A process for coloring keratin fibers using an acetoacetate compound, a (poly)amine compound, and a direct dye

Abstract

The present invention relates to a method for coloring keratin fibers using at least one compound with acetoacetate functions, at least one (poly)amine compound and at least one direct dye.

Description

Title of the invention: A method for coloring keratin fibers using a compound with acetoacetate functional groups, a (poly)amine compound, and a direct dye. Technical field of the invention

[0001] The present invention relates to a method for coloring keratin fibers using at least one compound with acetoacetate functions, at least one (poly)amine compound and at least one direct dye. Context of the invention

[0002] It is known to dye keratin fibers, and in particular human hair, with dye compositions containing oxidation dye precursors, generally called oxidation bases, such as ortho- or para-phenylenediamines, ortho- or para-aminophenols, and heterocyclic compounds. These oxidation bases are generally associated with couplers. These bases and couplers are colorless or weakly colored compounds which, when combined with oxidizing agents, can give rise, through an oxidative condensation process, to colored compounds. This type of oxidation coloring makes it possible to obtain so-called permanent hair colors.

[0003] Furthermore, it is known to dye keratin fibers, and in particular human hair, with dye compositions containing direct dyes. The conventional dyes used are, in particular, benzene nitrate, anthraquinone, nitropiridine, azo, xanthenic, acridine, azinic, triarylmethane, or natural dyes. These dyes are colored molecules or colorants having a certain affinity for keratin fibers.

[0004] Compositions containing one or more direct dyes are applied to keratin fibers for a time necessary to obtain the desired color, and then rinsed. The resulting colors are particularly chromatic, but are temporary or semi-permanent, because the nature of the interactions that bind the direct dyes to the keratin fiber, and their desorption from the surface and / or the core of the fiber, are responsible for their lower dyeing power and reduced resistance to washing or perspiration, which can also lead to problems of selectivity and / or potential color change when several direct dyes are used.

[0005] Direct coloring products allow, in particular, for modifying the natural color of the hair, or for covering gray hair. However, the intensity of The color obtained by using these products is sometimes considered too weak compared to users' expectations on the day of application.

[0006] In addition, direct colorings have the disadvantage of fading over time, in particular under the action of UV, weathering, and successive shampooing, which can also lead to problems of selectivity and / or possible color change when several direct colorings are used.

[0007] There is therefore a real need to develop a process for coloring keratin fibers using direct dyes which allows for good color development, intense and chromatic colors and improved persistence to shampoos, in particular at least 5 or 10 shampoos, and allows to limit possible problems of selectivity and / or possible color change, when several direct dyes are used, or even to bring shine to the hair.

[0008] The applicant has surprisingly discovered that all or part of these objectives can be achieved by the process according to the present invention. Summary of the invention

[0009] According to a first aspect, the present invention relates to a method for coloring keratin fibers by applying the following to the keratin fibers: (i) one or more compounds A chosen from among the compounds of formula (I), their optical isomers, their geometric isomers, their salts, their solvates such as hydrates, and their mixtures: Formula (I) in which: - R1 represents a versatile hydrocarbon radical in C2 to CM, linear or branched, saturated or unsaturated, conjugated or not, acyclic or cyclic, aromatic or not, R1 being further: a) possibly substituted by one or more hydroxy groups OH, dialkylamino-N(R)2 with R representing a (Ci-C4)alkyl group, carboxy-C(O)-OH, a vinyl group, and / or b) possibly interrupted by one or more heteroatoms or groups selected from O, S, carbonyl -C(O)-, amine -N(R'), or combinations thereof, in which R' represents a hydrogen atom, a linear or branched alkyl group having from 1 to 4 carbon atoms possibly substituted by at least one hydroxy group (OH) or possibly substituted by -XC(O)-C(Ra)(Rb)-C(O)-R2; - R2 represents a monovalent hydrocarbon radical in C1 to C6, linear or branched, saturated or unsaturated; - Ra, and Rb, identical or different, represent a hydrogen atom or a (CrC4)alkyl group; - X is a heteroatom or group chosen from O, S, N(R') or , -S-CH2-C(O)-O-, -OC(O)-CH2-S-, -OC(O)-N(R')-, -N(R')-C(O)-O-, -N(R')-C(O)-N(R')-, R' being as defined previously; - n denotes an integer ranging from 2 to 10, particularly from 3 to 9; and ii) one or more (poly)amine compounds; and iii) one or more direct dyes.

[0010] According to a second aspect, the present invention relates to a composition (C) comprising the compound(s) A as defined above, the (poly)amine compound(s) and the direct colorant(s).

[0011] According to a third aspect, the present invention relates to a two- or three-compartment device comprising: - a first compartment containing a composition comprising the compound(s) A as defined above and possibly one or more direct dyes; - a second compartment separate from the first compartment containing a composition comprising the (poly)amine compound(s) and possibly one or more direct dyes; - possibly a third compartment separate from the first and second compartments containing one or more direct dyes, it being understood that at least one of the compartments includes one or more direct dyes.

[0012] According to a fourth aspect, the present invention relates to the use of one or more compounds A as defined above associated with one or more (poly)amine compounds or of a composition (B) comprising the compound(s) A as defined above and the (poly)amine compound(s) to improve the residual effect of direct dyeing of keratin fibers on shampoos. Detailed description of the invention

[0013] For the purposes of the present invention, and unless otherwise indicated:

[0014] ■ By "keratin fibers" we mean fibers of human or animal origin such as that hair, body hair, eyelashes, eyebrows, wool, angora, cashmere or the fur. According to the present invention, the keratin fibers are preferably human keratin fibers, more preferably hair;

[0015] ■ an "aryl" radical represents a mono- or polycyclic hydrocarbon group, condensed or not, comprising from 6 to 14 carbon atoms, and of which at least one ring is aromatic; preferably the aryl radical is a phenyl, biphenyl, naphthyl, indenyl, anthracenyl, or tetrahydronaphthyl;

[0016] ■ a "heteroaryl" radical represents a mono- or polycyclic group, condensed or not, comprising 5 to 14 links, 1 to 6 heteroatoms chosen from nitrogen, oxygen, sulfur and selenium atoms, and of which at least one ring is aromatic; preferably a heteroaryl radical is chosen from acridinyl, benzimidazolyl, benzobistriazolyl, benzopyrazolyl, benzopyridazinyl, benzoquinolyl, benzothiazolyl, benzotriazolyl, benzoxazolyl, pyridinyl, tetrazolyl, dihydrothiazolyl, imidazopyridinyl, imidazolyl, indolyl, isoquinolyl, naphthoimidazolyl, naphthooxazolyl, naphthopyrazolyl, oxadiazolyl, oxazolyl, oxazolopyridyl, phenazinyl, phenooxazolyl, pyrazinyl, pyrazolyl, pyrilyl, pyrazoyltriazyl, pyridyl, pyridinoimidazolyl, pyrrolyl, quinolyl, tetrazolyl, thiadiazolyl, thiazolyl, thiazolopyridinyl, thiazoylimidazolyl, thiopyrylyl, triazolyl, xanthylyl; ■ by "(hetero)aryl" we mean the aryl or heteroaryl groups;

[0017] ■ by "(hetero)cycloalkyl" means cycloalkyl or heterocycloalkyl groups;

[0018] ■ the "aryl" or "heteroaryl" radicals or the aryl or heteroaryl part of a radical can be substituted by at least one substituent attached to a carbon atom, chosen from: - an alkyl radical in Ci-C6, preferably in Ci-C4; - a halogen atom such as chlorine, fluorine or bromine; - a hydroxy group; - a C1-C2 alkoxy radical; a C2-C4 (poly)-hydroxyalkoxy radical; - an amino radical; - an amino radical substituted by one or two alkyl radicals, identical or different, in Ci-C6, Ci-C6, preferably in CrC4; - an acylamino radical (-N(R)-C(O)-R') in which the radical R is a hydrogen atom; - an alkyl radical in CrC4 and the radical R' is an alkyl radical in CrC4; a carbamoyl radical (R2N-C(O)-) in which the radicals R, identical or not, represent a hydrogen atom, an alkyl radical in CrC4; - an alkylsulfonylamino radical (R'S(O)2-N(R)-) in which the radical R represents a hydrogen atom, a Ci-C4 alkyl radical and the radical R' represents a C1-C4 alkyl radical, a phenyl radical; - an aminosulfonyl radical (R2N-S(O)2-) in which the R radicals, identical or not, represent a hydrogen atom, an alkyl radical in CrC4; - a carboxylic radical in acidic or salified form (preferably with an alkali metal or an ammonium, substituted or unsubstituted); - a cyano group (CN); - a polyhalogeno(Ci-C4)alkyl group, preferably trifluoromethyl (CF3); ■ The cyclic or heterocyclic part of a non-aromatic radical can be substituted by at least one substituent attached to a carbon atom chosen from the following groups: - hydroxy; - CrC4 alkoxy, (poly)hydroxy C2-C4 alkoxy; - alkylearbonylamino (RC(O)-NR'-) in which the radical R' is a hydrogen atom, an alkyl radical in Ci-C4 and the radical R is an alkyl radical in CrC4, amino substituted by one or two identical or different alkyl groups in CrC4; - alkylearbonyloxy (RC(O)-O-) in which the radical R is an alkyl radical in CrC4, amino substituted by one or two identical or different alkyl groups in CrC4; - alkoxycarbonyl (RO-C(O)-) in which the radical R is an alkyl radical in CrC4;

[0019] ■ a cyclic radical, heterocyclic radical, or a non-aromatic part of an aryl radical or heteroaryl, can also be substituted by one or more oxo groups;

[0020] ■ A hydrocarbon chain is unsaturated when it comprises one or more double bonds and / or one or more triple bonds; preferably one or more double bonds;

[0021] ■ A "cyclic" or "cycloalkyl" radical is a non-cyclic hydrocarbon radical aromatic, mono or polycyclic, condensed or not, containing from 5 to 14 carbon atoms, which may have from 1 to several unsaturations, preferably the cycloalkyl is a cyclohexyl group;

[0022] ■ A "heterocyclic" or "heterocycloalkyl" radical is a non-cyclic radical aromatic mono or polycyclic, condensed or non-condensed, containing 3 to 9 links, comprising 1 to 4 heteroatoms chosen from nitrogen, oxygen, sulfur and selenium atoms, preferably the heterocycloalkyl is chosen from epoxide, piperazinyl, piperidinyl, morpholinyl, or dithiolane;

[0023] ■ an "alkyl" radical is a saturated hydrocarbon radical, linear or branched, in particularly in Ci-C6, preferably in Ci-C4;

[0024] ■ an "alkoxy" radical is an alkyl-oxy radical for which the alkyl radical is a hydrocarbon radical, linear or branched, in Ci-C6 preferably in Ci-C4;

[0025] ■ a "(poly)(hydroxy)alkyl" radical designates a Ci-C6 alkyl radical, of preferably in Ci-C4 possibly substituted by one or more hydroxy radicals, preferably substituted by 1 to 4 hydroxy groups, more particularly between 1 and 3;

[0026] ■ a "sugar" radical is a monosaccharide or disaccharide radical; Examples include as sugar radical: sucrose (or saccharose), glucose, galactose, ribose, fucose, maltose, fructose, mannose, arabinose, xylose, or lactose;

[0027] ■ By "monosaccharide", we mean a monosaccharide sugar comprising at least 5 carbon atoms, preferably of formula CX(H2O)X, with x an integer greater than or equal to 5, preferably x is greater than or equal to 6, in particular x is inclusively between 5 and 7, preferably x = 6, they may be of D or L configuration, and of alpha or beta anomer, as well as their salts and solvates such as hydrates;

[0028] ■ By "disaccharide", we mean a disaccharide sugar which is a compound made up of two sugars linked together by O-glycosidic bonds said compounds being made up of two monosaccharides (also called mono-glycosidics) as defined above said monosaccharide units comprising at least 5 carbon atoms, preferably 6, particularly the monosaccharide units being linked together in 1,4 or 1,6 in anomer a (alpha) or |3# (beta), each sugar unit being able to be of L or D configuration, as well as its salts and solvates such as the hydrates of said monosaccharides; more specifically, it concerns compounds formed of two sugars (or monosaccharides) having the general formula: -[Cx(H2O)y)]2- or -[(CH2O)X ]2-, with x an integer greater than or equal to 5, preferably x is greater than or equal to 6, in particular x is inclusively between 5 and 7, preferably x = 6, and y an integer which represents x - 1;

[0029] ■ By "polysaccharide", we mean a polysaccharide sugar which is a polymer consisting of at least 3 monosaccharides linked together by O-glycosidic bonds, said polymers being composed of monosaccharide units (also called monosaccharides) as defined above, said monosaccharide units comprising at least 5 carbon atoms, preferably 6, particularly the monosaccharide units being linked together in 1,4 or 1,6 anomers in α (alpha) or β (beta) configuration, each monosaccharide unit being able to be of L or D configuration, as well as its salts and solvates such as the hydrates of said monosaccharides; more particularly, these are polymers formed of a certain number of monosaccharides having the general formula: -[Cx(H2O)y)]w- or -[(CH2O)X]W-, with x an integer greater than or equal to 5, preferably x greater than or equal to 6, in particular x inclusively between 5 and 7, preferably x = 6, and y an integer that represents x - 1, and w is an integer greater than or equal to 2, particularly inclusively between 3 and 3000, more particularly between 5 and 2500, preferably between 10 and 2300, particularly inclusively between 15 and 1000, more particularly between 20 and 500, preferably between 25 and 200;

[0030] ■ By "salt", we mean an addition salt with an organic acid or base or mineral. The addition salts with an organic or mineral acid are in particular chosen from the salts derived i) from hydrochloric acid HCl, ii) from hydrobromic acid HBr, iii) from sulfuric acid H2SO4, iv) from alkylsulfonic acids: Alk-S(O)2OH such as methylsulfonic acid and ethylsulfonic acid; v) from arylsulfonic acids: Ar-S(O)2OH such as benzenesulfonic acid and toluenesulfonic acid; vi) from alkoxysulfinic acids: Alk-OS(O)OH such as methoxysulfinic acid and ethoxysulfinic acid; vii) from aryloxysulfinic acids such as tolueneoxysulfinic acid and phenoxysulfinic acid; viii) from phosphoric acid H3PO4; ix) of triflic acid CF3SO3H and x) of tetrafluoroboric acid HBF4;xi) of carboxylic organic acids R°-C(O)-OH (l'z) formula (Fz) in which R° represents a (hetero)aryl group such as phenyl, (hetero)aryl(Ci-C4)alkyl such as benzyl, or (Ci-Cio)alkyl said alkyl group being optionally substituted preferably by one or more hydroxy groups, amino radicals, or carboxy groups, R° preferably designating a (Ci-C6)alkyl group optionally substituted by 1, 2 or 3 hydroxy groups, or more preferably the monocarboxylic acids of formula (l'z) are chosen from acetic acid, glycolic acid, lactic acid, and mixtures thereof, and more particularly from acetic acid and lactic acid; and the polycarboxylic acids are chosen from tartaric acid, succinic acid, fumaric acid, citric acid and mixtures thereof;and xii) amino acids containing more carboxylic acid radicals than amino groups, such as gamma-carboxyglutamic acid, aspartic acid, glutamic acid, and in particular gamma-carboxyglutamic acid. Addition salts with an organic or mineral base are particularly chosen, such as alkali metal hydroxides, alkaline earth metal hydroxides, alkali or alkaline earth metal carbonates, alkali or alkaline earth metal bicarbonates, addition salts with so-called basic amino acids such as arginine and lysine, and addition salts with amines, possibly hydroxylated;

