, represent a hydrogen atom or a (C1-C6) alkyl group optionally substituted by one or more hydroxyl groups; preferably R6 and R7 represent a hydrogen atom or else R6 and R7 form, with the nitrogen atom which carries them, a monocyclic heterocycle comprising from 5 to 7 members such as pyrrolidino optionally; piperazino may be substituted with one or more (C1-C8) alkyl groups; C8) alkylpiperidino and (di) azepano; R8 represents a hydrogen atom; a (C1-C6) alkyl group optionally substituted by one or more hydroxyl groups; or a group S (O) 2 -R9 with R9 representing a hydrogen atom or a (C1-C6) alkyl group; it being understood that when G represents a bond then R8 can not represent a hydrogen atom; n 'is 0, 1, 2 or 3 particularly 0, 1 or 2, preferably 0 or 1; R, b represents a halogen atom, or a group chosen from: 1) (C1-C6) alkyl optionally substituted by one or more atoms or halogen, hydroxy or cyano groups, 2) (C1-C6) alkoxy optionally substituted by one or more groups selected from hydroxy, 3) -SO3H, and 4) R'9-SO3- with R'9 representing a hydrogen atom or a (C1-C6) alkyl group According to another advantageous variant of the invention the couplers are of formula (Ib) with n 'and Rib as defined above and R6 forms together with a rib - - - - - - 30 radical contiguous monocyclic heterocycle comprising from 5 to 7 members such as morpholinyl, pyperidinyl, optionally pyperazynyl substituted by one or more (C1C4) alkyl PYRIDINIC group According to a particular embodiment of the invention, the coupler or couplers are chosen from pyridine couplers of formula (Ic) or (Id): N / N (Rid) r, R6 e) ,, GH R7 (Ic) (Id) as well as their salts of acids or mineral or gold bases ganes, their optical, geometric isomers, their tautomers, and / or their solvates such as hydrates; Formulas (Ic) or (Id) in which: G is an oxygen or sulfur atom, preferably oxygen; R 6 and R 7, which may be identical or different, represent a hydrogen atom or a (C 1 -C 6) alkyl group optionally substituted with one or more hydroxyl groups; preferably, R6 and R7 represent a hydrogen atom or else R6 and R7 form, with the nitrogen atom carrying them, a monocyclic heterocycle comprising from 5 to 7 members, such as pyrrolidino optionally substituted with a (di) (C1-) group; C4) (alkyl) amino or a cationic group such as tri (C1C6) alkylammonium; piperazino optionally substituted with one or more (C1-C6) alkyl groups; (C1-C6) (alkyl) piperidino or (di) azepano; n 'is 0, 1, 2 or 3 particularly 0, 1 or 2, preferably 0 or 1; - Rid or Rie, represents a halogen atom, or a group chosen from: 1) (C1C6) alkyl optionally substituted by one or more atoms or halo or hydroxy groups; 2) (C1-C6) alkoxy optionally substituted with one or more groups selected from hydroxy; 3) cyano; 4) amino; 5) (di) (C1-C12) alkylamino wherein one or both alkyl groups of the amino are optionally substituted by one or more hydroxyl groups; 6) R2- (VV ') pC (VV) - (VV ") q- such that carboxy with p, q = 0 or 1, R2 representing a hydrogen atom or a group selected from (C1-C6) alkyl, W representing an oxygen atom, sulfur atom or an N (R 3) amino group, preferably an oxygen atom and W and W 'representing an oxygen atom, sulfur atom or an N (R 4) group with R 3, and R4, identical or different, representing a hydrogen atom or a (C1-C4) alkyl group, preferably a hydrogen atom, and 7) hydroxyl.

According to a particular embodiment of the invention, the coupler or couplers are chosen from 2-aminopyrimidine couplers of formula (Ic) and 2-aminopyrazine of formula (If): ## STR2 ## R7 R7 (Ie) (Ie) as well as their salts of mineral or organic acids or bases, their optical, geometric isomers, their tautomers, and / or their solvates such as hydrates; Formulas (Ie) or (If) in which: R6 and R7, which may be identical or different, represent a hydrogen atom or a (C1-C6) alkyl group optionally substituted by one or more hydroxyl groups or a (hetero) cycloalkyl group such as cyclohexyl; preferably R6 and R7 represent a hydrogen atom; or else R6 represents a hydrogen atom or a (C1-C6) alkyl group and R7 represents a R2- (W) pC (VV) group - with p = 0 or 1, preferably p = 1, R2 representing a hydrogen atom. hydrogen or a group (C1-C6) alkyl, W and W, identical or different, representing an oxygen atom, sulfur or an amino group N (R3), preferably or an amino group N (R3), with R3 representing a hydrogen atom or a (C 1 -C 4) alkyl group, preferably a hydrogen atom; or else R6 and R7 form with the nitrogen atom which carries them a monocyclic heterocycle comprising from 5 to 7 members such as pyrrolidino; piperazino optionally substituted with one or more (C1-C6) alkyl groups; piperidino or (di) azepano; - n 'is as defined above, preferably n is 0, 1 or 2 preferably 1 or 2 - R1f and Rig are as defined above in R1, preferably R1f and R1g represent a halogen atom, or a group selected from 1) (C1-C6) alkyl optionally substituted by one or more atoms or halogen or hydroxy groups, 2) (C1-C6) alkoxy optionally substituted by one or more groups selected from hydroxy, (di) (C1-C4) (alkyl) amino; 3) alkylthio optionally substituted by one or more hydroxy or (di) (C1-C4) (alkyl) amino groups; 4) arylthio such as pehnylthio; 5) R2- (VV ') pC (VV) - (VV ") g- such as carboxy or RC (O) -N (R') - with R and R 'as defined above, p and q = 0 or 1, R2 representing a hydrogen atom or a group selected from (C1-C6) alkyl, W representing an oxygen atom, sulfur or an amino group N (R3), preferably an oxygen atom and W ' and W "representing an oxygen atom, sulfur atom or a group N (R4) with R3, and R4, identical or different, representing a hydrogen atom or a (C1-C4) alkyl group, preferably an atom of hydrogen; 6) (di) (C1-C4) (alkyl) amino, 7) heterocycloalkyl such as pyrrolidino, pyperidino, N '(C1-C4) (alkyl) -N-pyperazino, morpholino, 8) cycloalkylamino such as cyclohexylamino; 9) R'9-S0p- with p = 1, 2 or 3 and R'9 representing a hydrogen atom or a (C1-C6) alkyl group; and 10) hydroxyl. By way of example, the couplers of the invention of formula (I), and (Ib) to (If) may be mentioned those of the following formulas: ## STR1 ## ## STR2 ## wherein the couplers of the invention are chosen from the following groups: ## STR2 ## ## STR2 ## ## STR2 ## compounds 2 to 7 and 21 above. According to another advantageous variant the couplers of the invention are of formula (II) and more particularly for which Y represents a carbon atom and comprise at least one amino group X, or (di) (C1-C6) alkylamino whose or the two alkyl groups are optionally substituted with one or more radicals chosen from hydroxyl, (C1-C6) alkoxy, (di) (C1-C6) (alkyl) amino, carboxy, sulphonic acid preferably in position 1 or 2, particularly in position 1, and optionally substituted with one or more groups R1, preferably in position 4, 6 or 9; particularly in position 6. According to one particular embodiment of the invention, the coupler or couplers are chosen from naphthalenic couplers of formula (11a) or (11b): RR 6N (R '(R' 6 4 (11a) 6 4 (11b) as well as their salts of acids or inorganic or organic bases, their optical isomers, geometric, their tautomers, and / or their solvates such as hydrates; Formulas (11a) or (11b) in which: - R6 and R7 , identical or different, represent a hydrogen atom or a (C 1 -C 6) alkyl group optionally substituted with one or more hydroxyl groups, preferably R 6 and R 7 represent a hydrogen atom; n "is 0, 1, 2 or 3, preferably 0 or 1; R'ia represents a halogen atom, or a group selected from 1) (C1-C6) alkyl optionally substituted by one or more halogen atoms or hydroxyl groups, 2) ( C1-C6) alkoxy optionally substituted with one or more groups selected from hydroxy, (di) (C1-C4) (alkyl) amino, carboxy, it being understood that the alkyl group of the alkoxy may be interrupted by one or more heteroatoms such as oxygen; 3) an alkylthio optionally substituted with one or more hydroxy groups; 4) carboxy; 5) R "9-S0-sulphonic or (C 1 -C 6) alkylsulphonylamino with p = 1, 2 or 3 and R" 9 representing a hydrogen atom or a (C 1 -C 6) alkyl group, (di) (C 1 -C 6) C6) (alkyl) amino, 6) RR'NC (O) - with R and R 'representing a hydrogen atom or a (C1-C6) alkyl group; 7) (di) (Cr C4) (alkyl) amino and 8) hydroxyl. Especially R''is is selected from 5) R "9-S0p- with p = 2 and R" 9 representing a hydrogen atom or a (C1-C6) alkyl, (C1-C6) alkoxy group; (di) (C1-C6) (alkyl) amino, more preferably R'1a is a halogen atom such as chlorine, (C1-C6) alkyl, (C1-C6) alkoxy, sulfonic, carboxy, or (C1 C6) alkylsulfonylamino.

Preferably when n "is greater than or equal to 1, then at least one R'ia group is in the 6-position, preferably n" is 0 or 1. According to another advantageous variant, the couplers of the invention are of formula (II) ) and more particularly for which one or two radicals Y represent a nitrogen atom and comprise at least one amino group X, or (di) (C1-C6) alkylamino whose or both alkyl groups are optionally substituted by one or more radicals selected from hydroxyl, (C1-C6) alkoxy, (di) (C1-C6) (alkyl) amino, carboxy, sulfonic optionally substituted in the 1-position and optionally substituted by a group R1 preferably in the 6-position. Particular embodiment of the invention the coupler or couplers are chosen from couplers (iso) quinoline or quinoxaline of formula (11c) or (11d): 2 R6 (R '\ R7 (IIC) (R' 6 4 6 4 R6 N R7 (IId) and their salts of acids or inorganic or organic bases, their optical isomers s, geometric, their tautomers, and / or their solvates such as hydrates; Formulas (11c) or (IId) in which: R6 and R7, which may be identical or different, represent a hydrogen atom or a (C1-C6) alkyl group optionally substituted with one or more hydroxyl groups; preferably R6 and R7 represent a hydrogen atom; preferably the amino group NR6R7 is on the benzo ring of the formula (11c) and more particularly in the 6, 7 or 9 position; or else in position 3 of the formula (11d); Y is as defined previously in formula (II); n "is 0, 1, 2 or 3, preferably 0 or 1; R'ia is as defined above more particularly R'ia represents a group (C1-C6) alkoxy.