[0031] ■ an "anionic counter-ion" is an associated anion or anionic group to a cationic charge; more particularly the anionic counter-ion is chosen from i) halides such as chloride, bromide; ii) nitrates; iii) sulfonates, including the Ci-C6 alkylsulfonates: Alk-S(O)2O such as methylsulfonate or mesylate and ethylsulfonate; iv) arylsulfonates: Ar-S(O)2O such as benzenesulfonate and toluenesulfonate or tosylate; v) citrate; vi) succinate; vii) tartrate; viii) lactate; ix) alkyl sulfates: Alk-OS(O)O such as methyl sulfate and ethyl sulfate; x) aryl sulfates: Ar-OS(O)O such as benzene sulfate and toluene sulfate; xi) alkoxy sulfates: Alk-OS(O)2O such as methoxy sulfate and ethoxy sulfate; xii) aryloxysulfates: Ar-OS(O)2O, xiii) phosphates: O=P(OH)2-O-, O=P(O-)2-OH, O=P(O-)3, HO-[P(O)(O-)]wP(O)(O-) 2, where w is an integer; xiv) acetate; xv) triflate; xvi) borates such as tetrafluoroborate; xvii) disulfate (O=)2S(O-)2 or SO42; and xviii) monosulfate HSO4

[0032] ■ the "solvates" represent the hydrates as well as the association with alcohols linear or branched CrC4 such as ethanol, isopropanol, n-propanol;

[0033] 'By "chromophore" is meant a radical derived from a colorless or colored compound capable of absorbing in the UV and / or visible radiation at a wavelength Xabs between 250 and 800 nm; Preferably the chromophore is colored i.e. it absorbs wavelengths in the visible i.e. preferably between 400 and 800 nm. Preferably the chromophores appear colored to the eye; particularly between 400 and 700 nm (Ullmann's Encyclopedia^ 2005, Wiley-VcH, Verlag "Dies, General Survey", § 2.1 Basic Principle of Color);

[0034] ■ By "direct colorant" is meant a natural and / or synthetic colorant, including in extract form(s), different from oxidation dyes. These are colored compounds that diffuse superficially onto the fiber. They can be ionic or non-ionic, i.e., anionic, cationic, neutral, or non-ionic.

[0035] The expressions "at least one" and "one or more" are synonymous and can be used interchangeably.

[0036] The expressions "between ... and ...", "includes from ... to ...", "made up of ... to ...", and "ranging from ... to ..." should be understood inclusive of bounds, unless otherwise specified. Keratin fiber coloring process

[0037] According to a first aspect, the present invention relates to a method for coloring keratin fibers as defined above.

[0038] The applicant has found, surprisingly, that the coloring process according to the present invention makes it possible to obtain good color development, intense and chromatic colors, improved color retention after shampooing, in particular after at least 5 or 10 shampoos, and to limit any potential problems of selectivity and / or possible color change, when several direct dyes are used, or even to add shine. Compounds A

[0039] The compound(s) A used in the coloring process according to the present invention are chosen from compounds of formula (I), their optical isomers, their geometric isomers, their salts, their solvates such as hydrates, and their mixtures: Formula (I) in which: - R1 represents a versatile hydrocarbon radical in C2 to CM, linear or branched, saturated or unsaturated, conjugated or not, acyclic or cyclic, aromatic or not, R1 being further: a) possibly substituted by one or more hydroxy groups OH, dialkylamino-N(R)2 with R representing a (Ci-C4)alkyl group, carboxy-C(O)-OH, a vinyl group, and / or b) possibly interrupted by one or more heteroatoms or groups selected from O, S, carbonyl -C(O)-, amine -N(R'), or their combinations, in which R' represents a hydrogen atom, a linear or branched alkyl group having from 1 to 4 carbon atoms possibly substituted by at least one hydroxy group (OH) or possibly substituted by -XC(O)-C(Ra)(Rb)-C(O)-R2; - R2 represents a monovalent hydrocarbon radical in C1 to C6, linear or branched, saturated or unsaturated; - Ra, and Rb, identical or different, represent a hydrogen atom or a (Ci-C4)alkyl group; - X is a heteroatom or group chosen from O, S, N(R') or , -S-CH2-C(O)-O-, -OC(O)-CH2-S-, -OC(O)-N(R')-, -N(R')-C(O)-O-, -N(R')-C(O)-N(R')-, R' being as defined previously; - n denotes an integer ranging from 2 to 10, particularly from 3 to 9.

[0040] Preferably, the compound(s) A are chosen from compounds of formula (la), their optical isomers, their geometric isomers, their salts, their solvates such as hydrates, and their mixtures: (la) 19 9 1 Formula (the) in which: - R1 is as defined above, particularly represents a versatile hydrocarbon radical in the range C2 to CM, preferably C3-C12, preferably C4-C10, linear or branched, saturated or unsaturated, conjugated or not, acyclic or cyclic, aromatic or not, R1 being further: a) possibly substituted by one or more hydroxy groups OH, and / or b) possibly interrupted by one or more heteroatoms or groups chosen from O, S, -N(R'), preferably interrupted by one or more oxygen atoms in which R' is as defined above; - R2 is as defined previously, preferably R2 represents a (Ci-C6)alkyl group, linear or branched, preferably a (Ci-C4)alkyl group, more preferably methyl or tert-butyl such as methyl; and - n is as defined previously, preferably n denotes an integer from 2 to 9.

[0041] According to one embodiment, the compounds of formula (I) or (la) are such that R1 represents a C6 to C8 C6-C ...

[0042] According to another embodiment, the compounds of formula (I) or (la) are such that R1 represents a C5 to C12 saturated monocyclic or bicyclic hydrocarbon polyvalent radical, optionally interrupted by one or more heteroatoms or groups selected from O, S, -N(R'), in which R' represents a hydrogen atom, an alkyl group having from 1 to 4 carbon atoms, preferably interrupted by one or more oxygen atoms. Preferably, according to this other embodiment, R1 represents a monosaccharide or polysaccharide motif, in particular a disaccharide, on which n hydroxyl groups have been substituted by n -OC(O)-CH2-C(O)-R2 groups, with R2 and n as defined above.

[0043] Suitable monosaccharides according to the invention include, but are not limited to, ribose, glucose, mannose, galactose, fructose, sorbose and inositol.

[0044] According to one embodiment, the disaccharides are selected from cellobiose, maltose, lactose, raffinose, sucrose, trehalose, melibiulose, melibiose, mannobiose, kojibiose, nigerose, isomaltose, rutinose, rutinulose, xylobiose, preferably sucrose.

[0045] According to another preferred embodiment of the invention, the compounds of formula (I) or (la) are such that R1 represents a C2-C12 acyclic hydrocarbon polyvalent radical, preferably linear or branched, saturated or unsaturated, preferably saturated.

[0046] Preferably, the compounds of formula (I) or (la) are such that R1 represents a versatile acyclic hydrocarbon radical, selected from the radicals mannitol, xylitol, sorbitol, trimethylolpropane, di(trimethylolpropane), 2-methyl-1,3-propanediol, 2-hydroxymethyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, erythritol, pentaerythritol or dipentaerythritol, more preferably mannitol, xylitol, sorbitol, trimethylolpropane, di(trimethylolpropane), 2-methyl-1,3-propanediol, 2-hydroxymethyl-1,3-propanediol, erythritol, pentaerythritol or dipentaerythritol.

[0047] According to a particular embodiment of the invention, the compounds of formula (I) or (la) are such that n denotes an integer from 2 to 9, more particularly n denotes an integer from 3 to 9, even more particularly n denotes an integer from 4 to 9 such as 6 or 8.

[0048] According to one embodiment, the compounds of formula (I) or (la) are such that n equals 2. According to another embodiment, the compounds of formula (I) or (la) are such that n equals 3. According to another embodiment, the compounds of formula (I) or (la) are such that n equals 4. According to another embodiment, the compounds of formula (I) or (la) are such that n equals 5. According to another embodiment, the compounds of formula (I) or (la) are such that n equals 6. According to another embodiment, the compounds of formula (I) or (la) are such that n equals 7. According to another embodiment, the compounds of formula (I) or (la) are such that n equals 8. According to another embodiment, the compounds of formula (I) or (la) are such that n equals 9.

[0049] Preferably, the compound(s) A are chosen from the following compounds, their optical isomers, their salts, their solvates such as hydrates, and their mixtures: (Composed) ■HW' . Structure;^ (1) 700865-73-2 3-oXo-1,1^1,7-heptanectiyQ butanoic acid ester 57 & V "W 'X-.-"'' '-y' 'X'Y' 'V1 (2) 632336,1-20-0 1.8-octaned^yl) butaroic acid ester X-' ■,« jv --y X-' \ex> (3) 501426-98-8 3-oxo-1,T-(1,1Q-decan^yl) butanoic acid ester x-' X' ''' ''.-' 'x<''' (4) 174498-06-7 3-oxo-tT-(13-propanediyî) to add butanoïqœ y ? vy x.-- ■ ' Vs--- X (5J 160187-52-0 3-0xa-1 .2-dimefty^- 1,2-ethanediyl butanoic acid ester 0 0 s oy*Xx y^X (S) 145020-19-5 3-oxo-2-biftyk2-êthyk 1,3-propanedjyi butanoic acid ester -7 v 7-' (7} 87530-36-7 3-oxo-l, 1,2,2-tetramethylM ,2-ethanediyl butanoic acid ester tî \ / * vox X" X' ''X / \ ;j :t . (Gum-like) CAS Name ohihi^ Chemical Structure R 58213-75-5 3-oxo* 1,1X1 -methy k 153-prDpanediyl) butanoic acid ester !.< <■' (S) 58213-74-4 3-OX0-1.1-122-dimethylM-(1-methylethyl)-1,3-propanediyl] butanoic acid ester u û X'Y"' (W) 39564-28-8 3-oxo-1fT-(1t5-pentanediyl) butanoic acid ester ..Y ' (11) 14276-67-6 3-oxo- 1,f -(2,2-dimethylMG-propanediyl) butanoic acid ester O £5 •? a (12) 13018-41-2 3-oxo-154-butanediy( butanoic acid ester -'•''•K (13) 6079-90-9 3-oxo-l -methylM .2-ethanediyi butanoic acid ester r' v (14) 5459-04-1 3-üxo-1.2-êtharædiyi butanosic acid ester GG ■< .xx. (Compound) M°ÇAS Chemical Name Structure (15) 2388-18-3 3-dxo-1T-(1,6-hexanediyl) ester of urtanoic acid 3-oxo-1,6-hexanediyl ester of butanoic acid (9C0 m -, . Xx. (16) 32818-60-3 bjs(3-oxobütawate) of 1,142.,2-81^(1,3-dioxobotoxyjmethylt]-1,3-propanediyO SX X (17) 51980-20-2 bis(3-oxqbufan:àaté) of MH2t2-Bts(hydroxymethyl 0-l^propanediyQ : <? AXWiWÇ ^... / 'y T G 0 (18) 0 Q | / —OH d" '7X ..,0.. __ / 'y' y p d (18) 130973-05-6 3-0X0-13,5- benzènetriyl ester d'acide butanol que 0 G G 0 ■’^x'x "'^x -Xxx .X%. (Compound) WCAS Chemical Name Chemical Strœteæ (20) 139264-86-1 3-oxo-1,2,4-benzenetriyl butanoic acid ester L, CO XrX 'XOQ 1 I 1 1 1 1 X / X$ / (21) 22208-25-9 Trimethyloipropane triacetoacetate K-FLEX7301 \ / ~\ F t 0--X \ (22) 2360524-48-5 C >7 x -. .A. .A. .A. Àx -^x ---''x ■ <<"• A" X.-'" xf XV'- x<' V (23) 66229-33-2 3-oxo-2-butyl-2-I(1,3-dioxobutoxy)methylO-1,3-propanediyt butanoic acid ester •jX 11-(2,2-^5(((4,4-dimethyi-1.3- dioxopeoty|i)oxylmeth y^-13-prapanediy^ pentanoic acid ester. A—X / :> (Compounded) N'GAS Chemical name Structural (25) 6079-98-7 tris(3-oxobutanoate ) of 147^-(1,2,3-propanetriyO 0 ¢3 < © © \“ (26) tetra-acetoace7-Xertate de 1 meso*ent wwp"^ “XT (27) 169533-29-3 qD- Glucopy ranunuse t 1 ;2.3î4;6-peritakis(3- oxobutanoate) a 0 xv V $ <> (28) 2254710-55- 7 S-amno-2.3-4-[2 )-D -xyopyranoxyjoxy]-benzoic acid 'xx ( Corn posed i NXAS Nçm chîmsqu© Strufîtw chmwÉ|ue (29) 1236300-10- 9 2,3.4,6-18031^3(3-QXDbutanoateJ de aD-Glucppyranoside, 1,3.4,6-te 1,3-d»xcbutyl)-pD- fructofumTOsyl, . IXXIA (30) 96481-26-4 D-Glücqpyranose, penlakis(3-oxbutanoale) £j <> x--- ' 'x--' (31) D-944-5 1,4:3,6-dianhydra-, 2,5-bts(3-pxobutanoate) JX __________< j (32) 2254710-49- 9 J '' XS: v •^''X î <>. (Quomppse) R* CAS Chemical Name Chemical Structure (33) sorbitol hexa-acetoacetate (34) 216756-89-7 D-Giucitol, 4-O-D-galadopyranos^-, poiyacetoacetate / 0 C-—R1 „ / \ n V. v / \ . / \ / ' "' / \ Sî □ 81 with R1 chosen from -C(O)-CH2-C(OJ-CHî. H with at least two radicals RI represent -G(O)-CH>O ( 0 )-C Hs (35) 101655-52-1 Sucrose, poiyaoetaacetate 1 x-.. ri v / RI__ Y, with R1 chosen from -C(O)-GH2-G(O)-CH3S H with at least two radicals RI represent -C(G)-CHs-C(G)-CHa (Compound) itcas Name shock Chemical structure (36) Ghœse polyacetoacetate "Il or - o J i V (37) Mannose polyacetoacetate y RÏ \ / (38) Xylfel polyacetoacetate ■'--rV-' Q 0 &r (39) SorbM polyacetoacetate ^,0 o of preferenœô radicals RI represent -C(O)-CHz-G(O)-CHs (CGmppsé) hF CAS' Chemical name (40) RI Ri (jf ? Rt yû RV xR:i three RI radicals represent ^(9>CH2-C(O)-CH3, and three RI radicals represent a hydrogen atom (41) 147^_g4_9 i 3 0 l 1 _ Ü _ . 'x / 'Y yy Q 0 (42) 2552-36-5 iî h H ,X ,,X ..X -y 'y* y (43) 139814-56-5 9 9 / \X hh (44) 96189-30-1 ' ^■;x .-' "x ■ x ° X x_ x, '•■ " y •■'■' (45) 75639-01-9 :.5 t? (Compound) CAS No. Homch^ Chemical Stnictoœ (46) Dipentaerythrifo] poîyacetoacetate K > z $ o / / Sx preferably 5 or 6 RI radicals, plus, preferably S RI radicals represent -G(O>CH2-C(O>GH3) in which identical or different RIs represent a hydrogen atom or a -C(O)-CH2-C(O)-CH3 group, it being understood that at least two RI radicals represent -C(O)-CH2-C(O)-CH3, preferably at least three RI radicals represent -C(O)-CH2-C(O)-CH3.