By way of example, the couplers of the invention of formula (II), (11a), (11b), (11c) and (11d) may be mentioned those of the following formulas: 17 28 31 34 H2 37 27 26 '29 More preferably, the coupler of the invention is selected from compound 28 above. According to another advantageous variant, the couplers of the invention are of formula (III) and more particularly for which Z represent a heteroatom: oxygen, sulfur or nitrogen and comprise at least one amino group X, or (di) (C1-C6) alkylamino wherein the one or both alkyl groups are optionally substituted by one or more radicals selected from hydroxyl, (C1-C6) alkoxy, (di) (C1-C6) (alkyl) amino, carboxy, sulfonic preferably X represents an amino group . According to a particular embodiment of the invention, the coupler or couplers are chosen from the couplers (111a), (111b) or (111c): (R "R7 \ (R" N 6 8 (IIIa) (111b) (111c ) as well as their salts of acids or mineral or organic bases, their optical isomers, geometrical, their tautomers, and / or their solvates such as hydrates; Formulas (IIIa), (IIIb) or (IIIc) in which: - R6 and R7, which may be identical or different, represent a hydrogen atom or a (C1-C6) alkyl group optionally substituted with one or more hydroxyl groups, preferably R6 and R7 represent a hydrogen atom; Y is as defined previously in the formula (111), more particularly Y represents CH, CR "ia or N, preferably CH or CR" ia; -Z of the formula (IIIa) or (IIIc) represents an oxygen or sulfur atom or a group NR 5, more particularly Z represents a group NR 5, and Z of formula (IIIb) represents a nitrogen atom, a CH group, or CR "ia; preferably CH, or CR" ia; R5 represents a hydrogen atom or a (C1-C6) alkyl group optionally substituted by one or more radicals a) hydroxyl, b) (C1-C6) alkoxy, c) (di) (Cr C6) (alkyl) amino d) heterocycloalkyl or preferably cationic 5 or 6-membered heteroaryl such as N, NL (di) (C 1 -C 6) alkylpyperazinium, N- (C 1 -C 6) alkylpyperidinium, N- (C 1 -C 6) alkylmorpholinium or N- ( C1-C6) alkylimidazolum, e) carboxy, or f) sulfonic acid; preferably, R5 represents a hydrogen atom or a (C1-C6) alkyl group optionally substituted by a hydroxy group or a heterocycloalkyl or cationic heteroaryl group such as N, NL (di) (C 1 -C 6) alkylpyperazinium or N- (C 1) -C6) alkylimidazolum; n "is 0, 1, 2 or 3, preferably 0 or 1; - R" ia represents a halogen atom, or a group selected from 1) (C1-C6) alkyl optionally substituted by one or more atoms of halogen or hydroxyl or heterocycloalkyl or cationic heteroaryl groups such as N, NL (di) (C 1 -C 6) -alkylpyperazinium or N- (C 1 -C 6) alkylimidazolum, 2) (C 1 -C 6) alkoxy optionally substituted by one or more groups selected from hydroxy, it being understood that the alkyl group of the alkoxy may be interrupted by one or more heteroatoms such as oxygen; 3) an alkylthio optionally substituted with one or more hydroxy groups; 4) carboxy; 5) R "9-S0-sulphonic or (C 1 -C 6) alkylsulphonylamino with p = 1, 2 or 3 and R" 9 representing a hydrogen atom or a (C 1 -C 6) alkyl, (di) ( C1-C6) (alkyl) amino, 6) RR'NC (O) - with R and R 'representing a hydrogen atom or a (C1-C6) alkyl group; 7) (di) (C1C4) (alkyl) amino and 8) hydroxyl; 9) R2- (VV ') pC (VV) - (VV ") q- such as carboxy or (C- C6) alkoxycarbonyl, p and q = 0 or 1, R2 representing a hydrogen atom or a group selected from (C1-C6) alkyl, W representing an oxygen atom, sulfur or an amino group N (R3), preferably an oxygen atom and W and W "representing an oxygen atom, sulfur or a group N (R4) with R3, and R4, identical or different, representing a hydrogen atom or a (CiC4) alkyl group, preferably a hydrogen atom; and 10) aryl such as phenyl; in particular R "ia is chosen from: - halogen, - hydroxyl, - (C1-C6) alkyl optionally substituted by a group chosen from hydroxyl, heteroaryl and heterocycloalkyl with 5 or 6 chain members, preferably cationic, such as: N, AIL ( di) (C1-C6) -alkylpyperazinium or N- (C1-C6) alkylimidazolum; - (C1-C6) alkoxy; - (C1-C6) alkoxycarbonyl; - (di) (C1-C6) (alkyl) amino such that (C1-C4) alkylamino and carboxy, it being understood that the nitrogen atom in position 3 may carry a (CiC6) alkyl group optionally substituted by one or more hydroxyl groups, in which case the nitrogen atom carrying said alkyl group is cationic, preferably the NR6R7 group is in position 6,7 or 8, more particularly in position 7. By way of example the couplers of the invention of formula (III), (111a), (111b) and (111c) there may be mentioned those of the following formulas: NH 4 NH 4 NH 4 NH 4 NH 4 NH 4 NH 4 NH 4 NH 4 NH 4 NH 4 NH 4 NH 4 NH 4 NH 4 NH 4 NH 4 NH 4 More particularly, the compounds of the formula Couplers of the invention are selected from compounds 40 and 44 above. According to another particular variant, the couplers of the invention are of formula (IV) and more particularly those which comprise, in the cycles, at least three Z = heteroatom groups preferably chosen from nitrogen and sulfur. According to a particular embodiment of the invention the coupler or couplers are chosen from couplers (IVa), or (IVb): (R "'(R"' 7 8 1 Z 'N 2 R7 an "' Z 40 R6 (IVa) 7 1 Z / a1 n "4 3 R6 (IVb) as well as their salts of mineral or organic acids or bases, their optical, geometric isomers, their tautomers, and / or their solvates such as hydrates; (IVa), or (IVb) in which: R6 and R7, which may be identical or different, represent a hydrogen atom or a (C1-C6) alkyl group optionally substituted with one or more hydroxyl groups, preferably R6 and R7; represent a hydrogen atom; - Z of the formula (IVa) represents CH, CR "ia, N or a group NR5, more particularly Z of the formula (IVa) represents a group NR5 at the 5-position and a nitrogen N at the position And Z of formula (IVb) represents an oxygen atom, sulfur atom or an NR5 group, more particularly Z of formula (IVb) represents a sulfur atom; represents a hydrogen atom or a (C1-C6) alkyl group optionally substituted by one or more radicals a) hydroxyl, b) (C1-C6) alkoxy, c) (di) (C1C6) (alkyl) amino, d) 5- or 6-membered optionally cationic heterocycloalkyl or heteroaryl such as N, A- (di) (C 1 -C 6) alkylpyperazinium, N- (C 1 -C 6) alkyl kypiperidin, N- (C 1 -C 6) alkylmorpholinium or N- (C1-C6) alkylimidazolum, e) carboxy, or f) sulfonic acid; preferably R5 represents a hydrogen atom or a (C1-C6) alkyl group more particularly R5 represents a hydrogen atom; n "'is 0, 1, or 2, preferably 0 or 1; Rmia represents a halogen atom, or a group selected from 1) (C1-C6) alkyl optionally substituted by one or more halogen atoms; or hydroxyl or (di) (C 1 -C 6) (alkyl) amino, 2) (C 1 -C 6) alkoxy optionally substituted by one or more groups selected from hydroxy, it being understood that the alkyl group of the alkoxy may be interrupted by one or more heteroatoms such as oxygen, 3) an alkylthio optionally substituted with one or more hydroxy groups, 4) carboxy, 5) R "9-S0 p- such as sulfonic or (C1-C6) alkylsulfonylamino with p = 1 , 2 or 3 and R "9 representing a hydrogen atom or a (C 1 -C 6) alkyl, (di) (C 1 -C 6) (alkyl) amino; 6) (di) (C 1 -C 4) (alkyl) amino group and 7) hydroxyl; 8) R2 '(VVI-C (VV) - (VV ") q- such as carboxy or (C1-C6) alkoxycarbonyl, p and q = 0 or 1, R2 representing a hydrogen atom or a group selected from (C1-C6) alkyl, W representing an oxygen atom, sulfur or an amino group N (R3), preferably an oxygen atom and W 'and W "representing an oxygen atom, sulfur atom or a group N (R4) with R3, and R4, identical or different, representing an atom hydrogen or a (C1-C4) alkyl group, preferably a hydrogen atom; 10) aryl such as phenyl and 11) -W-aryl with W as previously defined in particular -W-aryl is a phenoxy group; particularly R-1, is selected from halogen such as chlorine; C6) alkyl optionally substituted with a (di) (C1-C4) (alkyl) amino group; C6) alkylthio; and aryloxy such as phenoxy; preferably the NR6R7 group is in the 2 or 3 position. By way of example, the couplers of the invention of formula (IV), (IVa) and (IVb) may be mentioned those of the following formulas: 95 NH2 97 NH2 98 99 100 NH2 According to one particular embodiment of the invention, the couplers are such that in the formulas (I) to (IV): n = 0, or in the formulas (Ia) to (If): n '= 0, or in the formulas (11a) to (11d): n "= 0, or in the formulas (111a) to (111c): n" = 0 or in the formulas (IVa) or (IVb): n "'= 0 .

According to another advantageous embodiment of the invention, the couplers are such that in the formulas (I) to (IV): n = 1, or in the formulas (Ia) to (If): n '= 1, or in the formulas (11a) to (11d): n "= 1, or in the formulas (111a) to (111c): n" = 1 or in the formulas (IVa) or (IVb): n "= 1. According to Yet another particular embodiment of the invention the couplers are such that in the formulas (I) to (IV): n = 2, or in the formulas (la) to (If): n '= 2, or in formulas (11a) to (11d): n "= 2, or in formulas (111a) to (111c): n" = 2 or in formulas (IVa) or (IVb): n "'= 2. a preferred embodiment of the invention the couplers are such that in the formulas (I) to (IV): n = 3, or in the formulas (la) to (If): n '= 3, or in the formulas (11a ) to (11d): n "= 3, or in the formulas (111a) to (111c): n" = 3 or in the formulas (IVa) or (IVb): n "= 3. coloring agents according to the invention are cho isis among the poly (1b) including poly (3-pyrrolidin-1-yl-phenol), poly (3-aminophenol), poly (2,5-dimethoxyaniline) and poly (3,4-dihydro- 2H-1,4-benzoxazin-6-ol); poly (Ic) in particular poly (2,6-diamino-pyridine) and poly (2-amino-3-hydroxy-pyridine, poly (IIc) especially poly (6-aminoquinoxaline), poly (IIIa) in particular poly (6-hydroxy-indole) and poly (IIIb) especially poly (6-aminoindazole) ii) radical initiators or chemical oxidizing agents The process for preparing the coloring agent (s) employs ingredient ii) one or more radical initiators and / or one or more chemical oxidizing agents. It is understood that ingredient ii) is different from hydrogen peroxide in basic or neutral medium i.e. at a pH at 25 ° C inclusive between 7 and 11; ingredient ii) may represent hydrogen peroxide in a strongly acidic medium ie at a pH at 25 ° C of less than or equal to 5, preferably less than or equal to 3, in particular at a pH at 25 ° C of between 1 and According to a preferred embodiment of the invention ingredient ii) is different from hydrogen peroxide irrespective of the pH of the medium in which it is located.

By the term "and / or" is meant that the ingredient comprises one or more radical initiators alone, or one or more chemical oxidizing agents alone, or comprises one or more radical initiators with one or more chemical oxidizing agents; or while ingredient ii) has a radical initiator character and also a chemical oxidizing agent.

According to a particular embodiment of the invention, the process for preparing the coloring agent (s) uses one or more ingredients ii) chosen from radical initiators. By "radical initiator" is meant any chemical compounds which can generate a radical compound under mild conditions, and which induces a radical reaction (see eg J. March, Advance Organic Chemistry, reactions, mechanisms, and structure, 4th Ed. , John Willey & sons, 1992 Chapter 14: Free-radical substitution). In particular, these initiators comprise a weak bond i.e. a low dissociation energy. Typically there may be mentioned halogenated initiators, azo or organic peroxides. They can be generated by thermal pathways, at room temperature (25 ° C) or at higher temperature or photochemically. These radical initiators are different from hydrogen peroxide. In particular, we mean the free radical initiators generated by thermal pathways or from light sources (see, for example, Macromol, Rapid Commun, Christian Decker, 23, 1067-1093 (2002), Encyclopedia of Polymer Science and Technology, Photopolymerization Free. radical "http://onlinelibrary.wiley.com/doi/10.1002/0471440264.pst490/pdf; ibid," photopolymerization, cationic ", http://onlinelibrary.wiley.com/doi/10.1002/0471440264.pst491/pdf; Macromol Symp 143, 45-63 (1999)). Two major families are to be distinguished: - Type I in which the initiators of radicals will cause, under irradiation or heat, a unimolecular cut of the covalent bond to lead to a free radical compound also symbolized by a "point", and - of type II in which the radical initiators will lead to a biomolecular reaction in which the excited state of the photoactive compounds interact with a second molecule (or co-initiator) to generate free radicals. More particularly, the radical initiators are chosen from compounds of formula (V) and (VI), as well as their salts of organic or inorganic acid, their optical isomers, geometric, tautomers and their solvates such as hydrates: Ri Rr Wherein R 1, R 2, R 3 and R 4, which may be identical or different, represent a hydrogen atom or R 3 R 3 AE N = N R 2 R 4 R 4 (VI) (V) (C 1 -C 8) alkyl, linear or branched, optionally substituted, (C-C 8) alkoxy, linear or branched; optionally substituted aryl such as phenyl; or else R1 and R2 and / or R3 and R4 together with the carbon atoms which carry them an optionally substituted (hetero) cycloalkyl comprising from 3 to 7 members, particularly (C3-C6) cycloalkyl such as cyclohexyl; preferably, R1, R2, R3 and R4, which may be identical or different, represent a hydrogen atom or a linear or branched (C1-C6) alkyl group; x and y, identical or different, represent an integer inclusive between 0 and 6, preferably x and y = 0; - EA and EA ', identical or different, preferably identical, represent an electron-withdrawing group, preferably electroattractant by the mesomere effect -M, such as cyano, -C (X1) -X2-Ra, phosh (on) ate, sulf ( on), nitro, or nitroso; more particularly EA = EA '= cyano; - R, and R 'identical or different, preferably identical, represent i) an EA or EA' radical as defined above, or a selected group ii) from (CiC8) alkyl, linear or branched, optionally substituted, iii) aryl optionally substituted, iv) optionally substituted aryl ((C1-C8) alkyl, or else R with R1 and / or R 'with R3 together with the carbon atom carrying them a group C (X1) and R2 and R4 being as defined above or R 2 and R 4, which are identical or different, represent a group R 5 - (X 2) w - in which w is 0 or 1, R 5 represents a hydrogen atom, a (C 1 -C 8) alkyl group, linear or branched, an optionally substituted (hetero) aryl group such as phenyl or a (hetero) cycloalkyl group optionally substituted in particular by a (C 1 -C 6) alkyl group such as cyclohexyl optionally substituted by a (C 1 -C 6) alkyl group and X 2 is as defined hereinafter: Xa, identical or different, represent a heteroatom selected from oxygen and sulfur, a group -C (O) -O- or -O-C (O) -, a group -O-C (O) -O- or -O-O (0) -O -; preferably Xa represent an oxygen atom; X1, and X2, identical or different, representing a heteroatom chosen from oxygen, sulfur and amino N (R ") with R" being a hydrogen atom or a linear or branched (CiC6) alkyl group; preferably X1 and X2 represent an oxygen atom; It is also possible to mention diatomic halogen molecules such as O12 which will generate as a radical initiator a CC (4 CC) halogen radical; the azo initiators of RN = NR 'type which generate the radicals R and R' (4 R and R ') by elimination of N2 gases such as AIBN (AzobislsoButyroNitrile) and ABCN (1,1'15 AzoBis (CyclohexanecarboNitrile) which generate as isobutyronitrile radical and cyclohexanecarbonitrile respectively According to one particular embodiment of the invention, the radical initiator (s) are chosen from organic peroxides, in particular those of formula (VI) as defined above, these latter comprising at least one -OO bond which can be easily cleaved into two radicals -O, and more particularly those of the following general formulas: Ra-C (R'aR'b) -O-O-C (R'aR'b) -Rb (V11) ) or R, - (O), -O-C (R'aR'b) -O-O-C (R'aR'b) -O- (O), - Rd (VI2) Formulas (V11) and (VI2) in which: - Ra, Rb, R'a and R'b, which may be identical or different, represent an optionally substituted (C1-C10) alkyl group, preferably (C1-C6) alkyl; (hetero) aryl optionally substituted such as phenyl; (hetero) cycloalkyl optionally substituted such as cyclohexyl optionally substituted with (C1-C4) alkyl groups; or R'a and R'b together with the carbon atom carrying them a (thio) carbonyl group, preferably carbonyl; - R, and Rd, identical or different represent a hydrogen atom or a group as defined for Ra or Rb; preferably R 1 and Rd represent a hydrogen atom or a cycloalkyl group such as cyclohexyl optionally substituted with a (C 1 -C 6) alkyl group; Xa and Xb, which may be identical or different, represent a heteroatom such as the oxygen or sulfur atom, preferably oxygen; and - s is 0 or 1.

According to one embodiment, the radical initiator (s) have the following formula: According to one particular embodiment of the invention, the radical initiator is AIBN (azobisisobutyronitrile). This initiator generates free radicals i) under the influence of heat at a temperature greater than or equal to 45 ° C, preferably at a temperature greater than or equal to 55 ° C, more particularly at 60 ° C; and / or ii) photochemically. According to another particular embodiment of the invention, the radical initiator is ABDV (2,2'-azo-bis- (2,4-dimethylvaleronitrile)). The latter makes it possible to be used under thermally "softer" polymerization conditions. Preferably, when the ABDV is used, the polymerization process is carried out at a temperature greater than or equal to 28 ° C., preferably at a temperature greater than or equal to 35 ° C., such as at 40 ° C.

According to another particular embodiment of the invention, the process for preparing the coloring agent or agents uses one or more ingredients ii) chosen from chemical oxidizing agents. By "chemical oxidizing agent" is meant an agent different from the oxygen of the air which has the property of being able to oxidize the molecules, ie removing an electron from a molecule. According to a particularly advantageous embodiment, the ingredient (s) ii) are chosen from persulfates of formula (VII): ## STR2 ## Formula (VII) in which W represents a cationic, mineral or organic counterion, in particular chosen from alkali metal cations such as sodium or potassium, or alkaline-earth, and ammonium RaRbRcRdN + with Ra, Rb, Rc, and Rd, identical or different, represent a hydrogen atom or a (C1-C6) alkyl group such as NH4. + Especially the ingredient (s) ii) are chosen from: organic or inorganic persulfates of formula (VII) such as ammonium persulfates; organic peroxides such as di-tert-butyl peroxide, benzoyl peroxide (POB), methyl ethyl ketone peroxide (MEKP); organic peroxides such as benzoyl peroxide, dicumyl peroxide and di-tert-butyl peroxide; azo compounds such as 2,2'-azobisisobutyronitrile (AIBN) or 1,1'-azobis (cyclohexanecarbonitrile) (ABCN); and the reaction products between hydrogen peroxide and ascorbic acid between the hydrogen peroxide and the metal salts, in particular the metal salts of transition metals such as Fe, in particular the metal salts of Fe 2+ ; between organic peroxides such as ammonium persulfate and metabisulphites; alkali metal or alkaline earth metal dichromate, such as sodium dichromate; copper halides, in particular Cu (II) copper such as CuCl 2; the reaction product between hydrogen peroxide and ascorbic acid; and the reaction product between hydrogen peroxide and metal salts such as Fe2 + (Fenton reaction).

Preferably, the ingredient (s) ii) are chosen from the persulfates of formula (VII) as defined above, in particular the persulfates with organic cationic counterions such as those of which W represent an ammonium group RaRbRcRdN + with Ra, Rb, Rc and Rd, which may be identical or different, represent a hydrogen atom or a (C1-C6) alkyl group such as NH4. + A process for preparing the coloring agent (s): Preferably, the coloring agent (s) of the invention are carried out by polymerization of the couplers i) as defined above in the presence of initiator radicals or chemical oxidizing agents ii) as defined above at a temperature between 0 ° C and 80 ° C, more particularly between 0 ° C and 35 ° C. According to another particular embodiment of preparation of the coloring agents of the invention, are prepared from couplers i) as defined above, initiators of photoactive radicals as ingredients ii) in the presence of one or more identical or different, light sources. The light source (s) photoirradient by electromagnetic waves of wavelengths included in the UV to the IR.

By "photoirradiation with an electromagnetic wave" is meant any exposure of the composition or part of the composition to a light wave during the hair dyeing process. The light spectrum may include wavelengths in the region of UV (200-400 nm), visible (400-745 nm), infrared (745 nm to 3 pm).

Ultraviolet radiation, visible light or infra-red can be used. The choice depends on the characteristic absorption of the photoactive radical initiator. If the photoactive radical initiator absorbs ultraviolet wavelengths then ultraviolet radiation is used to activate it. If the initiators of photoactive radicals absorb in the visible wavelengths then the visible radiation is used. Absorption spectra of photoactive radical initiators are available in the literature. The amount of light energy varies according to the initiators of photoactive radicals. Just enough light energy is needed to activate said photoactive initiator. Sometimes daylight is enough. According to one particular embodiment of the invention, the dyeing process takes place in the natural light of the sun or of the day. According to another process for preparing the coloring agents of the invention, the source of the photoirradiation is artificial. For the UV-emitting lamps, those described in Ullmann's Encyclopedia "Ultraviolet and Visible Spectroscopy" 2008 Wiley-VCH Verlag GmbH & Co KGaA, Weinheim, 10.1002 / 14356007.b05 383.pub2, point 3.2. For lamps in general, mention may be made of those mentioned in Ullmann's Encyclopedia "Lamps" 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 10.1002 / 14356007.a15 115 and Ullmann's Encyclopedia "Photochemistry" 2005 WileyVCH Verlag GmbH & Co. KGaA, Weinheim 10.1002 / 14356007.a19 573, point 3.2 "light sources".