[0050] More preferably, the compound(s) A are chosen from compounds (16), (18), (21), (35), (36), (37), (38), (39), (40) and (46), their optical isomers, their salts, their solvates such as hydrates, and their mixtures.

[0051] Even more preferably, the compound(s) A are chosen from compounds (16), (21), (35), (38), (39) and (46), their optical isomers, their salts, their solvates such as hydrates, and their mixtures.

[0052] Most preferably, the compound(s) A are chosen from compounds (16), (35) and (46), their optical isomers, their salts, their solvates such as hydrates, and their mixtures.

[0053] The compounds of formula (I) can be obtained by (poly)condensation(s) of n equivalents of dicarbonyl reagent with a nucleophilic reagent R'(XH)n comprising n equivalents of -XH nucleophilic functions according to the following scheme: | Q ro $ i Scheme n| [ R ' R R3 >■ - n FÔCH 1 X XX 'X 4'R? L r3 VX in which: - R1, R2, Ra, Rb and n are such as defined for the compound of formula (I); - R3 represents a hydrogen atom, an (Ci-C4)alkyl group such as methyl, ethyl, isobutyl, t-butyl, or an electrofuge group such as CHal3, or Hal3C-SO2- as triflate, with Hal, identical or different, representing a halogen atom; and - X' represents an oxygen atom, or sulfur, preferably O.

[0054] These (poly)condensation methods are known to those skilled in the art; examples include “From rigid and flexible foams to elastomers via Michael addition chemistry”, Polymer, 106, 128-139, (2016), “Dynamic Curing Agents for Amine-Hardened Epoxy Vitrimers with Short (Re)processing Times”, Macromolecules, 53(7), 2485-2495 (2020), “Super photo-base initiated organic-inorganic hybrid coatings by plural-cure mechanisms”, Progress in Organic Coatings, 127, 222-230 (2019) or patent application PL159100: Method for manufacturing acetylacetate esters.

[0055] According to a particular embodiment of the invention, R'(XH)n is selected from the acyclic polyols R'(OH)n, in particular selected from glycerol, trimethylolpropane, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, trimethylolethane, pentamethylene glycol, trimethylpentanediol, pentyl glycol, isosorbide, pentaerythritol, dipentaerythritol, hexamethylene glycol, hexylene glycol, hexandediol, neopentyl glycol, 1,2-propanediol; 1,3-propanediol; 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol; 2,4-butanediol, 3,4-butanediol; 1,4-Pentanediol; 1,5-pentanediol, 2,2,4-Trimethyl-l,3-pentanediol, 1,6-hexanediol, 1,2 octanediol, 1,8 octane diol, 1,10-decanediol, 2-methyl-l,3-propane diol, hexylene glycol, isoprene glycol.

[0056] According to one variant, R'(XH)n is chosen from among the cyclic polyols R'(OH)n in particular chosen from among the monosaccharides and disaccharides, as defined above, alone or in mixture.

[0057] Preferably, R'(XH)n is chosen from the polyols R'(OH)n alone or in mixtures in particular from mannitol, xylitol, sorbitol, glycerol, glucose, trimethylolethane, trimethylolpropane, di(trimethylolpropane), 2-methyl-1,3-propanediol, 2-hydroxymethyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 1' erythritol, pentaerythritol, dipentaerythritol, and mixtures thereof, more particularly from trimethylolethane, trimethylolpropane, erythritol, pentaerythritol, glycerol, glucose, sucrose and sorbitol, and mixtures thereof.

[0058] According to another embodiment, R'(XH)n is chosen from among the diamines R'(NH2)2 in particular the hydroxyalkylated aliphatic diamines such as ro,o'-bis(diethanolaminomethyl)-p-nonylphenol, the N,N,N,N'-tetra(2-hydroxypropyl)ethylenediamine (Quadrol L, available from BASF) and N,N,N, N-tetra(2-hydroxyethyl)ethylenediamine, and their mixture.

[0059] According to another advantageous embodiment, the compound(s) of formula (I) or (la) are obtained by (poly)condensation(s) of n equivalents of propylenedioxy carbonyl reagent with a polyamine nucleophilic reagent R'(NH2)n comprising n equivalents of -NH2 nucleophilic functions according to the following scheme: Diagram in which: - R1, R2, Ra, and n are such as defined for the compound of formula (I); - R'-NH2 is notably chosen from among ethylenediamine, 1,3-diaminopropane, cadaverine, hexamethylenediamine, 1,2-diaminopropane, 1,2-diaminocyclohexane, phenylenediamine; and - Rb, and Rc', identical or different, represent a hydrogen atom, a (Ci-C4)alkyl group.

[0060] This type of synthesis process is known to those skilled in the art; for example, "Acetoacetylation with 2,2,6-trimethyl-4H-l,3-dioxin-4-one: a convenient alternative to diketene", Journal of Organic Chemistry, 50(14), 2431-5, (1985) or "Synthesis of new Biginelli polycondensates: renewable materials with tunable high glass transition temperatures", Polymer International, 70(5), 506-513 (2021).

[0061] According to another advantageous embodiment, the compounds of formula (I) or (la) are obtained by (poly)condensation(s) of n equivalents of diketene reagent with a nucleophilic reagent R*(X)n comprising n equivalents of -XH nucleophilic functions according to the following scheme: Diagram in which: - R1, and n are such that defined for the compound of formula (I); and - X' represents an oxygen atom, or sulfur atom, or N(R') with R'=H.

[0062] This type of process is known to those skilled in the art. For example, one can cite "Acetoacetamides, 2-hydroximinoacetoacetamides, and 2,3-bis(hydroximino)-bu tyramides", Journal für Praktische Chemie (Leipzig), 323(2), 337-44, (1981) or Angewandte Makromolekulare Chemie, 9, 96-105, (1969). (Poly)amine compounds

[0063] The (poly)amine compound(s) used in the coloring process according to the present invention can in particular be chosen from among polyamine compounds having several primary and / or secondary amine groups or from among amino alkoxysilanes, and more particularly from among amino alkoxysilane compounds, diaminic compounds, triamine compounds, and mixtures thereof.

[0064] The (poly)amine compound(s) may be chosen from compounds comprising from 2 to 20 carbon atoms, including non-polymer compounds; they may be acyclic or cyclic, linear or branched, saturated or unsaturated, conjugated or non-conjugated, aromatic or non-aromatic, optionally interrupted by one or more heteroatoms or groups chosen from -O-, -S-, -Si(R')2-, -N(R”)- preferably -O-, -Si(R')2-, or their combinations such as -Si(R')2- -O- or -O-Si(R')2-, with R', identical or different, representing a (CrC4)alkyl group such as methyl, and R” representing a hydrogen atom or a (C1-C4)alkyl group, preferably a hydrogen atom.

[0065] By "non-polymer compound" is meant a compound that is not directly obtained by a polymerization reaction of monomers.

[0066] Examples of (poly)amine compounds include N-methyl-1,3-diaminopropane, N-propyl 1,3-diaminopropane, N-isopropyl 1,3-diaminopropane, N-cyclohexyl 1,3-diaminopropane, 2-(3-aminopropylamino)ethanol, 3-(2-aminoethyl)aminopropylamine, bis(3-aminopropyl)amine, methyl bis(3-aminopropyl)amine, N-(3-aminopropyl)-1,4-diaminobutane, N,N-dimethyldipropylene triamine, 1,2-bis(3-aminopropylamino)ethane, N,N'-bis(3-aminopropyl)-1,3-propanediamine, ethylenediamine, 1,3-propylenediamine, 1,4-butylenediamine, lysine, polylysine, cystamine, xylene diamine, tris(2-aminoethyl)amine, l,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, diaminopropanol such as l,3-diamino-2-propane-1 ol, 4,7,10-Trioxa-l,13-tridecanediamine, spermidine, lysinol and C36-alkylenediamines (respectively Priamine™ 1071, 1073, 1074, 1075 marketed by CRODA), preferably 1,3-diamino-2-propane-l-ol,Polylysine, spermidine, and mixtures thereof...

[0067] According to a particular embodiment of the invention, the (poly)amine compound(s) are monoamine, namely they contain a single primary and / or secondary amine group, preferably primary (NH2).

[0068] According to a particular embodiment of the invention, the (poly)amine compound(s) are diaminized, namely they contain two primary and / or secondary amine groups, preferably primary (NH2). An example of a diaminized compound is 1,3-diamino-2-propane-l ol.

[0069] According to a particular embodiment of the invention, the (poly)amine compound(s) are triamine, namely they contain three primary and / or secondary amine groups. Spermidine is an example of a triamine compound.

[0070] According to a particular embodiment of the invention, the (poly)amine compound(s) are polyamines, namely they contain more than two primary and / or secondary amine groups, preferably primary (NH2). Polylysine is an example of a (poly)amine compound.

[0071] The (poly)amine compound(s) may be chosen from among the amino alkoxysilanes, in particular those of formula R'iSi(OR'2)z(R'3)x, in which: - R'i is a Ci-C6 hydrocarbon chain, linear or branched, saturated or unsaturated, cyclic or acyclic, substituted by a group chosen from the primary amine group NH2 or the secondary amine group -N(H)R, with R representing a CrC4 alkyl, an aryl, a benzyl substituted by an amino group or by an aminoalkyl group in Ci-C4; R'i may be interrupted in its chain by a heteroatom (O, S, NH) or a carbonyl group C(O), R'i being linked to the silicon atom directly via a carbon atom, - R'2 and R'3, whether identical or different, represent a (Ci-C6)alkyl group, linear or branched. - z denotes an integer from 1 to 3, and - x denotes an integer from 0 to 2, with z + x = 3.

[0072] In particular, R'i is an acyclic chain. Preferably, R'i is a linear or branched, saturated or unsaturated C1-C6 hydrocarbon chain substituted with an amine group -NH2 or -N(H)R, where R represents a C1-C6 alkyl, a C3-C6 cycloalkyl, or a C6 aromatic. More preferably, R'i is a linear saturated C1-C6 hydrocarbon chain substituted with an amine group NH2. Even more preferably, R'i is a linear saturated C2-C4 hydrocarbon chain substituted with an amine group NH2.

[0073] In particular, R'2 represents an alkyl group comprising 1 to 4 carbon atoms, preferably R'2 represents a linear alkyl group comprising 1 to 4 carbon atoms, and more preferably R'2 represents the ethyl group.

[0074] In particular, R'3 represents an alkyl group comprising from 1 to 4 carbon atoms; preferably, R'3 represents a linear alkyl group comprising from 1 to 4 carbon atoms; and more preferably, R'3 represents the methyl or ethyl group. Preferably, z is equal to 3.

[0075] In particular, the (poly)amine compound(s) are chosen from among the amino alkoxysilanes having only one primary and / or secondary amine group, preferably primary (NH2), such as 3-aminopropyltriethoxysilane (APTES), 3-aminoethyltriethoxysilane (AETES), 3-aminopropylmethyldiethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, 3-(m-aminophenoxy)propyltrimethoxy-silane, p-aminophenyltrimethoxysilane, and N-(2-aminoethylaminomethyl)-phenethyltrimethoxysilane.

[0076] Preferably, the (poly)amine compound(s) are chosen from 3-aminopropyltriethoxysilane (APTES), 3-aminoethyltriethoxysilane (AETES), 3-aminopropylmethyldiethoxysilane, and N-(2-aminoethyl)-3-aminopropyltriethoxysilane, and more preferably 3-aminopropyltriethoxysilane (APTES), in particular that marketed by Sigma Aldrich.

[0077] The (poly)amine compound(s) may also be chosen from among amine polymers, in particular having a weight average molecular weight ranging from 500 g.mol1 to 1000000 g.mol1, preferably ranging from 500 g.mol1 to 500000 g.mol1, and preferably ranging from 500 g.mol1 to 100000 g.mol1.

[0078] According to a particular embodiment of the invention, the (poly)amine compound(s) are monoamine and selected from polydialkylsiloxanes, in particular of formula (IV): H2N-ALK-Si(R'2)(R'3)-O-[ Si(R'2)(R'3)-O]n- Si(R'2)(R'3)-R'4(IV) formula (IV) in which: - ALK represents a (Ci-C4)alkylene group, linear or branched, preferably linear, such as propylene, - R'2 and R'3, whether identical or different, preferably identical, represent a (CrC4)alkyl group such as methyl, and - R'4 represents a (Ci-C6)alkyl group, linear or branched, preferably at C4, such as n-butyl, ne represents an integer greater than or equal to 2, preferably the value of n is such that the average molecular weight by weight of the polydimethylsiloxane ranges from 500 to 3000 g.mol1. As an example of polydimethylsiloxanes (IV), we can cite those sold under the names "MCR-A11" and "MCR-A12" by the company Gelest.

[0079] According to a particular embodiment of the invention, the (poly)amine compound(s) are diaminized, namely they contain two primary and / or secondary amine groups, preferably primary (NH2).