The lamps used in the process of the invention are in particular incandescent, halogen, fluorescent, mercury, low pressure lamps, low pressure lamps, for example sodium or neon lamps, high pressure lamps, for example mercury, halide lamps, flash lamps for example xenon, fluorescent excimer lamps such as xenon, light emitting diodes or LEDs from 0.01 to 1000mW, lamps emitting black light or Wood's light, and lasers. Preferably, the artificial sources come from mercury, halogen and tungsten lamps, white neon tube, LEDs, UV lamp emitting at 254 nm, or at 365 nm.

According to an advantageous embodiment of the invention, the process for preparing the coloring agents implements a first step in which the couplers i) as defined above which are solubilized in a liquid solution, preferably in a hydroalcoholic solution, and then in the second step is added one or more alkaline agents as defined above, in particular with ammonia to reach a basic pH preferably between 8 and 10, then in a third step is added the initiator (s) of radicals ii) as defined above, in particular persulfates of formula (VII), more particularly those with organic cationic counter-ions such as those of which W represent an ammonium group RaRbRcRdN + with Ra, Rb, Rc, and Rd, which are identical or different, represent a hydrogen atom or a (C 1 -C 6) alkyl group such as NH 4 + as defined above. In particular, the preparation process is carried out at ambient temperature (25 ° C.). According to a particular embodiment, the preparation process is carried out with stirring for between 30 minutes and two days, preferably between one hour and three hours. According to a variant in a fourth step, the precipitate formed is filtered, preferably washed with water and then preferably dried under vacuum.

Preferably, the amount of i) and ii) respect a ratio by weight of i) the coupler (s) / ii) of the radical initiator (s) or chemical oxidizing agent (s) between 0.5 and 1.5, more particularly the report is worth 1.

Coloring agents - oligomers or colored polymers: According to one embodiment of the invention, the coloring agent (s) are obtained from the polycondensation (i) of couplers as defined previously reacting with each other in the presence of (ii) from at least one initiator of radicals or at least one chemical oxidizing agent as defined previously; it being understood that the couplers are different from 2,5-dimethoxyaniline, 2-methyl-5-methoxyaniline, 2-methoxy-5-methylaniline, 3-aminophenol. More particularly, the coloring agent (s) are chosen from poly (Ib) with (Ib) as defined above, in particular poly (3-pyrrolidin-1-yl-phenol), poly (3,4-dihydro-2H) -1,4-benzoxazin-6-ol); poly (1c) with (1c) as defined above, especially poly (2,6-diamino-pyridine) and poly (2-amino-3-hydroxy-pyridine, poly (11c) with (11c) such defined above, in particular poly (6-aminoquinoxaline), poly (111a) with (111a) as defined above, in particular poly (6-hydroxy-indole) and poly (111b) with (111b) such that defined above, especially poly (6-aminoindazole) being understood that the agent is different from poly (2,5-dimethoxyaniline), poly (2-methyl-5-methoxyaniline), poly (2-methoxy-5- methylaniline), and poly (3-aminophenol).

Another subject of the invention is a coloring agent that can be obtained by chemical polycondensation: i) couplers between them as defined above in the presence of at least one ingredient ii) chosen from radical initiators and chemical oxidants as defined above; free of oxidation base and free of hydrogen peroxide with preferably a weight ratio of i) / ii) of between 0.5 and 1.5, more particularly the ratio is 1. Another object relates to the use dyeing agent, preferably pigment, as defined above for dyeing keratinous fibers. The composition of the invention Another subject of the invention is a composition comprising at least one coloring agent as defined above.

Preferably, the composition of the invention does not comprise an oxidation base and / or hydrogen peroxide. More preferably, the coloring agent included in the composition is prepared respecting a molar ratio i) of the coupler (s) / ii) of the radical initiator (s) or chemical oxidizing agent (s) c which is between 0.5 and 1, 5, more particularly the ratio is 1. The cosmetic medium: The term "cosmetic medium" means a suitable medium for dyeing keratinous fibers, also called dye support, which is a cosmetic medium generally consisting of water or by a mixture of water and one or more organic solvents or a mixture of organic solvents. Preferably the composition comprises water and in a content inclusive of, in particular, between 5% and 95% relative to the total weight of the composition.

By "organic solvent" is meant an organic substance capable of dissolving another substance without chemically modifying it. Organic solvents: As an organic solvent, mention may be made, for example, of lower C1-C4 alkanols, such as ethanol and isopropanol; polyols and polyol 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, and mixtures thereof.

The organic solvents are preferably present in proportions preferably ranging between 0.1 and 40% by weight, with respect to the total weight of the dyeing composition, and more preferably between 1 and 30% by weight, and even more preferentially. inclusive of between 5 and 25% by weight relative to the total weight of the composition. The composition according to the invention contains, in a cosmetic medium, an amount of coloring agent as defined above, generally ranging between 0.001% and 30% by weight relative to the total weight of the composition.

Preferably, the amount of coloring agents of the invention is between 0.01 and 5% by weight, based on the total weight of the composition. By way of example, the dye (s) is in an amount of between 0.01% and 2% inclusive. Preferably, the composition of the dyeing method of the invention is in liquid form and contains one or more coloring agents as defined above. alkaline agents; The dyeing process may employ one or more alkaline agents. More particularly, the composition of the invention may further comprise one or more alkaline agents. This agent may be chosen from inorganic or organic or hybrid alkaline agents or mixtures thereof. The inorganic alkaline agent (s) is (are) preferably chosen from ammonia, alkali carbonates or bicarbonates, such as sodium or potassium carbonates and sodium or potassium bicarbonates, sodium or potassium hydroxides, or mixtures thereof. According to an advantageous embodiment of the invention, the alkaline agent (s) are organic amines i.e. they contain at least one substituted or unsubstituted amino group. The organic alkaline agent (s) is (are) preferably chosen from organic amines whose pKb at 25 ° C. is less than 12, and preferably less than 10, and even more advantageously less than 6. It should be noted that this is pKb corresponding to the highest basicity function. As hybrid compounds, mention may be made of the salts of the amines mentioned above with acids such as carbonic acid and hydrochloric acid.

The organic alkaline agent (s) are, for example, chosen from alkanolamines, oxyethylenated and / or oxypropylenated ethylenediamines, amino acids and compounds of the following formula (VIII): ## STR2 ## Formula (VIII) in which: W is a divalent C 1 -C 6 alkylene radical optionally substituted by a hydroxyl group or a C 1 -C 6 alkyl radical, and / or optionally interrupted by one or more heteroatoms such as oxygen or NRu; - Rx, RY, Rz Rt and Ru, identical or different, represent a hydrogen atom, a C1-C6 alkyl or C1-C6 hydroxyalkyl, C1-C6 aminoalkyl.

Examples of such amines include 1,3-diaminopropane, 1,3-diaminopropanol, spermine and spermidine. By alkanolamine is meant an organic amine comprising a primary, secondary or tertiary amine function, and one or more linear or branched C 1 -C 8 alkyl groups carrying one or more hydroxyl radicals. The composition of the invention preferably contains one or more alkanolamines. Even more preferentially, the organic amine is monoethanolamine. In one variant of the invention, the composition comprises as alkaline agent one or more alkanolamines (preferably ethanolamine) and ammonia. In this variant, the alkanolamine or alkanolamines are present in major amount relative to the ammonia. According to another variant, the coloring composition comprises ammonia. Advantageously, the composition according to the invention has a content of alkaline agent (s), ranging from 0.01 to 30% by weight, preferably from 0.1 to 20% by weight, better still from 1 to 10% by weight relative to the weight of said composition. Adjuvants: The composition comprising the coloring agent (s) as defined above may also contain various adjuvants conventionally used in compositions for dyeing hair, such as anionic, cationic, nonionic surface-active agents; or mixtures thereof, anionic, cationic, nonionic, amphoteric or zwitterionic polymers or mixtures thereof, inorganic or organic thickeners, penetrating agents, sequestering agents, perfumes, buffers, dispersing agents, packaging such as, for example, volatile or non-volatile silicones, modified or unmodified, film-forming agents, ceramides, preserving agents, opacifying agents. The adjuvants above are generally present in an amount for each of them between 0.01 and 20% by weight relative to the weight of the composition. Of course, one skilled in the art will take care to choose this or these optional additional compounds in such a way that the advantageous properties intrinsically attached to the dyeing composition according to the invention are not, or not substantially, impaired by the or the additions envisaged.

Additional dyes: The composition comprising the dyeing agent (s) as defined above of the process of the invention may also contain one or more additional direct dyes. These direct dyes are, for example, chosen from those conventionally used in direct dyeing, and among which may be mentioned all the aromatic and / or nonaromatic dyes of current use such as neutral, benzene neutral, acidic or cationic direct dyes, direct dyes neutral azo, acidic or cationic, natural direct dyes, quinone direct dyes and in particular neutral, acidic or cationic anthraquinone dyes, direct dyes azine, triarylmethane, indoamine, methines, styrils, porphyrins, metalloporphyrins, phthalocyanines, methine cyanines, and fluorescent dyes. Among the natural direct dyes that may be mentioned are lawsone, juglone, alizarin, purpurin, carminic acid, kermesic acid, purpurogalline, protocatechaldehyde, indigo, isatin, curcumin, spinulosin, apigenidine, orceins. It is also possible to use the extracts or decoctions containing these natural dyes, and in particular poultices or extracts made from henna. According to the invention, the additional direct dye (s) used according to the invention preferably represent from 0.001% to 10% by weight approximately of the total weight of the dyeing composition comprising the coloring agent (s) as defined above and even more preferably from 0.05% to 5% by weight approximately. PH: The pH of the composition according to the invention is generally between 2 and 12 approximately, and preferably between 3 and 11 approximately. It can be adjusted to the desired value by means of acidifying or alkaline agents usually used for dyeing keratinous fibers or else using conventional buffer systems. The pH of the composition is preferably between 6 and 11 inclusive, particularly between 7 and 10.5 and more particularly between 8 and 10, such as 9.5. Among the acidifying agents, mention may be made, by way of example, of mineral or organic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid, lactic acid, sulphonic acids.

Among the alkaline agents that may be mentioned, for example, are ammonia, alkaline carbonates, alkanolamines such as mono-, di- and triethanolamines and other conventional alkaline agents used in cosmetics in hair dyeing as defined above. .