[0080] More specifically, they are chosen from compounds of formula (V) or (VI): ■ ALK[(O-ALK')m-NH2]2 (V) or ■ H2N-ALK-Si(R')2-[O-Si(R')2]mO-Si(R)2-ALK'-NH2 (VI) formulas (V) and (VI) in which: - ALK and ALK', whether identical or different, represent a (Ci-C6)alkylene group, linear or branched, preferably linear, such as propylene, - R', identical or different, represents an (Ci-C4)alkyl group, such as methyl, - m represents an integer greater than or equal to 0, preferably the value of m is such that the average molecular weight by weight of the compound (V) or (VI) goes from 500 g.mol1 to 55000 g.mol*.

[0081] Examples of compounds of formula (VI) include those sold under the names “DMS-A11”, “DMS-A12”, “DMS-A15”, “DMS-A21”, “DMS-A31”, “DMS-A32” and “DMS-A35” by the company Gelest.

[0082] The (poly)amine compound(s) which are diaminized are particularly the diaminized polyethers in particular of formula H2N-ALK-O-[ALK'-O]m-ALK”-NH2 with ALK, ALK' and ALK”, identical or different representing a (Ci-C6)alkylene group, linear or branched, and m representing an integer greater than or equal to 0, such as 4,7,10-trioxa-l,13-tridecanediamine or the compounds known under the reference Jeffamine of the Huntsman company, and more particularly polyethylene glycol and / or polypropylene glycol a, co-diamine (with amine function at the end of the chain) such as those sold under the names Jeffamine D-230, D-400, D-2000, D-4000, ED-600, ED-9000, ED-2003.

[0083] According to a particular embodiment of the invention, the (poly)amine compound(s) are triamine, namely they contain three primary and / or secondary amine groups, preferably primary (NH2). More particularly, they are chosen from triamine polyethers, notably of formula ALK'”[(O-ALK')m-NH2]3, with ALK' as defined above and ALK”' representing a trivalent (Ci-C6)alkylene group, linear or branched, and m representing an integer greater than or equal to 0.

[0084] Triamine polyethers, such as those sold under the name Jeffamine T-403, are particularly cited as (poly)amine compounds that are triamined.

[0085] According to another particular embodiment of the invention, the (poly)amine compound(s) comprise more than three primary and / or secondary amine groups, preferably primary (NH2).

[0086] In this variant, the (poly)amine compound(s) are in particular chosen from poly(meth)acrylates or poly(meth)acrylamides bearing primary or secondary lateral amine functions, such as poly(3-aminopropyl)methacrylamide and poly(2-aminoethyl)methacrylate.

[0087] Preferably, the (poly)amine compounds are chosen from chitosans (in particular poly(D-glucosamine)), and polydimethylsiloxanes comprising primary amine groups at the end of the chain and / or on side chains.

[0088] According to this variant, the (poly)amine compound(s) are in particular chosen from poly(alkylene (C2-C5)imines), and preferably polyethyleneimines and polypropyleneimines, in particular poly(ethyleneimine), in particular that sold under reference 408700 by Aldrich Chemical or under the trade name Lupasol by BASF, in particular with a molecular weight between 1,200 and 25,000; poly(allylamine), in particular that sold under reference 479136 by Aldrich Chemical; polyvinylamines and their copolymers, in particular with vinylamides, in particular vinylamine / vinylformamide copolymers such as those marketed under the name Lupamin® 9030 by BASF; polyamino acids having NH2 groups such as polylysine, in particular that sold by JNC Corporation (formerly Chisso); amino dextran, in particular that sold by the company CarboMer Inc;Polyvinyl amino alcohol, in particular that sold by CarboMer Inc., acrylamido(Ci-C6)alkylamine-based copolymers, notably acrylamidopropylamine-based; and poly(D-Glucosamine), for example, sold under the reference Kionutrime CSG® by Kytozyme.

[0089] According to a particular embodiment, polydimethylsiloxanes comprising primary amine groups at the end of the chain and / or on side chains are selected from compounds of the following formula (VII): Ra-Si(Rb)(Rc)-O-[Si(Rb)(Rc)-O]m-[Si(ALK1-NH2)(Ra)-O]n-Si(Rb)(Rc)-Ra(VII) formula (VII) in which: - Ra, identical or different, represents a hydroxyl or (Ci-C4)alkyl group, - Rb and Rc, identical or different, preferably identical, represent a (Ci-C4)alkyl group, such as methyl, - ALK1 represents a (Ci-C6)alkylene group, linear or branched, possibly interrupted by an N(H) group, - m and n are integers greater than or equal to 1, preferably m and n are such that the average molecular mass by weight of the compound of formula (VII) goes from 1000 g.mol1 to 500000 g.mol1.

[0090] According to a preferred embodiment, formula (VII) is such that Ra, Rb, and Rc represent a methyl group, ALK1 represents a propylene group, n and m are such that the values ​​of n and m are such that the weight average molecular weight of polydimethylsiloxane ranges from 1000 g.mol1 to 55000 g.mol1.

[0091] Examples of polydimethylsiloxanes of formula (VII) include those sold under the names "AMS-132", "AMS-152", "AMS-162", "AMS-163", "AMS-191" and "AMS-1203" by the company Gelest.

[0092] According to another variant, formula (VII) is such that Ra represents a hydroxyl or (Ci-C4)alkyl group, such as methyl, ALK1 represents a (C5-C6)alkylene group substituted by an NH group, preferably ALK1 represents -(CH2)3-N(H)-(CH2)2-, and m and n are such that the weight average molecular mass of the compound of formula (VI) ranges from 5000 g.mol1 to 500000 g.mol1.

[0093] As an amino polymer, polytetrahydrofuran (or polytetramethylene glycol) α, co-diamine, and polybutadienes α, co-diamine may also be cited.

[0094] According to a particular embodiment of the invention, the (poly)amine compounds are chosen from hyperbranched polymers comprising at least one amino group and dendrimers bearing at least one amino group, such as PAMAM polyamidoamine dendrimers with an ethylenediamine core and a terminal amine function.

[0095] Preferably, the (poly)amine compound(s) are chosen from: a) (Poly)amine compounds containing more than three primary and / or secondary amine groups, preferably primary (NH2), in particular chitosans such as poly(D-Glucosamine) and polylysine, b) polyether diamines, in particular polyethylene glycol a, co-diamine, with an amine function at the end of the chain, c) triamine polyethers, such as Jeffamine T-403, d) aminoalkoxysilanes, in particular APTES, e) NH2-alk-NH2 polyamine compounds, in which alk denotes a C2-C20 hydrocarbon divalent chain, possibly substituted by a hydroxyl group (-OH) and / or possibly interrupted by one or more heteroatoms selected from -O-, -N(R)- with R denoting a hydrogen atom or a C1-C4 alkyl radical, in particular spermidine, 4,7,10-Trioxa-l,13-tridecanediamine, 1,3-diamino-2-propan-l-ol and lysinol, (f) Polydialkylsiloxanes comprising primary amine groups at the ends of the chain or on side chains, in particular polydimethylsiloxanes comprising primary amine groups, more particularly bis(3-aminopropyl)-terminated poly(dimethoxysiloxane) (PDMS-diNH2) and amodimethicones comprising amine groups on side chains, even more particularly bis-cetearyl amodimethicone; and mixtures thereof.

[0096] More preferably, the (poly)amine compound(s) are chosen from a), c), e), and their mixtures.

[0097] Even more preferably, the (poly)amine compound(s) are chosen from polylysine, triamine polyethers, such as Jeffamine T-403, spermidine, l,3-diamino-2-propan-l-ol, and mixtures thereof. Direct dyes

[0098] The direct dye(s) used in the coloring process according to the present invention are preferably chosen from ionic direct dyes and non-ionic direct dyes, more preferably from cationic direct dyes, amphoteric direct dyes, anionic direct dyes, non-ionic direct dyes, and mixtures thereof.

[0099] Direct dyes are for example chosen from among benzene nitrate direct dyes, azo direct dyes, tetraazapentamethinic dyes, quinonic dyes and in particular anthraquinone dyes, azinic direct dyes, triarylmethanic direct dyes, azomethine direct dyes, natural direct dyes, and mixtures thereof.

[0100] By way of benzene nitro direct dyes according to the invention, the following may be mentioned: 2-Amino-6-chloro-4-nitrophenol, 2-Chloro-6-ethylamino-4-nitrophenol, 2-Hydroxyethylamino-5-nitroanisole, 2-Nitro-5-glyceryl methylaniline, 3-Methylamino-4-nitrophenoxyethanol, 3-Nitro-p-hydroxyethylaminophenol, 4-Amino-3-nitrophenol, 4-Hydroxypropylamino-3-nitrophenol, 4-Nitro-o-phenylenediamine, HC Blue No. 2, HC Orange No. 2, HC Red No. 3, HC Red No. 7, HC Violet No. 1, HC Violet No. 2, HC Yellow No. 10, HC Yellow No. 13, the HC Yellow No.2, HC Yellow No.4, Hydroxyethyl-2-nitro-p-toluidine, N,N'-bis(2-Hydroxyethyl)-2-nitro-p-phenylenediamine and picramic acid.

[0101] As a preferred benzene nitro direct dye according to the invention, 2-Hydroxyethylamino-5-nitroanisole may be mentioned.

[0102] The process according to the present invention may employ one or more non-ionic direct dyes.

[0103] Among non-ionic direct dyes, we can mention neutral benzene nitro direct dyes, neutral azo direct dyes, neutral anthraquinone dyes.

[0104] The process according to the present invention can employ one or more cationic direct dyes.

[0105] By "cationic direct dye" is meant any dye other than oxidation dyes, commonly called "basic" direct dyes or "basic dyes". They are called basic because of their affinity for acidic substances, having in their structure at least one endo- or exocyclic cationic or cationizable group.

[0106] Cationic direct dyes contain at least one quantified cationic chromophore or at least one chromophore bearing a quantified or quantizable cationic group.

[0107] According to a particular embodiment of the invention, the cationic direct dyes comprise at least one quantified cationic chromophore.

[0108] Examples of cationic direct dyes according to the invention include acridines; acridones; anthranthrones; anthrapyrimidines; anthraquinones; azines; (poly)azoic, hydrazono or hydrazones, in particular arylhydrazones; azomethines; benzantrones; benzimidazoles; benzimidazolones; benzindoles; benzoxazoles; benzopyrans; benzothiazoles; benzoquinones; bisazines; bisisoindolines; carboxanilides; coumarins; cyanines such as azacarbocyanines, diazacarbocyanines, diazahemicyanines, hemicyanines, or tetraazacarbocyanines; diazines; diketopyrrolopyrroles; dioxazines; diphenylamines; diphenylmethanes; dithiazines; flavonoids such as flavanthones and flavones; fluorindines; formazans; indamines; indanthrones; indigoids and pseudo-indigoids; indophenols; indoanilines; isoindolines; isoindolinones; isoviolanthones; lactones; (Poly)methines such as stilbene or styryl-type dimethines; naphthalimides; naphthanilides; naphtholactams; naphthoquinones; nitro, including (hetero)aromatic nitro; oxadiazoles; oxazines; perilones; perinones; perylenes; phenazines; phenoxazine; phenothiazines; phthalocyanine; polyenes / carotenoids; porphyrins; pyrantrones; pyrazolantrones; pyrazolones; pyrimidinoantrones; pyronines; quinacridones; quinolines; quinophthalones; squaranes; tetrazoliums; thiazines, thioindigo; thiopyronines; triarylmethanes, or xanthenes.

[0109] For cationic azo dyes, particular mention can be made of those derived from the cationic dyes described in the Kirk-Othmer Encyclopedia of Chemical Technology, “Dyes, Azo”, J. Wiley & sons, updated on 19 / 04 / 2010.

[0110] Among the azo dyes that can be used according to the invention, cationic azo dyes described in patent applications WO 95 / 15144, WO 95 / 01772 and EP 714954 can be mentioned.

[0111] The following compounds may be cited among the azo dyes described in the Colour Index International, 3rd edition: -Basic Red 22 -Basic Red 76 -Basic Yellow 57 -Basic Brown 16 -Basic Brown 17 - HC Brown No. 1 - HC Brown No. 2.

[0112] Among the cationic quinone dyes, those mentioned in the aforementioned Colour Index International are suitable, and among these, the following dyes may be cited, among others: -Basic Blue 22 -Basic Blue 99.

[0113] Suitable azinic dyes include those listed in the Colour Index International, for example the following dyes: -Basic Blue 17 -Basic Red 2 -Basic Blue 124.

[0114] Among the cationic triarylmethane dyes that can be used according to the invention, in addition to those listed in the Colour Index, the following dyes may be mentioned: -Basic Green 1 -Basic Violet 3 -Basic Violet 14 -Basic Blue 7 -Basic Blue 26.

[0115] Cationic dyes can also be cited in documents US 5888252, EP 1133975, WO 03 / 029359, EP 860636, WO 95 / 01772, WO 95 / 15144, EP 714954. Also cited are those listed in the encyclopedia "The chemistry of synthetic dye" by K. VENKATARAMAN, 1952, Academy Press vol 1 to 7, in the "Kirk-Othmer" encyclopedia "Chemical technology", chapter "Dyes and Dye intermediate", 1993, Wiley and sons, and in various chapters of the encyclopedia "ULLMANN's ENCYCLOPEDIA of Industrial chemistry" 7th edition, Wiley and sons.

[0116] According to a particular manufacturing method, the direct colorants are cationic azoïques, described in EP 850636, FR 2788433, EP 920856, WO 9948465, FR 2757385, EP 850637, EP 918053, WO 9744004, FR 2570946, FR 2285851, DE 2538363, FR 2189006, FR 1560664, FR 1540423, FR 1567219, FR 1516943, FR 1221122, DE 4220388, DE 4137005, WO 0166646, US 5708151, WO 9501772, WO 515144, GB 1195386, US 3524842, US 5879413, EP 1062940, EP 1133976, GB 738585, DE 2527638, FR 2275462, GB 1974-27645, Acta Histochem. (1978), 61(1), 48-52 ; Tsitologiya (1968), 10(3), 403-5 ; Zh. Obshch. Khim. (1970), 40(1), 195-202 ; Ann. Chem. (Rome) (1975), 65(5-6), 305-14 ; Journal of the Chinese Chemical Society (Taipei) (1998), 45(1), 209-211 ; Rev. Roum. Chem. (1988), 33(4), 377-83 ; Text. Res. J. (1984), 54(2), 105-7 ; Chem. Ind. (Milan) (1974), 56(9), 600-3 ; Khim. Technol. (1979), 22(5), 548-53; Ger. Monatsh. Chem. (1975), 106(3), 643-8; MRL Bull. Res. Dev. (1992), 6(2), 21-7; Lihua Jianyan, Huaxue Fence (1993), 29(4), 233-4; Dyes Pigm. (1992), 19(1), 69-79; Dyes Pigm. (1989), 11(3), 163-72.

[0117] Cationic direct dyes include, for example, a cationic radical: - with an exocyclic charge (di / tri)(Ci-C8)alkylammonium, or - à charge endocyclique tels que comprenant un groupe hétéroaryle cationique choisi parmi : acridinium, benzimidazolium, benzobistriazolium, benzopyrazolium, benzopyridazinium, benzoquinolium, benzothiazolium, benzotriazolium, benzoxazolium, bi-pyridinium, bis-tétrazolium, dihydrothiazolium, imidazopyridinium, imidazolium, indolium, isoquinolium, naphthoimidazolium, naphthooxazolium, naphthopyrazolium, oxadiazolium, oxazolium, oxazolopyridinium, oxonium, phénazinium, phénooxazolium, pyrazinium, pyrazolium, pyrazoyltriazolium, pyridinium, pyridinoimidazolium, pyrrolium, pyrylium, quinolium, tétrazolium, thiadiazolium, thiazolium, thiazolopyridinium, thiazoylimidazolium, thiopyrylium, triazolium ou xanthylium.

[0118] De préférence, les colorants directs cationiques comprennent un groupe ammonium quaternaire, plus préférentiellement la charge cationique est endocyclique.

[0119] Examples include the following hydrazono cationic dyes of formula (C-II) and (C-III), azo dyes of formulas (C-IV) and (C-V), as well as their optical, geometric, and tautomeric isomers, their salts of organic or mineral acids or bases, and their solvates such as the hydrates: Het+-C(Ra)=NN(Rb)-Ar, Q (C-II) Het+-N(Ra)-N=C(Rb)-Ar, Q (C-III) Het+-N=N-Ar, Q (C-IV) Ar+-N=N-Ar”, Q (CV), formulas (C-II) to (C-V) in which: * Het+ represents a cationic heteroaryl radical, preferably with endocyclic cationic charge such as imidazolium, indolium, or pyridinium, possibly preferentially substituted by at least one (CrC8)alkyl group such as methyl; * Ar+ represents an aryl radical, such as phenyl or naphthyl, with an exocyclic cationic charge, preferably ammonium, particularly tri(Ci-C8)alkyl-ammonium such as trimethylammonium; * Ar represents an aryl group, in particular phenyl, possibly substituted, preferably by one or more electron-donating groups such as i) (Ci-C8)alkyl possibly substituted, ii) (CrC8)alkoxy possibly substituted, iii) (di) (Ci-C8)(alkyl)amino possibly substituted on the alkyl group(s) by a hydroxyl group, iv) aryl(Ci-C8)alkylamino, v) N-(Ci-C8)alkyl-N-aryl(Ci-C8)alkylamino possibly substituted or Ar represents a julolidine group; *Ar” represents a (hetero)aryl group possibly substituted such as phenyl or pyrazolyl possibly substituted, preferably by one or more (CrC8)alkyl, hydroxyl, (di)(Ci-C8)(alkyl)amino, (CrC8)alkoxy or phenyl groups; * Ra and Rb, identical or different, representing a hydrogen atom or a (Ci-C8)alkyl group possibly substituted, preferably by a hydroxyl group; * or the substituent Ra with a substituent of Het+ and / or Rb with a substituent of Ar together form with the atoms that bear them a (hetero)cycloalkyl; particularly Ra and Rb, representing a hydrogen atom or a (Cr C4)alkyl group possibly substituted by a hydroxyl group; * Q represents an organic or mineral anionic counter-ion such as a halide or alkyl sulfate.

[0120] In particular, one may cite the endocyclic cationic direct dyes of azo and hydrazono of formula (C-II) to (CV) as defined above; more particularly the endocyclic cationic direct dyes of formula (C-II) to (CV) described in patent applications WO 95 / 15144, WO 95 / 01772 and EP-714954.

[0121] Preferably, the following direct dyes may be mentioned: (C-IV-1),

[0122] formulas (C-II-1) and (C-IV-1) wherein: - R1 represents an (Ci-C4)alkyl group such as methyl; - R2 and R3, whether identical or different, represent a hydrogen atom or an (Ci-C4)alkyl group such as methyl; and - R4 represents a hydrogen atom or an electron-donating group such as (Ci -C8)alkyl possibly substituted, (CrC8)alkoxy possibly substituted, (di)(C i-C8)(alkyl)amino possibly substituted on the alkyl group(s) by a hydroxyl group; particularly R4 is a hydrogen atom, - Z represents a CH group or a nitrogen atom, preferably CH, - Q is an anionic counterion as defined previously, particularly a halide such as chloride or an alkyl sulfate such as methyl sulfate or mesytyl.

[0123] In particular, colorants of formula (C-II-1) and (C-IV-1) are selected from Basic Red 51, Basic Yellow 87 and Basic Orange 31 or their derivatives: with Q' an anionic counter-ion as defined previously, particularly a halide such as chloride or an alkyl sulfate such as methyl sulfate or mesytyl.

[0124] According to a particular embodiment of the invention, the direct dyes are fluorescent, that is to say they contain at least one fluorescent chromophore as defined above.

[0125] Examples of fluorescent dyes include radicals derived from acridine, acridone, benzantrone, benzimidazole, benzimidazolone, benzindole, benzoxazole, benzopyran, benzothiazole, coumarin, and difluoro(2-[(2H-pyrrol-2- ylidene-kN)methyl]-1H-pyrrolato-kN}bores (BODIPY®), diketopyrrolo-pyrroles, fluorindines, (poly)methines (including cyanines and styryls / hemicyanines), naphthalimides, naphthanilides, naphthylamine (such as dansyls), oxadiazoles, oxazines, perilones, perinones, perylenes, polyenes / carotenoids, squaranes, stilbenes, xanthenes.

[0126] Also of note are the fluorescent dyes described in documents EP 1133975, WO 03 / 029359, EP 860636, WO 95 / 01772, WO 95 / 15144, EP 714954 and those listed in K. Venkataraman's "The Chemistry of Synthetic Dye," 1952, Academy Press, vols. 1-7, in the Kirk-Othmer Encyclopedia "Chemical Technology," chapter "Dyes and Dye Intermediate," 1993, Wiley and Sons, and in various chapters of Ullmann's Encyclopedia of Industrial Chemistry, 7th edition, Wiley and Sons, and in The Handbook — A Guide to Fluorescent Probes and Labeling Technologies, 1st ed. Molecular Probes / Invitrogen - Oregon 2005 distributed via the Internet or in previous printed editions.

[0127] According to one embodiment of the invention, the cationic dye(s) are fluorescent and comprise at least one quaternary ammonium radical such as those of the following (C-VI) formula, as well as their optical, geometric, tautomeric isomers, their salts of organic or mineral acids or bases, and their solvates such as hydrates: W+-[C(Rc)=C(Rd)]m'-Ar, Q (C-VI), formula (C-VI) in which: * W+ represents a cationic heterocyclic or heteroaryl group, particularly comprising a quaternary ammonium possibly substituted by one or more (CrC8)alkyl groups possibly substituted in particular by one or more hydroxyl groups; * Ar representing an aryl group such as phenyl or naphthyl, possibly substituted preferably by i) one or more halogen atoms, such as chlorine, fluorine; ii) one or more (Ci-C8)alkyl groups, preferably in Ci-C4 such as methyl; iii) one or more hydroxyl groups; iv) one or more (CrC8)alkoxy groups such as methoxy; v) one or more hydroxy(Ci-C8)alkyl groups such as hydroxyethyl; vi) one or more amino or (di)(Ci-C8)alkylamino groups, preferably with the alkyl portion in Ci-C4 possibly substituted by one or more hydroxyl groups such as (di)hydroxyethylamino; vii) by one or more acylamino groups; viii) one or more heterocycloalkyl groups such as pyperazinyl, pyperidinyl or 5 or 6-membered heteroaryl groups such as pyrrolidinyl, pyridinyl and imidazolinyl; * m' represents an integer between 1 and 4 inclusive, particularly m is 1 or 2; more preferably 1; * Rc, Rd, identical or different, represent a hydrogen atom or a (Ci-C8)alkyl group possibly substituted, preferably in Ci-C4, or else Rc contiguous to W+ and / or Rd contiguous to Ar form with the atoms that bear them a (hetero)cycloalkyl, particularly Rc is contiguous to W+ and form a (hetero)cycloalkyl such as cyclohexyl; * Q is an organic or mineral anionic counterion as defined above.

[0128] Among cationic direct dyes, triarylmethane cationic dyes may also be mentioned.

[0129] Preferably, the triarylmethane cationic direct dyes according to the invention are chosen from the following cationic dyes of formulas (C-VII) and (C-VII'): (C-VII), as well as its addition salts with an acid or a base, organic or mineral, its geometric, optical, tautomeric isomers, and its mesomeric forms, its solvates such as hydrates,

[0130] preceding formulas (C-VII) and (C-VII') in which: * Ri, R2, Ri, and R4, whether identical or different, represent a hydrogen atom or a (Ci-C6)alkyl group, possibly substituted, preferably by a hydroxyl group; aryl such as phenyl, aryl(Ci-C4)alkyl such as benzyl, heteroaryl, heteroaryl(Ci-C4)alkyl, or two groups Ri and R2, and / or R3 and IC, attached to the same nitrogen atom, together forming a group heterocycloalkyl possibly substituted such as morpholino, piparazino, piperidino, preferably R2, R3 and R4, identical or different, represents a hydrogen atom or a (Ci-C4)alkyl group, * R5, R6, R7, R8, R9, Rio, Ru, R12, R13, Ru, Rb and R[6, identical or different, represent a hydrogen atom, a halogen, or a group chosen from i) hydroxy, ii) thiol, iii) amino iv) (di)(Ci-C4)(alkyl)amino, v) (di)arylamino such as (di)phenylamino, vi) nitro, vii) acylamino (-NR-C(O)R') in which the radical R is a hydrogen atom, an alkyl radical in CrC4 possibly bearing at least one hydroxyl group and the radical R' is an alkyl radical in Ci-C2; viii) carbamoyl ((R)2N-C(O)-) in which the radicals R, identical or not, represent a hydrogen atom, an alkyl radical in CrC4 possibly bearing at least one hydroxyl group; ix) carboxylic acid or ester, (-OC(O)R') or

[0131] (-C(O)OR'), wherein the radical R' is a hydrogen atom, or an alkyl in Ci -C4 possibly bearing at least one hydroxyl group and the radical R' is an alkyl radical in CrC2; x) alkyl possibly substituted in particular by a hydroxy group; xi) alkylsulfonylamino (R'SO2-NR-) in which the radical R represents a hydrogen atom, an alkyl radical in CrC4 possibly bearing at least one hydroxyl group and the radical R' represents an alkyl radical in CrC4, a phenyl radical; xii) aminosulfonyl ((R)2N-SO2 ) in which the radicals R, identical or not, represent a hydrogen atom, an alkyl radical in CrC4 possibly bearing at least one hydroxyl group, xiii) (Ci-C4)alkoxy, and xiv) (Ci-C4)alkylthio;* Or, two radicals carried by two adjacent carbon atoms R5 and R6 and / or R7 and R8, and / or R9 and R10 and / or Ru and Rn and / or Rn and RM and / or R[5 and R[6] together with the carbon atoms that support them form a condensed 6-membered aryl or heteroaryl ring, preferably benzo, said ring possibly being further substituted, preferably an unsubstituted benzo ring; * Q represents an anionic counter-ion to achieve electroneutrality, preferably chosen from halides such as chloride, bromide, and phosphate.

[0132] When the cationic dye includes one or more anionic substituents such as COOR or SO3R with R denoting a hydrogen or a cation, it is understood that there are then more cationic substituents than anionic substituents, so that the overall resulting charge of the triarylmethane structure is cationic.

[0133] According to a preferred embodiment, the triarylmethane dyes are chosen from those of formula (C-VII) or (C-VII'), in which, taken together or separately, - Rb R2, R3 and Ri represent a hydrogen atom or an (CrC4)alkyl group such as methyl or ethyl, - R5, R6, R7, R8, R9, Rio, Ru, R12, Rb, Ru, Ris and Ri6, represent a hydrogen atom, a halogen such as chlorine, or a (Ci-C4)alkyl group such as methyl or ethyl, an amino group, a (di)(Ci-C4)(alkyl)amino group and, preferably, at least one of the groups R9, Rio, Ru or R[2 represents a hydrogen atom, a halogen (Cl), or an amino group, or a (Ci-C4)(alkyl)amino or (di)(CrC4) (alkyl)amino group, preferably in the para position of the phenyl group.

[0134] Preferably, the direct triarylmethane structure dyes are chosen from Basic Violet 1, Basic Violet 2, Basic Violet 3, Basic Violet 4, Basic Violet 14, Basic Blue 1, Basic Blue 7, Basic Blue 26, Basic green 1, Basic Blue 77 (also called HC Blue 15), and mixtures thereof.

[0135] Among cationic direct dyes, anthraquinone cationic dyes can also be mentioned.

[0136] Examples of cationic anthraquinone direct dyes include Disperse Violet 1, Hydroxyanthraquinone-aminopropyl Methyl Morpholinium Methosulfate, HC Orange No. 5 and HC Red No. 8

[0137] Preferably, the cationic anthraquinone direct dyes usable in the coloring process of the invention comprise a quaternary ammonium group.

[0138] Anthraquinone cationic direct dyes include, for example, a cationic radical: - à charge exocyclique (Ci-C8)alkylammonium, ou - à charge endocyclique tels que comprenant un groupe hétéroaryle cationique choisi parmi : acridinium, benzimidazolium, benzobistriazolium, benzopyrazolium, benzopyridazinium, benzoquinolium, benzothiazolium, benzotriazolium, benzoxazolium, bi-pyridinium, bis-tétrazolium, dihydrothiazolium, imidazopyridinium, imidazolium, indolium, isoquinolium, naphthoimidazolium, naphthooxazolium, naphthopyrazolium, oxadiazolium, oxazolium, oxazolopyridinium, oxonium, phénazinium, phénooxazolium, pyrazinium, pyrazolium, pyrazoyltriazolium, pyridinium, pyridinoimidazolium, pyrrolium, pyrylium , quinolium, tétrazolium, thiadiazolium, thiazolium, thiazolopyridinium, thiazoylimidazolium, thiopyrylium, triazolium ou xanthylium.

[0139] De préférence, la charge cationique est exocyclique.

[0140] Among anthraquinone cationic direct dyes, those of formula (C-VIII) having an exocyclic cationic charge are preferred: (c-vm)

[0141] in which: - R1, R2 and R3, identical or different, representing a hydrogen atom or a (Ci-C8)alkyl group possibly substituted; - R4 representing a hydrogen atom or a (CrC8)alkyl group possibly substituted; - R5 represents a hydrogen atom, a (CrC8)alkyl group (possibly substituted), a (Ci-C8)alkylene group (possibly substituted), a halogen, a hydroxyl group, or a (CrC8)alkoxy group - n representing a number between 1 and 8; - Q represents an organic or mineral anionic counter-ion such as a halide or an alkyl sulfate.