Forms of the Composition: The dye composition comprising the coloring agent (s) as defined above may be in various galenic forms, such as in the form of liquids, lotions, creams, gels, or in any other suitable form. for dyeing keratinous fibers. It may also be packaged under pressure in an aerosol flask in the presence of a propellant or in a non-aerosol flask and form a foam. Coloring Methods of the Invention: The Method of Coloring Keratinous Materials, in particular Keratin Fibers in particular of the invention uses at least one coloring agent, preferably a coloring agent, obtainable from the polycondensation of i) couplers in the presence of ii) at least one radical initiator such as previously defined. More specifically, the coloring agent (s) are applied to the keratinous fibers. Preferably, the coloring agent (s) are in a cosmetic composition as defined above, which is then applied to the keratinous fibers. The pause time of the dye composition on keratin materials i.e; comprising the coloring agent (s) as defined above is included between 5 minutes and 1 hour, preferably between 10 minutes and 40 minutes.

According to a particular embodiment of the invention, the dyeing method comprises the following steps: 1) The application to the keratin materials of a composition comprising at least one coloring agent as defined above; then 2) the dyeing composition is left paused on the keratin materials for a period inclusive between 5 minutes and 1 hour, preferably between 10 minutes and 40 minutes; then 3) optionally the keratin materials are shampooed with a conventional shampoo and / or rinsing and dried. The application of the dye composition i.e. the composition comprising the coloring agent (s) is generally carried out at ambient temperature. It can however be carried out at temperatures ranging from 20 to 180 ° C. The dyeing process according to the invention can be followed by shampooing with a conventional shampoo and / or drying the keratinous fibers.

The examples which follow serve to illustrate the invention without, however, being limiting in nature. EXAMPLE OF COLORING /) SYNTHESIS OF COLORING AGENTS: Compound 1: Synthesis of poly (2,6-diaminopyridine) 436.5 mg (4 mmol) of 2,6-diaminopyridine are solubilized in 4 ml of ethanol and 12 ml of water. The pH of this solution is brought back to 9.95 by adding a few drops of a 20% ammonia solution. 913 mg (4 mmol) of ammonium persulfate dissolved in 2 ml of water are then added dropwise over 10 minutes. During the addition the temperature rises to 35 ° C and the pH decreases. The reaction medium is left stirring for 2 h. The precipitate is filtered, washed with water and then dried under vacuum. After drying, 290 mg of compound 1 are obtained in the form of a black powder. An HPLC / HRMS analysis performed on an Accela chain coupled to an LTQ-Orbitrap (Thermo Fisher) High Resolution Mass Spectrometer (HRMS) allows the detection of the following ions: Retention time tR min m / z Gross formula 3.5 230 + C10H7N502 4.3 230+ C101-I11N7 13.5 318+ C151-111N9 Compound 2: Synthesis of poly (3-pyrrolidin-1-yl-phenol) to 652.8 mg (4 mmol) of 3-pyrrolidin-1 -yl-phenol 12 ml of water, 22 ml of ethanol are added; the pH of this solution is adjusted to 9.5-10 with 20% ammonia. Then a solution of 913 mg (4 mmol) of ammonium persulfate in 2 ml of water is added dropwise. The reaction mixture is stirred for 3 hours, filtered and the precipitate formed is washed with water-ethanol. After drying, 247 mg of compound 2 are obtained in the form of a black powder. An HPLC / HRMS analysis performed on an Accela chain coupled to an LTQ-Orbitrap (Thermo Fisher), High Resolution Mass Spectrometer (HRMS) allows the detection of the following ions: tR (min) m / z Gross Formula 17.6 321+ C201-120N202 21.6 339+ C20I-122N203 23.1 806 + / 403 2+ C501-155N505 Compound 3: Synthesis of poly (2-amino-3-hydroxypyridine) to 440 mg (4 mmol) of 2-amino 3-hydroxypyridine is added 12 ml of water, 4 ml of ethanol; the pH of this solution is adjusted to 9.5-10 with 20% ammonia.

Then a solution of 1.37 g (6 mmol) of ammonium persulfate in 10 ml of water is added dropwise. The reaction mixture is stirred for 5 hours, filtered and the precipitate formed is washed with water-ethanol. After drying, 440 mg of compound 3 are obtained in the form of a brown powder. An HPLC / HRMS analysis performed on an Accela chain coupled to an LTQ-Orbitrap (Thermo Fisher), High Resolution Mass Spectrometer (HRMS) allows the detection of the following ions: tR (min) m / z Gross Formula 8.2 232+ C10H9N502 13.8 341+ C15H12N604 18.2 233+ C10E-I81 \ 14.03 Compound 4: Synthesis of poly (3-aminophenol) To 436 mg (4 mmol) of 3-aminophenol was added 12 ml of water, 4 ml of ethanol; the pH of this solution is adjusted to 9.5-10 with 20% ammonia. Then a solution of 1.37 g (6 mmol) of ammonium persulfate in 10 ml of water is added dropwise. The reaction mixture is stirred for 5 hours, filtered and the precipitate formed is washed with water-ethanol. After drying, 150 mg of compound 4 are obtained in the form of a black powder. An HPLC / HRMS analysis performed on an Accela chain coupled to an LTQ-Orbitrap (Thermo Fisher), High Resolution Mass Spectrometer (HRMS) allows the detection of the following ions: tR m Formula m / z 18.5 335+ C18I Compound 5: Synthesis of poly (6-hydroxyindole) To 532 mg (4 mmol) of 6-hydroxyindole is added 12 ml of water, 4 ml of water. ml of ethanol; the pH of this solution is adjusted to 9.5-10 with 20% ammonia. Then a solution of 1.37 g (6 mmol) of ammonium persulfate in 10 ml of water is added dropwise. The reaction mixture is stirred for 5 hours, filtered and the precipitate formed is washed with water-ethanol. After drying, 525 mg of compound 5 are obtained in the form of a black powder. Compound 7: Synthesis of poly (2,5-dimethoxyaniline) 766 mg (5 mmol) of 2,5-dimethoxyaniline are solubilized in 20 ml of ethanol and 4 ml of water. The pH is then reduced to 10.3 by adding a few drops of a 20% ammonia solution. 1141 mg (5 mmol) of ammonium persulfate dissolved in 3 ml of water are then added dropwise over 11 min.

During the addition the temperature rises to 32 ° C and the pH decreases to 1.8. The reaction medium is left stirring for 3 h. The precipitate is filtered, washed with water and dried under vacuum. 513 mg of black powder is obtained. An HPLC / HRMS analysis performed on an Accela chain coupled to an LTQ-Orbitrap (Thermo Fisher), High Resolution Mass Spectrometer (HRMS) allows the detection of the following ions: tR min mz Formula gross 14.5 273+ C141-112N204 16 , 4 305+ C161-116N206 18.9 727+ C36H38N809 741 + / 371 2+ C39H40N4011 21.4 411+ C22H22N206 21.9 546+ C301-131 N307 Compound 8: Synthesis of poly (3,4-dihydro-2H) 1,4-benzoxazin-6-ol) To 604.6 mg (4 mmol) of 3,4-dihydro-2H-1,4-benzoxazin-6-ol was added 12 ml of water, 4 ml of ethanol; the pH of this solution is adjusted to 9.5-10 with 20% ammonia. Then a solution of 1.37 g (6 mmol) of ammonium persulfate in 10 ml of water is added dropwise. The reaction mixture is stirred for 5 hours, filtered and the precipitate formed is washed with water-ethanol. After drying, 440 mg of compound 8 is obtained in the form of a black powder. Compound 9: Synthesis of poly (6-aminoindazole) 665 mg (5 mmol) of 6-aminoindazole are solubilized in 15 ml of ethanol and 3 ml of water. The pH is then brought back to 10 by adding a 20% ammonia solution. To this medium is then added dropwise 1.141 g (5 mmol) of ammonium persulfate dissolved in 3 ml of water. Addition time 5 min. During the addition the temperature rises to 27 ° C. The pH decreases to 3; The solution during the addition darkens becomes brown red and a precipitate is formed. After stirring for 3 hours at room temperature, the solid is filtered off, washed with water and dried under vacuum. A black brown powder is obtained. Compound 10: Synthesis of poly (6-aminoquinoxaline) 435.5 mg (3 mmol) of 6-aminoquinoxaline are solubilized in 3 ml of ethanol and 3 ml of water. The pH is then brought back to 10.5 with 20% ammonia solution. 684 mg (3 mmol) of ammonium persulfate dissolved in approximately 3 ml of water are then added dropwise over a period of 4 minutes. The temperature goes from 15.6 ° C to 18 ° C during the addition, the pH becomes acidic a brown precipitate is formed. The reaction medium is left stirring for 5 h. After wringing off the precipitate, washing with water and ethanol and drying, 401 mg of brown powder are obtained. II) EVALUATION ON KERATIN FIBERS Protocol A: A formulation support is prepared by mixing respectively: - 0.5 g of benzoic acid - 5 g of benzyl alcohol - 15 g of ethanol - water until obtaining 100 g of 20% aqueous ammonia mixture until a pH of 9.5 is obtained. 0.5 g of colored oligomers are added to this formulation support, and the resulting mixture is then applied to 90% white natural strands (juice / hair ration 5/1) for 30 minutes at 20 ° C. The locks are then washed and shampooed. Protocol B: A formulation support is prepared by mixing respectively: - 5 g of a 30% aqueous solution of oleocetyl dimethyl hydroxyethyl ammonium chloride - 5 g of benzyl alcohol - 15 g of ethanol - water up to obtaining 100 g of 20% aqueous ammonia mixture until a pH of 9.5 is obtained. 0.5 g of colored oligomers are added to this formulation support, and the resulting mixture is then applied to 90% white natural strands (juice / hair ration 5/1) for 30 minutes at 20 ° C. The locks are then washed and shampooed. Precursors protocol Ascending Oligomers (AE) OH NA 52.9 2.2 12 11.7 lel OH B 52 2.2 19.9 10.6 NNH2 OH A 41.9 1.1 13.9 13.3 on 1 NH2 HO and 45.5 7.2 10.1 11.8 NH 0 A 54.2 0 8.49 10.4 NH2 -0.58 the / I HO gli 0 A 51.8 2.6 12.35 10.8 N H2N iel \ A 47.9 7.1 15.51 14.8 NH * A 57.33 0.75 13.64 4.27 H2N N

Claims (18)