[0142] Preferably, in formula (C-VIII): - R1, R2 and R3, identical or different, representing a (Ci-C6)alkyl group possibly substituted; - R4 representing a hydrogen atom or possibly substituted (Ci-C6)alkyl group; - R5 representing a hydrogen atom or a (Ci-C8)alkyl group, possibly substituted, - n representing a number between 1 and 6; - Q representing a halide or an alkyl sulfate.

[0143] More preferably, in formula (C-VIII): - R1, R2 and R3, identical or different, representing a (Ci-C3)alkyl group possibly substituted; - R4 representing a hydrogen atom or a methyl group; preferably a methyl group - R5 representing a hydrogen atom or a methyl group, preferably a hydrogen atom; - n representing a number between 2 and 4; - Q representing a halide or an alkyl sulfate, preferably a halide.

[0144] Among the dyes of formula (C-VIII), the following dyes of formula (C-VIII') or formula (C-VIII”) may be used in particular: with Q an anionic counterion, particularly a halide such as bromide or chloride, or an alkyl sulfate such as methyl sulfate or mesytyl. Preferably Q is a halide, better still, a bromide.

[0145] A dye of formula (C-VIII') particularly preferred is HC Blue 17.

[0146] A dye of formula (C-VIII”) particularly preferred is HC Blue 16 (l-methylamino-4-(3'-dimethylpropylammoniumpropylamino)antraquinone bromide).

[0147] Preferably, the anthraquinone cationic direct dyes are chosen from dyes of formula (C-VIII') and (C-VIII”), and more preferably from dyes of formula (C-VIII”), better from HC Blue 16.

[0148] Preferably, the cationic direct dyes are chosen from Basic Blue 124, Basic Blue 26, Basic Brown 16, Basic Brown 17, Basic Orange 31, Basic Red 51, Basic Red 76, Basic Violet 10, Basic Violet 2, Basic Yellow 57, Basic Yellow 87, Basic Violet 14, Hydroxyanthraquinone-aminopropyl Methyl Morpholinium Methosulfate, HC Blue 15, HC Blue 16, HC Blue 17, HC Orange No. 5, HC Brown No. 1, HC Brown No. 2, HC Red No. 8, and mixtures thereof.

[0149] The process according to the present invention may employ one or more anionic direct dyes.

[0150] The anionic direct dyes of the invention are dyes commonly called "acid" direct dyes because of their affinity for alkaline substances. Anionic direct dyes are understood to mean any direct dye containing in its structure at least one CO2R or SO3R substituent with R denoting a hydrogen atom or a cation from a metal or amine, or an ammonium ion.

[0151] Anionic direct dyes may be selected from acidic nitro direct dyes, acidic azo dyes, acidic azinic dyes, acidic triarylmethanic dyes, acidic indoamine dyes, acidic anthraquinone dyes, acidic indigoid dyes and acidic natural dyes.

[0152] According to the invention, the anionic direct dye(s) can be chosen, alone or in mixture, from the following anionic direct dyes of formulas (A-II), (A-II'), (A-III), (A-m'), (A-IV), (A-IV'), (AV), (A-V'), (A-VI), (A-VII), (A-VIII) and (A-IX):

[0153] a) Diaryl anionic azo dyes of formula (A-II) or (A-II'): formulas (A-II) and (A-II') in which: * R7, R8, R9, Rio, R'7, R'8, R'9 and R'1O, whether identical or different, represent a hydrogen atom or a group chosen from: - alkyl; - alkoxy, alkylthio; - hydroxy, mercapto; - nitro, nitroso; - R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X”- with R° representing a hydrogen atom, an alkyl or aryl group; X, X' and X”, identical or different, representing an oxygen, sulfur or NR atom with R representing a hydrogen atom or an alkyl group; - (O)2S(O )-, M+ with M+ representing a hydrogen atom or a cationic counter-ion; - (O)CO -, M+ with M+ as defined previously; - R”-S(O)2-, with R” representing a hydrogen atom, an alkyl group, an aryl group, (di)(alkyl)amino, aryl(alkyl)amino; preferably a phenylamino or phenyl group; - R”'-S(O)2-X'- with R'” representing an alkyl group, possibly substituted aryl, X' as defined previously; - (di)(alkyl)amino; - aryl(alkyl)amino possibly substituted by one or more groups chosen from i) nitro; ii) nitroso; iii) (O)2S(O-)-, M+ and iv) alkoxy with M+ as defined above; - heteroaryl possibly substituted; preferably a benzothiazolyl group; - cycloalkyl; in particular cyclohexyl, - Ar N=N with Ar representing an aryl group possibly substituted; preferably a phenyl possibly substituted by one or more alkyl groups, (O)2S(O )-, M+ or phenylamino; - or two contiguous groups R7 with R8 or R8 with R9 or R9 with R10 together form a fused group benzo A'; and R'7 with R'8 or R'8 with R'9 or R'9 with R'10 together form a fused group benzo B'; with A' and B' possibly substituted by one or more groups chosen from i) nitro; ii) nitroso; iii) (O)2S(O-)-, M+; iv) hydroxy; v) mercapto; vi) (di)(alkyl)amino; vii) R°-C(X)-X'-; viii) R°-X'-C(X)-; ix) R°-X'-C(X)-X”-; x) Ar-N=N- and xi) aryl(alkyl)amino possibly substituted; with M+, R°, X, X', X” and Ar as defined above; * W represents a sigma bond, an oxygen atom, a sulfur atom, or a divalent radical i) -NR- with R as defined previously, or ii) methylene -C(Ra)(Rb)- with Ra and Rb, identical or different, representing a hydrogen atom or an aryl group, or Ra and Rb together with the carbon atom bearing them form a spiro cycloalkyl; preferably W represents a sulfur atom or Ra and Rb together form a cyclohexyl; provided that formulas (A-II) and (A-II') comprise at least one sulfonate radical (O)2S(O )-, M+ or one carboxylate radical (O)CO -, M+ on one of the rings A, A', B, B' or C; preferably sodium sulfonate;

[0154] A titre d’exemple de colorants de formule (A-II), on peut citer : Acid Red 1, Acid Red 4, Acid Red 13, Acid Red 14, Acid Red 18, Acid Red 27, Acid Red 28, Acid Red 32, Acid Red 33, Acid Red 35, Acid Red 37, Acid Red 40, Acid Red 41, Acid Red 42, Acid Red 44, Pigment red 57, Acid Red 68, Acid Red 73, Acid Red 135, Acid Red 138, Acid Red 184, Food Red 1, Food Red 13, Acid Orange 6, Acid Orange 7, Acid Orange 10, Acid Orange 19, Acid Orange 20, Acid Orange 24, Yellow 6, Acid Yellow 9, Acid Yellow 36, Acid Yellow 199, Food Yellow 3; Acid Violet 7, Acid Violet 14, Acid Bine 113, Acid Bine 117, Acid Black 1, Acid Brown 4, Acid Brown 20, Acid Black 26, Acid Black 52, Food Black 1, Food Black 2 ; Food yellow 3 ou sunset yellow;

[0155] et à titre d’exemple de colorants de formule (A-IF), on peut citer : Acid Red 111, Acid Red 134, Acid yellow 38 ;

[0156] b) les colorants azo anioniques pyrrazolone de formule (A-III) et (A-IIF) : formulas (A-III) and (A-IIF) in which: * Ru, Rn and Rn, identical or different, represent a hydrogen atom, a halogen, an alkyl group or -(O)2S(O), M+ with M+ as defined previously; * Ru represents a hydrogen atom, an alkyl group or a -C(O)O group, M+ with M+ as defined previously; * Rb represents a hydrogen atom; * Ri6 represents an oxo group in which case R'i6 is absent, or else R[5 with R[6 together form a double bond; * Rn and Ri8, whether identical or different, represent a hydrogen atom, or a group chosen from: - (O)2S(O )-, M+ with M+ as defined previously; - Ar-OS(O)2- with Ar representing an aryl group possibly substituted; preferably a phenyl possibly substituted by one or more alkyl groups; * R19 and R2q together form either a double bond or a benzo D' group, possibly substituted; * R'16, R'19 and R'20, identical or different, represent a hydrogen atony or an alkyl, or hydroxy, group; * R2i represents a hydrogen atom, an alkyl group, or alkoxy; * Ra and Rb, identical or different, are as defined previously, preferably Ra represents a hydrogen atom and Rb represents an aryl group; * Y represents either a hydroxy group or an oxo group; * represents a single bond when Y is an oxo group; and represents a double bond when Y represents a hydroxy group; provided that formulas (A-III) and (A-III') comprise at least one sulfonate radical (O)2S(O )-, M+ or one carboxylate radical -C(O)O-, M+ on one of the rings D or E; preferably sodium sulfonate; Examples of colorants with formula (A-III) include: Acid Red 195, Acid Yellow 23, Acid Yellow 27, Acid Yellow 76, and examples of colorants with formula (A-III') include: Acid Yellow 17;

[0157] c) the anthraquinone dyes of formula (A-IV) and (A-IV'): formulas (A-IV) and (A-IV) in which: * R22, R23, R24, R25, R26 and R27, whether identical or different, represent a hydrogen atom, a halogen atom, or a group chosen from: - alkyl; - hydroxy, mercapto; - alkoxy, alkylthio; - aryloxy or arylthio possibly substituted, preferably substituted by one or more groups chosen from alkyl and (O)2S(O )-, M+ with M+ as defined above; - aryl(alkyl)amino possibly substituted by one or more groups chosen from alkyl and (O)2S(O )-, M+ with M+ as defined previously; - (di)(alkyl)amino; - (di)(hydroxyalkyl)amino - (O)2S(O )-, M+ with M+ as defined previously; * Z' represents a hydrogen atom or a group NR28R29 where R28 and R29, identical or different, represent a hydrogen atom or a group chosen from: - alkyl; - polyhydroxyalkyl such as hydroxyethyl; - aryl possibly substituted by one or more particularly i) alkyl groups such as methyl, n-dodecyl, n-butyl; ii) (O)2S(O )-, M+ with M+ as defined previously; iii) R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X”- with R°, X, X' and X” as defined previously, preferably R° represents an alkyl group; - cycloalkyl; in particular cyclohexyl; * Z, represents a group chosen from hydroxy and NR'28R'29 with R'28 and R'29, identical or different, represent the same atoms or groups as R28 and R29 as defined previously; provided that formulas (A-IV) and (A-IV') comprise at least one sulfonate radical (O)2S(O )-, M+ or one carboxylate radical -C(O)O, M+; preferably sodium sulfonate; As an example of dyes of formula (A-IV), we can cite: Acid Blue 25, Acid Blue 43, Acid Blue 62, Acid Blue 78, Acid Blue 129, Acid Blue 138, Acid Blue 140, Acid Blue 251, Acid Green 25, Acid Green 41, Acid Violet 42, Acid Violet 43, Mordant Red 3; EXT purple No. 2; and as an example of dyes of formula (A-IV') we can cite: Acid Black 48;

[0158] d) the nitro dyes of formula (AV), and (A-V'): ! (A-V') ALKSO, M' * Ju (V) NO? formulas (AV) and (A-V') in which: * R3o, R3i and R32, whether identical or different, represent a hydrogen atom, a halogen atom, or a group chosen from: - alkyl; - alkoxy possibly substituted by one or more hydroxy groups, alkylthio possibly substituted by one or more hydroxy groups; - hydroxy, mercapto; - nitro, nitroso; - polyhalogenoalkyl; - R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X”- with R° ; X, X' and X” as defined previously; - (O)2S(O )-, M+ with M+ as defined previously; - (O)CO -, M+ with M+ as defined previously; - (di)(alkyl)amino; - (di)(hydroxyalkyl)amino; - heterocycloalkyl such as piperidino, piperazino or morpholino; in particular R30, R3i and R32 represent a hydrogen atom; * Rc and Rd, whether identical or different, represent a hydrogen atom or an alkyl group; * W is as defined previously; W particularly represents a -NH- group; * ALK represents a divalent alkylene group, linear or branched, in Ci-C6; particularly ALK represents a -CH2-CH2- group; * n equals 1 or 2; * p represents an integer between 1 and 5 inclusive; * q represents an integer between 1 and 4 inclusive; * u is equal to 0 or 1;

[0159]

[0160] * when n equals 1, J represents a nitro, or nitroso, group; particularly nitro; * when n equals 2, J represents an oxygen atom, a sulfur atom, or a divalent radical -S(O)m- with m representing an integer 1 or 2; preferably J represents a radical -SO2-; * M' represents a hydrogen atom or a cationic counter-ion; * -- The presence or absence of x represents a benzo group, possibly substituted by one or more R30 groupings as defined above; provided that the formulas (AV) and (A-V') include at least one sulfonate radical (O)2S(O )-, M+ or one carboxylate radical -C(O)O-, M+; preferably sodium sulfonate; Examples of colorants with formula (AV) include: Acid Brown 13; Acid Orange 3; examples of colorants with formula (A-V') include: Acid Yellow 1, Sodium salt of 2,4-dinitro-l-naphthol-7-sulfonic acid, 2-piperidino-5-nitrobenzenesulfonic acid, 2(4'-N,N(2"-hydroxyethyl)amino-2'-nitro)aniline ethanesulfonic acid, 4-β-hydroxyethylamino-3-nitrobenzenesulfonic acid; EXT D&C yellow 7; e) triarylmethane dyes of formula (A-VI): U R. *2 ru. formula (A-VI) in which: * R33, R34, R35 and R36, identical or different, represent a hydrogen atom or a group chosen from alkyl, possibly substituted aryl and possibly substituted arylalkyl; particularly an alkyl and benzyl group possibly substituted by an (O)mS(O )-, M+ group with M+ and m as defined above; * R37, R38, R39, R40, R41, R42, R43 and R44, whether identical or different, represent a hydrogen atom or a group chosen from: - alkyl; - alkoxy, alkylthio; - (di)(alkyl)amino; - hydroxy, mercapto; - nitro, nitroso; - R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X”- with R° representing a hydrogen atom, an alkyl or aryl group; X, X' and X”, identical or different, representing an oxygen, sulfur or NR atom with R representing a hydrogen atom or an alkyl group; - (O)2S(O )-, M+ with M+ representing a hydrogen atom or a cationic counter-ion; - (O)CO -, M+ with M+ as defined previously; - or two contiguous groups R4[ with R42 or R2 with R41 or R43 with R44 together form a fused benzo group: I'; with I' possibly substituted by one or more groups chosen from i) nitro; ii) nitroso; iii) (O)2 S(O )-, M+; iv) hydroxy; v) mercapto; vi) (di)(alkyl)amino; vii) R°-C(X)-X'-; viii) R°-X'-C(X)- ; ix) R°-X'-C(X)-X”- ; with M+, R°, X, X', X” as defined above; particularly R37 at Rio represent a hydrogen atom, and Ri at IR, identical or different represent a hydroxy group or (O)2S(O )-, M+; and when R3 with R4 together form a benzo group, it is preferentially substituted by an (O)2S(O )- group; provided that at least one of the rings G, H, I, or I' comprises at least one sulfonate radical (O)2S(O)- or one carboxylate radical -C(O)O; preferably sulfonate. Examples of dyes with the formula (A-VI) include: Acid Blue 1; Acid Blue 3; Acid Blue 7; Acid Blue 9; Acid Violet 49; Acid Green 3; Acid Green 5; Acid Green 50;