REVENDICATIONS1. Process for dyeing keratinous substances, in particular keratinous fibers, in particular human fibers such as the hair, using at least one coloring agent obtained from the polycondensation between i) several couplers that react with each other in the presence of one or more ingredients ii) selected from radical initiators and chemical oxidizing agents. 2. Method according to the preceding claim wherein the couplers of the invention are chosen from those of formulas (I) to (IV) below: ## STR2 ## ) Y (Y) Y (Y) Y (Y) X (R) n X (R1) n (II) (III) X (R1) n as well as their salts of inorganic or organic acids or bases, their optical, geometric isomers, their tautomers, and / or their solvates such as hydrates; formulas (I) to (IV) in which: X represents a radical linked to the remainder of the molecule covalently to a carbon atom, said radical a group chosen from: i) hydroxyl, ii) amino, iii) (di) (O-O) alkylamino in which the one or both alkyl groups are optionally substituted by one or more radicals selected from hydroxyl, (C1-C6) alkoxy, (di) (O-06) (alkyl) amino, carboxy (-O (O) -OH), sulfonic (-SO3H), amino, sulfate-OSO3H - R1 represents a radical bonded to the remainder of the molecule covalently to an atom of carbon, said radical R1 is chosen from: i) halogen; ii) hydroxyl OH; iii) SH thiol; iv) amino; y) (di) (C1-C12) alkylamino wherein one or both alkyl groups of the amino are optionally substituted with one or more atoms or radicals selected from: 1) hydroxyl, 2) C1-C6 alkoxy, 3) amide or aminocarbonyl (-O (O) -NH 2), 4) (di) (Cr C6) alkylamino, 5) carboxy (-O (0) _OH), 6) sulfonic (-SO3H), 7) 5- to 7-membered heterocycloalkyl, monocyclic such as pyrrolidinyl, C6) alkylpyrrolidinyl, piperidinyl, morpholinyl, N- (O-C6) alkylpiperazinyl; 8) 5- to 7-membered heteroaryl, monocyclic such as pyridinyl, tetrahydrofuranyl or imidazolyl; 9) aryl such as phenyl; 10) halogen; 11) nitrile; 12) cationic heterocycloalkyl comprising from 5 to 7 chain members, monocyclic such as N, N-di (01-06) alkylpiperazinium, N- (01-06) alkyl, N '- (C1-06) alkylpiperazinium, N- (01-) C6) alkylpiperidinium, N- (O-C6) alkylmorpholinium, N- (O-C6) alkylpyrrolidinium; 13) cationic heteroaryl comprising from 5 to 7 chain members, monocyclic such as N- (01C6) alkylpyridinium, N- (01-C6) alkylimidazolium; 14) tri- (O-C6) alkylammonium; 15) (di) (C1-C6) alkylamino-carbonyl or (di) (C1-C6) alkylacetamido; 16) H-C (O) -N (CiC6) (alkyl) amino or (C1-C6) (alkyl) carbonyl (C1-C6) (alkyl) amino such as acetamido CH3-C (O) -NH-; 17) -NH-S (O) 2-R2, 18) C1-C6 alkylcarbonyl; and 19) urea (-NH-C (O) -NH 2) and 20) halo; vi) (C1-C6) alkyl optionally substituted with one or more atoms or groups selected from 1) to 20) as defined above for v); vii) (C1-C6) alkoxy optionally substituted with one or more atoms or groups selected from 1) to 20) as defined above for v); the alkyl chain of the alkoxy which can be interrupted by one or more oxygen atoms, preferably 1 oxygen atom; viii) (C1-C6) alkylthio optionally substituted with one or more atoms or groups selected from 1) to 20) as defined previously for vi); the alkyl chain of the alkylthio may be interrupted by one or more sulfur atoms, preferably 1 sulfur atom; ix) (hetero) aryl (C1-C6) (alkyl) amino such as phenylamino Ph-N (H) -; x) (hetero) (C 1 -C 6) cycloalkyl (alkyl) amino such as cyclohexylamino; xi) (hetero) aryloxy such as phenoxy Ph-O-; xii) (hetero) arylthio such as phenylthio Ph-S-; xiii) R2-C (W) -W'- with R2 representing a hydrogen atom or a group selected from (C1-C12) alkyl, aryl such as phenyl and aryl (C1-C6) alkyl such as benzyl, W representing an oxygen atom, a sulfur atom or an N (R 3) amino group, preferably oxygen, and W 'representing an oxygen, sulfur atom or N (R 4) group with R 3 and R 4, which may be identical or different representing a hydrogen atom or a (C 1 -C 4) alkyl group, preferably a hydrogen atom; xiv) R2- (W) p-C (VV) - with R2, and W, and W 'as previously defined and p is 0 or 1; xv) R2-W'-C (W) -W "- with R2 being as defined above, R3 and R4, identical or different, representing a hydrogen atom or a (C1-C4) alkyl group, preferably a a hydrogen atom, W being as defined above, preferably an oxygen atom and W 'being as defined for W, preferably representing a group N (R3) with R3 as defined above; xvi) R2-W - C (W) - with R2, W and Wétant as defined above; xvii) R2-S (0) p- (N) qwith R2 and W as previously defined and p vallant 1 or 2 and q vallant o or R2-WS (O) p- with R2 and p as previously defined; xix) aryl such as phenyl; xx) cationic or non-cationic heteroaryl such as imidazolyl or N- (C1-C6) alkylimidazolium; xxi) heterocycloalkyl monocyclic compound comprising from 5 to 7 members, cationic or non-cationic, preferably chosen from a) piperidino optionally substituted by one or more -C (O) NH 2 or (hydroxy) (C 1 -C 6) alkyl, N- groups ( C1-C6) alkylimidazolium, b) pyrrolidino optionally substituted by one or more hydroxyl, (C1-C6) alkyl, (di) (C1-C6) (alkyl) amino, tri (C1-C6) alkyl ammonium, N- ( C1-C6) alkylimidazolium; c) piperazino which can be functionalized with one or more (C1-C6) alkyl groups; d) N, N- (C1-C6) dialkylpiperazinium; e) (di) azepano; f) morpholino; xxii) a nitrile radical (-CN); n represents an integer between 0 and 6, preferably between 1 and 4; Y represents a carbon atom, a CH group or a nitrogen atom; Z represents i) a carbon atom, a CH group or a CRi group; ii) a heteroatom selected from oxygen or sulfur atom when Z is at position 3 of formula (III), or at position 3 or 5 of formula (IV); iii) a nitrogen atom when Z is in position 1 or 2 of formula (III) or in position 1, 2, 6 and 7 of formula (IV); iv) NR5 when Z is in the 3 position of the formula (III) or 3 and 5 of the formula (IV) with R5 representing a hydrogen atom or a (ClC6) alkyl group optionally substituted by one or more radicals a ) hydroxyl, b) (C 1 -C 6) alkoxy, c) (di) (C 1 -C 6) (alkyl) amino, d) heterocycloalkyl or heterraryl with 5 or 6 chain members preferably cationic such as N, N '- (C1- C6) alkylpyperazinium, N- (C1-C6) alkylpyperidinium, N- (C1-C6) alkyl-morpholinium or N- (C1-C6) alkylimidazolum, e) carboxy, or f) sulfonic acid; it being understood that: when n is greater than or equal to two, the radicals R 1 are identical or different; when the compounds of formula (I) to (IV) comprise a cationic group, an anionic control is associated to reach the electroneutrality of the molecule, two adjacent radicals R 1 may together form a ring a fused heterocyclic ring such as morpholino ; for the formula (II), X or R 1 are bound on carbon atoms 1 to 4 or 6 to 9; for the formula (III) X or R1 are bound on the carbon atoms 1, 2 to 5 or on a carbon or nitrogen atom 3; and - for the formula (IV) X or R1 are bound on one of the carbon atoms 1, 2, 6 and 7, or on a carbon or nitrogen atom 3 and 5. 3. Process according to any one of preceding claims in which the couplers are chosen from those of formulas (Ib) to (If) below: ## STR1 ## as well as their salts of acids or inorganic or organic bases, their optical isomers, geometric, their tautomers, and / or their solvates such as hydrates; formula (Ib) in which: L represents i) a halogen atom; or a group selected from: ii) R8-G- and iii) R2- (VV ') pC (VV) - (VV ") q- such as carboxy or (C1-C6) alkylcarbonyl with p, q = 0 or 1, R2 representing a hydrogen atom or a group selected from (C1-C6) alkyl, W representing an oxygen atom, sulfur or an amino group N (R3), preferably an oxygen atom and W 'and W "representing an oxygen atom, sulfur or a group N (R4) with R3, and R4, identical or different, representing a hydrogen atom or a (C1-C4) alkyl group, preferably a hydrogen atom; preferably L represents R8-O-; G representing a bond, an oxygen or sulfur atom, preferably oxygen; R6 and R7, which may be identical or different, represent a hydrogen atom or a (C1-C6) alkyl group optionally substituted by one or more hydroxyl groups; preferably R6 and R7 represent a hydrogen atom; or else R6 and R7 form with the nitrogen atom which carries them a monocyclic heterocycle comprising from 5 to 7 members such as optionally pyrrolidino; piperazino may be substituted with one or more (C1-C6) alkyl groups; C6) alkylpiperidino and (di) azepano; or else R6 forms together with a radical Ri b contiguous monocyclic heterocycle comprising 5 to 7 members such as morpholinyl, pyperidinyl, piperazynyl optionally substituted by one or more (C1-C4) alkyl group; R8 represents a hydrogen atom; a (C1-C6) alkyl group optionally substituted by one or more hydroxyl groups; or a group S (O) 2 -R9 with R9 representing a hydrogen atom or a (C1-C6) alkyl group; it being understood that when G represents a bond then R8 can not represent a hydrogen atom; n 'is 0, 1, 2 or 3 particularly 0, 1 or 2, preferably 0 or 1; R1b represents a halogen atom, or a group chosen from: 1) (C1-C6) alkyl optionally substituted by one or more atoms or halogen, hydroxy or cyano groups, 2) (C1-C6) alkoxy optionally substituted with one or several groups selected from hydroxy, 3) -SO3H, 4) R'9-SO3- with R'9 representing a hydrogen atom or a (C1-C6) alkyl, and 5) hydroxyl group; NN (R) R, (R 1) R, R 6 R NR 7 (Ic) (Id) as well as their salts of inorganic or organic acids or bases, their optical geometric isomers, their tautomers, and / or their solvates such as the hydrates; Formulas (Ic) or (Id) in which: G is an oxygen or sulfur atom, preferably oxygen; R 6 and R 7, which may be identical or different, represent a hydrogen atom or a (C 1 -C 6) alkyl group optionally substituted with one or more hydroxyl groups; preferably, R6 and R7 represent a hydrogen atom or else R6 and R7 form, with the nitrogen atom carrying them, a monocyclic heterocycle comprising from 5 to 7 members, such as pyrrolidino optionally substituted with a (di) (C1-) group; C4) (alkyl) amino or a cationic group such as tri (C1-C6) alkylammonium; piperazino optionally substituted with one or more (C1-C6) alkyl groups; (C1-C6) (alkyl) piperidino or (di) azepano; n 'is 0, 1, 2 or 3 particularly 0, 1 or 2, preferably 0 or 1; - Rid or Rie represents a halogen atom, or a group selected from: 1) (C1-C6) alkyl optionally substituted with one or more atoms