[0161] f) xanthene-derived dyes of formula (A-VII): % R (A-VII) fR R \ R, formula (A-VII) in which: * R5, R46, R7 and R48, whether identical or different, represent a hydrogen atom or a halogen atom; * R9, R50, R51 and R52, whether identical or different, represent a hydrogen atom, a halogen atom, or a group chosen from: - alkyl; - alkoxy, alkylthio; - hydroxy, mercapto; - nitro, nitroso; - (O)2S(O )-, M+ with M+ representing a hydrogen atom or a cationic counter-ion; - (O)CO -, M+ with M+ as defined previously; in particular R53, R54, R55 and R48 represent a hydrogen or halogen atom; * G represents an oxygen atom, sulfur atom or an NR group with R representing a hydrogen atom or an alkyl group; particularly G represents an oxygen atom; * L represents an alkoxide O M+; a thioalkoxide S , M+ or an NRf group, with Rf representing a hydrogen atom or an alkyl group, and M+ as defined previously; M+ is particularly sodium or potassium; * L' represents an oxygen atom, sulfur atom or ammonium group: N+ RfRg, with Rf and Rg, identical or different, representing a hydrogen atom, an alkyl group, aryl group possibly substituted; L' particularly represents an oxygen atom or a phenylamino group possibly substituted by one or more alkyl groups or (O)mS(O )-, M+ with m and M+ as defined previously; * Q and Q', whether identical or different, represent an oxygen or sulfur atom; particularly Q and Q' represent an oxygen atom; * M+ is as defined previously.

[0162] As an example of colorants of formula (A-VII), we can mention: Acid Yellow 73; Acid Red 51; Acid Red 52, Acid Red 87; Acid Red 92; Acid Red 95; Acid Violet 9;

[0163] g) dyes derived from indole of formula (A-VIII): (A-vni) formula (A-VIII) in which: * R53, R54, R55, R56, R57, Rss, R59 and R6o, whether identical or different, represent a hydrogen atom or a group chosen from: - alkyl; - alkoxy, alkylthio; - hydroxy, mercapto; - nitro, nitroso; - R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X”- with R° representing a hydrogen atom, an alkyl or aryl group; X, X' and X”, identical or different, representing an oxygen, sulfur or NR atom with R representing a hydrogen atom or an alkyl group; - (O)2S(O )-, M+ with M+ representing a hydrogen atom or a cationic counter-ion; - (O)CO -, M+ with M+ as defined previously; * G represents an oxygen atom, sulfur atom or an NR group with R representing a hydrogen atom or an alkyl group; particularly G represents an oxygen atom; * Ri and Rh, whether identical or different, represent a hydrogen atom or an alkyl group; provided that the formula (A-VIII) comprises at least one sulfonate radical (O)2 S(O )-, M+ or one carboxylate radical -C(O)O, M+; preferably sodium sulfonate;

[0164] As an example of colorants of formula (A-VIII), we can mention: Acid Blue 74.

[0165] h) quinoline-derived dyes of formula (A-IX): formula (A-IX) in which: * R6i represents a hydrogen atom, halogen or alkyl group; * R62, R63, and Rm, whether identical or different, represent a hydrogen atom or a (O)2S(O )- group, M+ with M+ representing a hydrogen atom or a cationic counter-ion; * or R6i with R62, or R6i with R64, together form a benzo group possibly substituted by one or more (O)2S(O )- groups, M+ with M+ representing a hydrogen atom or a cationic counter-ion; it being understood that the formula (A-IX) includes at least one sulfonate radical (O)2S(O )-, M+ preferably sodium sulfonate.

[0166] Examples of colorants of formula (A-IX) include: Acid Yellow 2, Acid Yellow 3 and Acid Yellow 5.

[0167] More particularly, the process according to the present invention may use one or more anionic direct dyes selected, alone or in mixture, from among the following anionic direct dyes:

[0168] [Tables 1] (C.L 45380) Acid Red 87 (A-VII) (C.L 10316) Sel de sodium de l’acide 2,4-dinitro-l-naphtol-7-sulfonique (A-V’ ) (C.L 10383) Acid Orange 3 (A-V) (C.L 13015) Acid Yellow 9 / Food Yellow 2 (A-II) (C.L 14780) / Direct Red 45 / Food Red 13 (A-II) (C.L 13711) Acid Black 52 (A-II) (C.L 13065) Acid Yellow 36 (A-II) (C.L 14700) Sel de sodium de l’acide l-hydroxy-2-(2',4'-xylyl-5-sufonatoazo)-naphtalène-4-sulfonique / Food Red 1 (A-II) (C.L 14720) Acid Red 14 / Food Red 3 / Mordant Blue 79 (A-II) (C. 1. 14805) Sel de sodium de l’acide 4-hydroxy-3-[(2-métoxy-5-. nitrophényl) diaza]-6-(phénylamino)naphtalène-2-sulfonique / Acid Brown 4 ( A-II) (C.L 15510) Acid Orange 7 / Pigment Orange 17 / Solvent Orange 49 (A-II) (C.L 15985) Food Yellow 3 / Pigment Yellow 104 (A-II) (C.L 16185) Acid Red 27 / Food Red 9 (A-II) (C.L 16230) Acid Orange 10 / Food Orange 4 (A-II) (C.L 16250) Acid Red 44 (A-II) (C.L 17200) Acid Red 33 / Food Red 12 (A-II) (C.L 15685) Acid Red 184 (A-II) (C.L 19125) Acid Violet 3 (A-II) (CL 18055) Sodium salt of l-hydroxy-2-(4'-acetamidophenylazo)-8-acetamido-naphthalene-3,6-disulfonic acid / Acid Violet 7 / Food Red 11 (A-II) (CL 18130) Acid Red 135 (A-II) (CL 19130) Acid Yellow 27(A-III) (CL 19140) Acid Yellow 23 / Food Yellow 4 (A-III) . (CL 20170) 4'-(sulfonato-2,4'-dimethyl)-bis-(2,6-phenylazo)-1,3-dihydroxybenzene / Acid Orange 24 (A-II) (Cl 20470) Sodium salt of l-amino-2-(4'-nitrophenylazo)-7-phenylazo-8-hydroxy-naphthalene-3,6-disulfonic acid / Acid Black 1 (A-II) (Cl 23266) (4-((4-methylphenyl)sulfonyloxy)-phenylazo)2,2'-dimethyl-4-((2-hydroxy-5,8-disulfonato)naphtylazo)biphenyl / Acid Red 111 (A-II') (Cl 27755) Food Black 2 (A-II) (Cl 25440) l-(4'-sulfonatophenylazo)-4-((2"-hydroxy-3"-acetylamino-6",8"-disulfonato)naphtylazo)-6-sulfonatonaphthalene (tetrasodium salt) / Food Black 1 (A-II) (Cl 42090) Acid Blue 9 (A-VI) (Cl 60730) Acid Violet 43 (A-IV) (Cl 61570) Acid Green 25 (A-IV) (Cl 62045) Sodium salt of l-amino-4-cyclohexylamino-9,10-anthraquinone 2-sulfonic acid / Acid Blue 62 (A-IV) (Cl 62105) Acid Blue 78 (A-IV) (Cl14710) Sodium salt of 4-hydroxy-3((2-methoxyphenyl)-azo)-1-naphthalene sulfonic acid / Acid Red 4 (A-II) 2-piperidino-5-nitrobenzene sulfonic acid (V') 2(4'-N,N(2"-hydroxyethyl)amino-2'-nitro)aniline ethane sulfonic acid (A-V') 4-β-hydroxyethylamino-3-nitrobenzene sulfonic acid (A-V') (Cl 42640) Acid Violet 49 (A-VI) (Cl 42080) Acid Blue 7 (A-VI) (Cl 58005) Sodium salt of 1,2-dihydroxy-3-sulfo-anthraquinone / Mordant Red 3 (A-IV) (Cl 62055) Sodium salt of acid l-amino-9,10-dihydro-9,10-dioxo-4-(phenylamino) 2-anthracene sulfonic acid / Acid Blue 25 (A-IV) (Cl 14710) Sodium salt of 4-hydroxy-3-((2-methoxyphenyl)-azo)-l-naphthalene sulfonic acid / Acid Red 4 (A-II) .

[0169] Most of these dyes are described in particular in the Color Index published by The Society of Dyers and Colorists, PO Box 244, Perkin House, 82 Grattan Road, Bradford, Yorkshire, BD1 2JBN England.

[0170] The anionic colorants most particularly preferred are the colorants designated in the Color Index under the code CI 58005 (monosodium salt of 1,2-dihydroxy-9,10-anthraquinone-3-sulfonic acid), CI 60730 (monosodium salt of 2-[(9,10-dihydro-4-hydroxy-9,10-dioxo-l-anthracenyl)-amino]-5-methylbenzenesulfonic acid), CI 15510 (monosodium salt of 4-[(2-hydroxy-l-naphthalenyl)-azo]-benzenesulfonic acid), CI 15985 (disodium salt of 6-hydroxy-5-[(4-sulfophenyl)-azo]-2-naphthalenesulfonic acid), CI 17200 (disodium salt of 5-amino-4-hydroxy-3-(phenylazo)-2,7-naphthalene disulfonic acid), CI 20470 (disodium salt of l-amino-2-(4'-nitrophenylazo)-7-phenylazo-8-hydroxy-3,6-naphthalene disulfonic acid), CI 42090 (disodium salt of N-ethyl-N-[4-[[4-[ethyl[3-sulfophenyl]-methyl]-amino]-phenyl](2-s-ulfophenyl)-methylene]-2,5-cyclohexadien-1-ylidene]-3-sulfobenzenemethanaminium hydroxide, internal salt), CI61570 (disodium salt of 2,2'-[(9,10-dihydro-9,10-dioxo-l,4-anthracenediyl)-diimino]-bis-[5-methyl]-benzenesulfonic acid. .

[0171] Compounds corresponding to the mesomeric, tautomeric forms of (A-II) to (A-IX) structures can also be used.

[0172] Among the natural direct dyes that can be used according to the invention, mention may be made of hennotannic acid, juglone, alizarin, purpurin, carminic acid, kermesic acid, purpurogallin, protocatechaldehyde, indigo, isatin, curcumin, spinulosin, apigenidine, and orcein. Extracts or decoctions containing these natural dyes, and in particular henna-based poultices or extracts, may also be used.

[0173] Preferably, the process according to the present invention uses one or more direct dyes selected from cationic direct dyes, amphoteric direct dyes, non-ionic direct dyes, and mixtures thereof, preferably selected from cationic direct dyes, more preferably selected from azo cationic direct dyes, hydrazono cationic direct dyes, anthraquinone cationic direct dyes, triarylmethane cationic direct dyes, and mixtures thereof.

[0174] More preferably, the direct colorant(s) are chosen from Basic Red 51, HC Blue 15, HC Blue 16, Disperse Violet 1, Basic Yellow 87, and mixtures thereof, preferably chosen from Basic Red 51, HC Blue 15, HC Blue 16, Disperse Violet 1, and mixtures thereof.

[0175] According to a first embodiment, the coloring process comprises applying to the keratin fibers a composition (A) comprising the direct colorants and possibly compound(s) A and then a composition (B) comprising the (poly)amine compound(s) and possibly compound(s) A, it being understood that at least one of the compositions (A) or (B) comprises compound(s) A, preferably composition (B) comprises compound(s) A.

[0176] Preferably, according to this first embodiment, the composition (B) does not include direct colorants.

[0177] According to a second embodiment, the coloring process includes the application to the keratin fibers of a composition (C) comprising the compound(s) A, the (poly)amine compound(s) and the direct dye(s).

[0178] According to another embodiment, the coloring process includes the application of compound(s) A and compound(s) (poly)amine(s) or of a composition (B) comprising compound(s) A and compound(s) (poly)amine(s) to keratin fibers previously colored using direct dye(s) or of a composition (A) comprising them.

[0179] According to another embodiment, the coloring process includes the application to the keratin fibers of the direct dye(s) or of a composition (D) comprising them and then of the compound(s) A or of a composition (A) comprising them and then of the (poly)amine compound(s) or of a composition (B) comprising them.

[0180] Compositions (A), (B), (C) and / or (D) can be applied to dry or wet keratin fibers, preferably with a weight ratio of the amount of composition applied relative to the amount of hair ranging from 0.1 to 10, preferably ranging from 0.3 to 5.

[0181] Preferably, the application of compositions (A), (B), (C) and / or (D) to keratin fibers is carried out at room temperature, i.e. at a temperature between 25 °C and 30 °C.

[0182] According to the first embodiment, the keratin fibers are preferably rinsed with water and / or dried after application of composition (A) and only dried after application of composition (B).

[0183] According to the second embodiment, the keratin fibers are preferably unrinsed and dried after application of composition (C).

[0184] When dried, keratin fibers can be air-dried or dried with a drying device such as a helmet, a hair dryer or a climazon.

[0185] Characteristics of compositions (A), (B) (C) and (D)

[0186] Preferably, compound(s) A are present in composition (A) or (B) or (C) in a total content of 0.2% to 80% by weight, preferably of 0.5% to 50% by weight, more preferably of 2% to 35% by weight, relative to the total weight of the composition comprising them.

[0187] Preferably, the (poly)amine compound(s) are present in composition (B) or (C) in a total content ranging from 0.2% to 60% by weight, preferably ranging from 0.5% to 40% by weight, more preferably ranging from 5% to 40% by weight, relative to the total weight of the composition comprising them.

[0188] Preferably, the direct colorant(s) are present in composition (A) or (C) or (D) in a total content ranging from 0.001% to 20% by weight, preferably ranging from 0.005% to 15% by weight, more preferably ranging from 0.01% to 10% by weight, even more preferably ranging from 0.05% to 5% by weight, most preferably ranging from 0.1% to 3% by weight, relative to the total weight of the composition comprising them.

[0189] Composition (B) can be obtained by extemporaneous mixing of a first composition comprising compound(s) A with a second composition comprising (poly)amine compound(s).