or halo or hydroxy groups; 2) (C1-C6) alkoxy optionally substituted with one or more groups selected from hydroxy; 3) cyano; 4) amino; 5) (di) (C1C12) alkylamino wherein the one or both alkyl groups of the amino are optionally substituted by one or more hydroxyl groups; 6) R2- (VV ') pC (VV) - (VV ") q- such that carboxy with p, q = 0 or 1, R2 representing a hydrogen atom or a group selected from (C1-C6) alkyl, W representing an oxygen atom, sulfur atom or an N (R 3) amino group, preferably an oxygen atom and W and W 'representing an oxygen atom, sulfur atom or an N (R 4) group with R 3, and R4, identical or different, representing a hydrogen atom or a (C1-C4) alkyl group, preferably a hydrogen atom, and 7) hydroxyl; N (R1f) n, RNNNN 6 R7 R7 (le) ) as well as their salts of inorganic or organic acids or bases, their optical isomers, geometric, their tautomers, and / or their solvates such as hydrates; Formulas (Ic) or (If) in which: - R6 and R7, identical or different, represent a hydrogen atom or a (C 1 -C 6) alkyl group optionally substituted by one or more hydroxyl groups or a (hetero) cycloalkyl group such as cyclohexyl, preferably R 6 and R 7 represent a hydrogen atom, or R6 represents a hydrogen atom or a (C1-C6) alkyl group and R7 represents a R2- (W) pC (VV) group - with p = 0 or 1, preferably p = 1 , R2 representing a hydrogen atom or a group (C1-C6) alkyl, W and W, identical or different representing an oxygen atom, sulfur or an amino group N (R3), preferably or an amino group N (R3), with R3 representing a hydrogen atom or a (C1-C4) alkyl group, preferably a hydrogen atom; orR6 and R7 together with the nitrogen atom carrying them form a 5- to 7-membered monocyclic heterocycle such as pyrrolidino; piperazino optionally substituted with one or more (C1-C6) alkyl groups; piperidino or (di) azepano; - n 'is as defined above, preferably n is 0, 1 or 2, preferably 1 or 2 - Rif and Rig are as defined previously in R1, preferably Rif and R19 represent a halogen atom, or a group selected from 1) (C1-C6) alkyl optionally substituted by one or more atoms or halogen or hydroxy groups, 2) (C1-C6) alkoxy optionally substituted by one or more groups selected from hydroxy, (di) (C1-C4) (alkyl) amino; 3) alkylthio optionally substituted by one or more hydroxy or (di) (C1-C4) (alkyl) amino groups; 4) arylthio such as pehnylthio; 5) R2- (VV ') pC (VV) - (VV ") g- such as carboxy or RC (O) -N (R') - with R and R 'as defined above, p and q = 0 or 1, R2 representing a hydrogen atom or a group selected from (C1-C6) alkyl, W representing an oxygen atom, sulfur or an amino group N (R3), preferably an oxygen atom and W ' and W "representing an oxygen atom, sulfur atom or a group N (R4) with R3, and R4, identical or different, representing a hydrogen atom or a (C1-C4) alkyl group, preferably an atom of hydrogen; 6) (di) (C1-C4) (alkyl) amino, 7) heterocycloalkyl such as pyrrolidino, pyperidino, N '(C1-C4) (alkyl) -N-pyperazino, morpholino, 8) cycloalkylamino such as cyclohexylamino; 9) R'9-S0p- with p = 1, 2 or 3 and R'9 representing a hydrogen atom or a (C1-C6) alkyl group; and 10) hydroxyl. 4. Process according to any one of claims 1 to 3 in which the couplers are chosen from those of formulas (11a) to (11d) below: R6N / R7 6 R7 6 4 (11a) 6 4 (11b) and their salts of acids or inorganic or organic bases, their optical isomers, geometrical, their tautomers, and / or their solvates such as hydrates; Formulas (11a) or (11b) in which: R6 and R7, which may be identical or different, represent a hydrogen atom or a (C1-C6) alkyl group optionally substituted by one or more hydroxyl groups; preferably R6 and R7 represent a hydrogen atom; n "is 0, 1, 2 or 3, preferably 0 or 1; R'ia represents a halogen atom, or a group selected from 1) (C1-C6) alkyl (R '(R' optionally substituted by one or more halogen atoms or hydroxyl groups, 2) (C1-C6) alkoxy optionally substituted by one or more groups selected from hydroxy, (di) (C1-C4) (alkyl) amino, carboxy, it being understood that the The alkyl group of the alkoxy may be interrupted by one or more heteroatoms such as oxygen, 3) an alkylthio optionally substituted by one or more hydroxy groups, 4) carboxy, 5) R "9 -SO 2 -sulfonic or ( C1C6) alkylsulfonylamino with p = 1, 2 or 3 and R "9 representing a hydrogen atom or a (C1-C6) alkyl, (di) (C1-C6) (alkyl) amino group, 6) RR'NC ( With R and R 'representing a hydrogen atom or a (C 1 -C 6) alkyl group; 7) (di) (C 1 -C 4) (alkyl) amino and 8) hydroxyl, particularly R' 1, is selected from 5) R "9-S0p- with p = 2 and R" 9 representing a hydrogen atom o a (C1-C6) alkyl, (C1-C6) alkoxy group; (di) (C1-C6) (alkyl) amino, especially R'1, represents a halogen atom such as chlorine, (C1-C6) alkyl, (C1-C6) alkoxy, sulphonic, carboxy, or ( C1-C6) alkylsulfonylamino; as well as their salts of mineral or organic acids or bases, their optical, geometric isomers, their tautomers, and / or their solvates such as hydrates; Formulas (11c) or (IId) in which: R6 and R7, which may be identical or different, represent a hydrogen atom or a (C1-C6) alkyl group optionally substituted with one or more hydroxyl groups; preferably R6 and R7 represent a hydrogen atom; preferably the amino group NR6R7 is on the benzo ring of the formula (11c) and more particularly in the 6, 7 or 9 position; or else in position 3 of the formula (11d); Y is as defined in formula (II) of claim 2; n "is 0, 1, 2 or 3, preferably 0 or 1; R'ia is as defined above more particularly R'1, represents a group (C1-C6) alkoxy 5. Process according to any of Claims 1 to 3 wherein the couplers are selected from those of formulas (111a) to (111c) below: ## STR1 ## R7 (R6) N6 (III) (IIIb) (IIIb) (IIIc) and their salts of acids or inorganic or organic bases, their optical isomers, geometrical, their tautomers, and / or their solvates such as hydrates; Formulas (IIIa), (IIIb) or (IIIc) in which: - R6 and R7, identical or different, represent a hydrogen atom or a (C1-C6) alkyl group optionally substituted with one or more hydroxyl groups, preferably R6 and R7 represent a hydrogen atom, Y is as defined previously in formula (III), more particularly Y represents CH, CR; "ia or N; férentiellement CH or CR "ia - Z of the formula (IIIa) or (111c) represents an oxygen or sulfur atom or a NR5 group; more particularly Z is NR5; and Z of the formula (IIIb) represents a nitrogen atom, a CH group, or CR "ia; preferably CH, or CR" ia; R5 represents a hydrogen atom or a (C1-C6) alkyl group optionally substituted by one or more radicals a) hydroxyl, b) (C1-C6) alkoxy, c) (di) (Cr C6) (alkyl) amino d) heterocycloalkyl or preferably cationic 5 or 6-membered heteroaryl such as N, A / L (di) (C 1 -C 6) alkylpyperazinium, N- (C 1 -C 6) alkylpyperidinium, N- (C 1 -C 6) alkylmorpholinium or N - (C1-C6) alkylimidazolum, e) carboxy, or f) sulfonic acid; preferably R5 represents a hydrogen atom or a (C1-C6) alkyl group optionally substituted by a hydroxy group or a heterocycloalkyl or cationic heteroaryl group such as N, A / L (di) (C 1 -C 6) alkylpyperazinium or N- (C1-C6) alkylimidazolum; n "is 0, 1, 2 or 3, preferably 0 or 1; - R" ia represents a halogen atom, or a group selected from 1) (C1-C6) alkyl optionally substituted by one or more atoms of halogen or hydroxyl or heterocycloalkyl groups or cationic heteroaryl such as N, A / L (di) (C 1 -C 6) -alkylpyperazinium or N- (C 1 -C 6) alkylimidazolum, 2) (C 1 -C 6) alkoxy optionally substituted with one or several groups selected from hydroxy, it being understood that the alkyl group of the alkoxy may be interrupted by one or more heteroatoms such as oxygen; 3) an alkylthio optionally substituted with one or more hydroxy groups; 4) carboxy; 5) R "9-S0-sulphonic or (C 1 -C 6) alkylsulphonylamino with p = 1, 2 or 3 and R" 9 representing a hydrogen atom or a (C 1 -C 6) alkyl, (di) ( C1-C6) (alkyl) amino, 6) RR'NC (O) - with R and R 'representing a hydrogen atom or a (C1-C6) alkyl group; 7) (di) (C1-C4) (alkyl) amino and 8) hydroxyl; 9) R2- (VV ') pC (VV) - (VV ") q- such as carboxy or (C- C6) alkoxycarbonyl, p and q = 0 or 1, R2 representing a hydrogen atom or a group selected from (C1-C6) alkyl, W representing an oxygen atom, sulfur or an amino group N (R3), preferably an oxygen atom and W and W "representing an oxygen atom, sulfur or a group N (R4) with R3, and R4, identical or different, representing a hydrogen atom or a (C1C4) alkyl group, preferably a hydrogen atom; and 10) aryl such as phenyl; it being understood that the nitrogen atom at the 3-position may carry a (C 1 -C 6) alkyl group optionally substituted by one or more hydroxyl groups, in which case the nitrogen atom carrying the said alkyl group is cationic; preferably the NR6R7 group is in position 6.7 or 8, more particularly in position 7. 6. Process according to any one of Claims 1 to 3 in which the couplers are chosen from those of formulas (IVa) and (IVb) ci below: (Rmla (IVa) 7 1 Z / 4 3 R6 (IVb) (R "'a1 n"' as well as their salts of mineral or organic acids or bases, their optical, geometrical isomers, their tautomers, and / or their solvates such as hydrates; Formulas (IVa), or (IVb) in which: R6 and R7, identical or different, represent a hydrogen atom or a (C1-C6) alkyl group optionally substituted by one or more groups; hydroxy, preferably R6 and R7 represent a hydrogen atom, Z of the formula (IVa) represents CH, CR "ia, N or a group NR5, more particularly Z of the formula (IVa) represents a group NR5; of the formula (IVb) represents an oxygen atom, sulfur atom or an NR5 group, more particularly Z of the form ule (IVb) represents a sulfur atom; R5 represents a hydrogen atom or a (C1-C6) alkyl group optionally substituted with one or more radicals a) hydroxyl, b) (C1-C6) alkoxy, (di) (C1-C6) (alkyl) amino, d ) optionally cationic 5- or 6-membered heterocycloalkyl or heteroaryl such as N, A- (di) (C 1 -C 6) alkylpyperazinium, N- (C 1 -C 6) alkyl-pyperidinium, N- (C 1 -C 6) alkylmorpholinium or N- (C1-C6) alkylimidazolum, e) carboxy, or f) sulfonic acid; preferably R5 represents a hydrogen atom or a (C1-C6) alkyl group more particularly R5 represents a hydrogen atom; n "'is 0, 1, or 2, preferably 0 or 1; Rmia represents a halogen atom, or a group selected from 1) (C1-C6) alkyl optionally substituted by one or more halogen atoms or groups hydroxyl or (di) (C 1 -C 6) (alkyl) amino, 2) (C 1 -C 6) alkoxy optionally substituted by one or more groups selected from hydroxy, it being understood that the alkyl group - - - - - of alkoxy may be interrupted by one or more heteroatoms such as oxygen, 3) an alkylthio optionally substituted by one or more hydroxy groups, 4) carboxy; 5) R "9-S0 p- such as sulfonic or (C1-C6) alkylsulfonylamino with p = 1, 2 or 3 and R "9 representing a hydrogen atom or a (C 1 -C 6) alkyl, (di) (C 1 -C 6) (alkyl) amino; 6) (di) (C 1 -C 4) group ) (alkyl) amino and 7) hydroxyl; 8) R2 '(VVI-C (VV) - (VV ") q- such as carboxy or (C1-C6) alkoxycarbonyl, p and q = 0 or 1, R2 representing a hydrogen atom or a group selected from (C 1 -C 6) alkyl, W representing an oxygen atom, sulfur or an amino group N (R3), preferably an oxygen atom and W 'and W "representing an oxygen atom, sulfur or a group N (R4) with R3, and R4, identical or different, representing a a hydrogen atom or a (C 1 -C 4) alkyl group, preferably a hydrogen atom; 10) aryl such as phenyl and 11) -W-aryl with W as previously defined in particular -W-aryl is a phenoxy group; particularly R-1, is selected from halogen such as chlorine; C6) alkyl optionally substituted with a (di) (C1-C4) (alkyl) amino group; C6) alkylthio; and aryloxy such as phenoxy; preferably the NR6R7 group is in the 2 or 3 position. 7. The process according to any one of the preceding claims wherein the couplers are selected from those of the formulas below; as well as their salts of organic or mineral acid, their optical isomers, geometric, tautomers and their solvates such as hydrates: OHOH 1 2 OH 3 NH 2 NH 4 NH 2 NH 2 NH 2 OH ## STR2 ## ## STR2 ## NH 2 23 26 28 31 cID, (D, 21 N, N 2 NH 2, NH 2, NH 2, NH 2, NH 2, NH 2, NH 2, NH 2, NH 2, NH 2, NH 2, NH 2, NH 2, NH 2, NH 2, NH 2, NH 2, NH 2, NH 2, NH 2 // ° 16 NI Yi NI NH2 14 O / OH .............. ', -,>' .........., .. o ......, ... '', ..-- 17 H NH2 NH2 36 NH2 38 39 NH2 NH241 44 HO 53 56 42 45 48 51 54 H2 57 60 63 66 40 43 46 49 52 55 53 47 59 62 65 NH2 NH2 NH2 NH2 73 74 N \ 75 sN OH 76 77 78 NN / NHNH 80 84 87 NH2 89 90 81 79 82 85 88 83 86 68 NH 7 NH 2 N -NH 2 N -NH-N-OH 67 70 69 72 91 92 93 95 94 NI-97 96 99 100 NH2 8. Process according to any one of the preceding claims in which the ingredient or ingredients ii) are chosen from those of formulas (V) to (VII) below, as well as their salts of organic or inorganic acid, their optical, geometrical isomers, tautomers and their solvates such as hydrates: R1 R1 R3 R3 AE EA ## STR5 ## Formula (V) or (VI) in which: R 1, R 2, R 3 and R 4, which may be identical or different, represent a hydrogen atom or a hydrogen atom; (C1-C8) alkyl, linear or branched, optionally substituted, (C-C8) alkoxy, linear or branched; optionally substituted aryl such as phenyl; or else R1 and R2 and / or R3 and R4 together with the carbon atoms which carry them an optionally substituted (hetero) cycloalkyl comprising from 3 to 7 members, particularly (C3-C6) cycloalkyl such as cyclohexyl; preferably, R1, R2, R3 and R4, which may be identical or different, represent a hydrogen atom or a linear or branched (C1-C6) alkyl group; x and y, which may be identical or different, represent an integer between 0 and 6, preferably x and y = 0. EA and EA ', which are identical or different, preferably identical, represent an electron-withdrawing group, preferably an electroattractant by effect. mesomer -M, such as cyano, phosh (on) ate, sulf (on) ate, nitro, or nitroso; more particularly EA EA '= cyano-R, and R' identical or different, preferably identical, represent i) an EA or EA 'radical as defined above, or a selected group ii) among (C1-C8) alkyl, linear or branched, optionally substituted, iii) optionally substituted aryl, iv) optionally substituted aryl ((C1-C8) alkyl, or else R with R1 and / or R 'with R3 together with the carbon atom which carry them a group C (X1) and R2 and R4 being as defined above or R2 and R4, which may be identical or different, represent a group R5- (X2), in which w is 0 or 1, R5 represents a hydrogen atom, a linear or branched (C1-C8) alkyl group, an optionally substituted (hetero) aryl group such as phenyl or a (hetero) cycloalkyl group optionally substituted in particular with a (C1-C6) alkyl group such as cyclohexyl optionally substituted by a (C1-C8) alkyl group and X2 is as defined below; X., which may be identical or different, represent a heteroatom chosen from oxygen and sulfur, a -C (O) -O- or -O-C (O) - group, a -O-C (O) -O- group or 0-C (O) -O-; preferably X. represent an oxygen atom; - X ', and X2, identical or different, representing a heteroatom selected from oxygen, sulfur and amino N (R ") with R" being a hydrogen atom or a group (C1-C6) alkyl, linear or branched; preferably X1 and X2 represent an oxygen atom. 9. Process according to any one of the preceding claims, in which the ingredient (s) ii) are chosen from: inorganic or organic persulfates, such as ammonium persulfates; organic peroxides such as di-tert-butyl peroxide, benzoyl peroxide (POB), methyl ethyl ketone peroxide (MEKP); organic peroxides such as benzoyl peroxide, dicumyl peroxide and di-tert-butyl peroxide; azo compounds such as 2,2 "-azobisisobutyronitrile (AIBN) or 1,1'-azobis (cyclohexanecarbonitrile) (ABCN), and - the reaction products: - between hydrogen peroxide and ascorbic acid between hydrogen peroxide and metal salts, in particular metal salts of transition metals such as Fe, in particular metal salts of Fe2 +, - between organic peroxides such as ammonium persulfate and metabisulfites, metal dichromates alkali or alkaline earth metal, such as sodium dichromate, and copper (Cu) II copper halides such as CuCl 2, 10. The process according to any one of the preceding claims, wherein the ingredient (s) ii) are selected from those of formulas (VII) below: ## STR2 ## wherein W represents a cationic, mineral or organic counterion, in particular chosen from alkali metals such as s odium or potassium, or alkaline earth metal, and ammonium RaRbRcRdN + with Ra, Rb, Rc, and Rd, identical or different, represent a hydrogen atom or a (C1-C6) alkyl group such as NH4. any one of the preceding claims wherein the coloring agent (s) are produced by a process which implements: in the first step, the solubilization of the couplers i) as defined in any one of claims 1 to 7, in a liquid solution preferably hydroalcoholic; then - in the second step the addition of one or more alkaline agents, especially with ammonia to reach a basic pH preferably between 8 and 10, then - in a third step the addition of the ingredient (s) ii) as defined in any one of claims 1, 8 to 10; in particular the preparation process is carried out at ambient temperature (25 ° C.) and with stirring for between 30 minutes and two days, preferably between one hour and three hours; optionally - in a fourth step the precipitate formed is filtered, washed preferably with water and then dried preferably in vacuo. 12. Process according to any one of the preceding claims, in which the coloring agent (s) is (are) carried out according to a process which uses a quantity of couplers (i) as defined in any one of Claims 1 to 7, and in ingredients (ii) such as as defined in any one of claims 1, 8 to 10 respecting a weight ratio i) / ingredient couplers ii) between 0.5 and 1.5, particularly the ratio = 1. 13. Process according to any one of the preceding claims in wherein the coloring agent (s) are selected from poly (Ib) with (Ib) as defined in claim 3, especially poly (3-pyrrolidin-1-yl-phenol) and poly (3-aminophenol) poly (2,5-dimethoxyaniline) and poly (3,4-dihydro-2H-1,4-benzoxazin-6-ol); poly (Ic) with (Ic) as defined in claim 3, especially poly (2,6-diaminopyridine) and poly (2-amino-3-hydroxy-pyridine, poly (IIc) with (11c) such as defined in claim 4, especially poly (6-aminoquinoxaline), poly (IIIa) with (IIIa) as defined in claim 5, in particular poly (6-hydroxy-indole) and poly (IIIb) with (111b) as defined in claim 5, in particular poly (6-aminoindazole) 14. A method according to any one of the preceding claims wherein the dyeing process comprises the following steps: 1) The application on keratin materials a composition comprising at least one coloring agent as defined in any one of the preceding claims; then 2) the dyeing composition is left paused on the keratin materials for a period inclusive between 5 minutes and 1 hour, preferably between 10 minutes and 40 minutes; then 3) optionally the keratin materials are shampooed with a conventional shampoo and / or rinsed and dried. 15. Coloring agent obtained from the polycondensation of i) couplers reacting with each other as defined in any one of claims 1 to 7, in the presence of ii) at least one radical initiator as defined in any one of the claims 1.8 to 10; optionally prepared according to the process of claim 12 or 13; it being understood that the couplers are different from 2,5-dimethoxyaniline, 2-methyl-5-methoxyaniline, 2-methoxy-5-methylaniline, 3-aminophenol. 16. Coloring agent as defined in the preceding claim wherein the coloring agent (s) are chosen from poly (Ib) with (Ib) as defined in claim 3, poly (3-pyrrolidin-1-yl) phenol), poly (3,4-dihydro-2H-1,4-benzoxazin-6-ol); poly (1c) with (Ic) as defined in claim 3, especially poly (2,6-diamino-pyridine) and poly (2-amino-3-hydroxy-pyridine, poly (11c) with (11c) ) as defined in claim 4, in particular poly (6-aminoquinoxaline), poly (111a) with (IIIa) as defined in claim 5, in particular poly (6-hydroxy-indole) and poly ( 111b) with (111b) as defined in claim 5, in particular poly (6-aminoindazole) being understood that the agent is different from poly (2,5-dimethoxyaniline), poly (2-methyl-5-methoxyaniline) ), poly (2-methoxy-5-methylaniline), and poly (3-aminophenol). 17. A composition comprising at least one coloring agent as defined in any one of claims 15 or 16; preferably not comprising an oxidation base and / or chemical oxidizing agent. 18. Use of coloring agent (s) as defined in any one of claims 1 to 16 for dyeing keratin materials, especially keratin fibers, in particular human fibers such as the hair.