[0190] Composition (C) can be obtained by extemporaneous mixing of a first composition comprising compound(s) A with a second composition comprising the (poly)amine compound(s) and a third composition comprising the direct colorant(s).

[0191] Compositions (A), (B), (C) and (D) are cosmetic compositions, i.e. which comprise a cosmetically acceptable medium, i.e. a medium compatible with human keratin fibers.

[0192] According to a preferred embodiment, the compositions (A), (B), (C) and / or (D) comprise water and optionally one or more polar and / or protic solvents, preferably selected from monoalcohols having 2 to 6 carbon atoms, more preferably selected from ethanol, propanol, n-butanol, isopropanol, isobutanol, tert-butanol, pentanol, hexanol, and mixtures thereof, even more preferably selected from n-butanol, ethanol, and mixtures thereof, most preferably ethanol.

[0193] According to a more preferred embodiment, compositions (A), (B), (C) and / or (D) comprise water and one or more polar and / or protic solvents, preferably selected from monoalcohols having 2 to 6 carbon atoms, more preferably selected from ethanol, propanol, n-butanol, isopropanol, isobutanol, tert-butanol, pentanol, hexanol, and mixtures thereof, even more preferably selected from n-butanol, ethanol, and mixtures thereof, most preferably from ethanol.

[0194] Preferably, compositions (A), (B), (C) and / or (D) comprise water in a total weight content of 20% to 90% by weight, preferably 30% to 80% by weight, relative to the total weight of the composition comprising it.

[0195] When present, the polar and / or protic solvent(s) are present in compositions (A), (B), (C) and / or (D) in a total weight content ranging from 1% to 99% by weight, preferably ranging from 5% to 80% by weight, relative to the total weight of the composition comprising them.

[0196] Compositions (A), (B), (C) and / or (D) may comprise one or more volatile or non-volatile oils, preferably selected from hydrocarbon oils, more preferably selected from C8-Ci6 hydrocarbon oils, even more preferably selected from iso-alkanes, and better selected from Ci3-C16 iso-paraffins, isododecane, isohexadecane, and mixtures thereof, and even better isododecane.

[0197] By "oil" is meant a non-aqueous compound, immiscible with water, liquid at room temperature (20 °C) and atmospheric pressure (760 mm Hg).

[0198] By "hydrocarbon oil" is meant an oil formed essentially, or even composed, of carbon and hydrogen atoms, and possibly of oxygen and nitrogen atoms, and not containing silicon or fluorine atoms. It may contain alcohol, ester, ether, carboxylic acid, amine and / or amide groups.

[0199] When present, the oil(s) are present in compositions (A), (B), (C) and / or (D) in a total weight content of 1% to 90% by weight, preferably of 5% to 70% by weight, relative to the total weight of the composition comprising them.

[0200] Compositions (A), (B), (C) and / or (D) may be presented in all galenic forms classically used for hair application. Composition (C)

[0201] According to a second aspect, the present invention relates to a composition (C) as defined above. Kit

[0202] According to a third aspect, the present invention relates to a two- or three-compartment device comprising: - a first compartment containing a composition comprising one or more compounds A as defined above and possibly one or more direct dyes as defined above; - a second compartment separate from the first compartment containing a composition comprising one or more (poly)amine compounds as defined above and possibly one or more direct dyes as defined above; - possibly a third compartment, separate from the first and second compartments, containing one or more direct dyes as defined previously, it being understood that at least one of the compartments includes one or more direct dyes. Use

[0203] According to a fourth aspect, the present invention relates to the use of one or more compounds A as defined above associated with one or more (poly)amine compounds as defined above or of a composition (B) comprising the compound(s) A as defined above and the (poly)amine compound(s) as defined above to improve the shampoo retention of a direct coloring of keratin fibers. Examples

[0204] The following examples serve to illustrate the invention without, however, being limiting in nature.

[0205] In the following examples, unless otherwise indicated, where compositions are implemented, the contents are indicated as a mass percentage in relation to the total weight of the composition considered.

[0206] The compounds A that can be used in the examples are as follows:

[0207] * Compound No. 1: K-FLEX 7301 marketed by KING Industrie o I j O CH, o

[0208] • Compound No. 2: Glucose with acetoacetate function (5eq)

[0209] Compound 2 was synthesized according to the following scheme:

[0210] Scheme in which identical or different RI represents a hydrogen atom or a -methylcarbonylmethylcarbonyl group -C(O)-CH2-C(O)-CH3, it being understood that at least two RI radicals represent -C(O)-CH2-C(O)-CH3, in particular 5 RI radicals represent -C(O)-CH2-C(O)-CH3.

[0211] In a one-liter three-necked flask equipped with a mechanical stirrer and a distillation column, 100 g of D-glucose and 482.90 g of tert-butyl acetoacetate are introduced. The reaction mixture is heated in an oil bath (oil bath temperature 150°C–160°C) for 5 hours. After 5 hours, NMR confirms the grafting of the acetoacetate group. The reaction mixture is then concentrated using a rotary evaporator at 150°C under continuous vacuum. A highly viscous, dark brown liquid is obtained, which, upon analysis, corresponds to the expected product.

[0212] • Compound No. 3 Mannose with acetoacetate function (5eq)

[0213] Compound 3 was synthesized according to the following scheme:

[0214] Scheme in which identical or different RI represents a hydrogen atom or a -C(O)-CH2-C(O)-CH3 group, it being understood that at least two RI radicals represent -C(O)-CH2-C(O)-CH3, in particular 5 RI radicals represent -C(O)-CH2-C(O)-CH3

[0215] In a one-liter three-necked flask equipped with a mechanical stirrer and a distillation column, 100 g of D-mannose and 482.90 g of tert-butyl acetoacetate are introduced. The reaction mixture is heated in an oil bath (oil bath temperature 140°C–150°C) for 5 h. After 5 h, NMR confirms the grafting of the acetoacetate group. The reaction mixture is then concentrated using a rotary evaporator at 150°C under continuous vacuum. A viscous yellow liquid is obtained, which, upon analysis, corresponds to the expected product.

[0216] • Compound No. 4 Xylitol with acetoacetate function (5eq)

[0217] Compound 4 was synthesized according to the following scheme:

[0218] Scheme in which identical or different RI represents a hydrogen atom or a -C(O)-CH2-C(O)-CH3 group, it being understood that at least two RI radicals represent -C(O)-CH2-C(O)-CH3, in particular 5 RI radicals represent -C(O)-CH2 -C(O)-CH3.

[0219] In a 500 mL three-necked flask equipped with a mechanical stirrer and a distillation column, 25 g of xylitol and 142.69 g of tert-butyl acetoacetate are introduced. The reaction mixture is heated in an oil bath (oil bath temperature 140°C–150°C) for 5 h. After 5 h, NMR confirms the grafting of the acetoacetate group. The reaction mixture is then concentrated using a rotary evaporator at 150°C under continuous vacuum. A highly viscous brown liquid is obtained, which, upon analysis, corresponds to the expected product.

[0220] • Compound No. 5 Sorbitol with acetoacetate function (6eq)

[0221] Compound 5 was synthesized according to the following scheme:

[0222] Scheme in which identical or different RI represents a hydrogen atom or a -C(O)-CH2-C(O)-CH3 group, it being understood that at least two RI radicals represent -C(O)-CH2-C(O)-CH3, in particular 6 RI radicals represent -C(O)-CH2 -C(O)-CH3.

[0223] In a one-liter three-necked container equipped with mechanical stirring and a column Distilled water, 100 g of sorbitol, and 573.20 g of tert-butyl acetoacetate are introduced. The reaction mixture is heated in an oil bath (oil bath temperature 140°C–150°C) for 5 h. After 5 h, NMR confirms the grafting of the acetoacetate group. The reaction mixture is then concentrated using a rotary evaporator at 150°C under continuous vacuum. A viscous, orange-yellow liquid is obtained, corresponding to the following after analysis. to the expected product. • Compound No. 6 Sorbitol with acetoacetate function (3eq) Compound 6 was synthesized according to the following scheme:

[0224]

[0225]

[0226] Scheme in which identical or different RI represents a hydrogen atom or a -C(O)-CH2-C(O)-CH3 group, it being understood that at least two RI radicals represent -C(O)-CH2-C(O)-CH3, in particular 3 RI radicals represent -C(O)-CH2-C(O)-CH3

[0227] In a one-liter three-necked flask equipped with a mechanical stirrer and a distillation column, 100 g of sorbitol and 260.54 g of tert-butyl acetoacetate are introduced. The reaction mixture is heated in an oil bath (oil bath temperature 140°C–150°C) for 5 h. After 5 h, NMR confirms the grafting of the acetoacetate group. The reaction mixture is then concentrated using a rotary evaporator at 150°C under continuous vacuum. A viscous yellow liquid is obtained, which, upon analysis, corresponds to the expected product.

[0228] • Compound No. 7 Dipentaerythritol with acetoacetate function (6eq)

[0229] Compound 7 was synthesized according to the following scheme:

[0230] Scheme in which identical or different RI represents a hydrogen atom or a -C(O)-CH2-C(O)-CH3 group, it being understood that at least two RI radicals represent -C(O)-CH2-C(O)-CH3, in particular 6 RI radicals represent -C(O)-CH2 -C(O)-CH3.

[0231] In a one-liter three-necked flask equipped with a mechanical stirrer and a distillation column, 50 g of dipentaerythritol and 195.33 g of tert-butyl acetoacetate are introduced. The reaction mixture is heated in an oil bath (oil bath temperature 140°C–150°C) for 4 hours. After 4 hours, NMR confirms the incorporation of the acetoacetate group. The reaction mixture is then concentrated using a rotary evaporator at 150°C under continuous vacuum. A viscous, orange-brown liquid is obtained, which, upon analysis, corresponds to the expected product.

[0232] * Compound No. 8 Pentaerythritol tetraacetoacetate

[0233] Compound 8 was synthesized according to the following scheme:

[0234] In a one-liter three-necked flask equipped with a mechanical stirrer and a distillation column, 100 g of Pentaerythritol and 510.89 g of Tert-butyl acetoacetate are introduced. The reaction mixture is heated in an oil bath (oil bath temperature 140°C-150°C) for 4 hours.

[0235] After 4 hours, NMR confirms the grafting of the acetoacetate group. The reaction mixture is then concentrated using a rotary evaporator at 150 °C under continuous vacuum. A translucent yellow viscous liquid is obtained, which, after analysis, corresponds to the expected product.

[0236] • Compound No. 9 Sucrose with acetoacetate function (8eq)

[0237] Compound 9 was synthesized according to the following scheme:

[0238] Scheme in which identical or different RI represents a hydrogen atom or a -C(O)-CH2-C(O)-CH3 group, it being understood that at least two RI radicals represent -C(O)-CH2-C(O)-CH3, in particular 8 RI radicals represent -C(O)-CH2-C(O)-CH3

[0239] In a one-liter three-necked flask equipped with a mechanical stirrer and a distillation column, 100 g of sucrose and 406.55 g of tert-butyl acetoacetate are introduced. The reaction mixture is heated in an oil bath (oil bath temperature 140°C–150°C) for 4 hours. After 4 hours, NMR confirms the grafting of the acetoacetate group. The reaction mixture is then concentrated using a rotary evaporator at 150°C under continuous vacuum. A viscous, orange-yellow liquid is obtained, which, upon analysis, corresponds to the expected product.

[0240] The compositions implemented in the examples were prepared from the following compositions: Compositions PI to P5

[0241] [Tables2] Ingredients PI P2 P3 P4 P5 Compound No. 8 19.9 19 - - - Compound No. 9 - - - 19.7 19.9 Compound No. 7 - - 19.2 - - Basic Red 51 - 0.2 - - - HC Blue 15 - - 0.2 - - HC Blue 16 - - - 0.2 - Disperse Violet 1 - - - - 1 50 / 50 Water / EtOH Qsp 100 Qsp 100 Qsp 100 Qsp 100 Qsp 100 NI to N5 compositions

[0242] [Tables3] Ingredients NI N2 N3 N4 N5 1,3-Diamino-2-propan-l-ol CAS: 616-29-5 Supplier: Sigma-A Aldrich 3.8 7.05 Spermidine CAS: 124-20-9 Supplier: Sigma-A Aldrich 6.2 - - - - Jeffamine T-403 Polyetheramine Mw = 440 g / mol AHEW = 81 g / eq CAS: 39423-51-3 Supplier: Huntsman 20.75 20.8 Polylysine PL-25 (as a 25% wt. solution in water) Supplier: JNC - - - 23 MA - 50 / 50 Water / EtOH Qsp 100 Qsp 100 Qsp 100 - Qsp 100 Water - - - Qsp 100 -

[0243] MA: Active Ingredient Compositions DI to D5

[0244] [Tables4] Ingredients DI D2 D3 D4 D5 2-Hydroxyethylamino-5- Nitroanisole 0.2 - - - - HC Blue 15 - 0.1 - - - Basic Yellow 87 - - - - - HC Blue 16 - - 0.1 - - Basic Red 51 - - - 0.1 - Disperse Violet 1 - - - - 0.5 50 / 50 Water / EtOH Qsp 100 Qsp 100 Qsp 100 Qsp 100 Qsp 100

[0245] Evaluation of the persistence of the color of highlights after shampooing

[0246] In the following examples, the persistence of the color of the highlights after shampooing was evaluated in the CIE L*a*b* system, using a Minolta Spectrophotometer CM3600A colorimeter (illuminant D65, angle 10°, specular component included).

[0247] In this L*a*b* system, L* represents the intensity of the color, a* indicates the green / red color axis and b* the blue / yellow color axis.

[0248] The color permanence is assessed by the color difference AE between the colored strands before shampooing, and then after 5 or 10 shampoos. The lower the AE value, the more the color persists after shampooing. The AE value is calculated according to the following equation: ■ L. + K

[0249] In this equation, L*, a* and b* represent the values ​​measured after hair coloring and after undergoing 5 or 10 shampoos, and Lo*, a0* and b0* represent the values ​​measured after hair coloring but before shampooing. Example 1

[0250] The process implemented in Example 1 is a two-step process:

[0251] - Step 1

[0252] Composition DI was applied to a strand of dry, 90% white natural hair placed on a heated plate maintained at 27°C, at a rate of 1g of composition DI per gram of hair. The hair was then left to rest for 20 minutes, rinsed with water, and finally dried with a hairdryer.

[0253] * Step 2

[0254] At the time of use, the PI and NI compositions were mixed together in a weight ratio of 1:1. The resulting mixture was then applied at room temperature to the strand obtained in step 1 at a rate of 1g of mixture per gram of strand, and the strand was finally dried with a hairdryer.

[0255] The residual effect of shampoos was evaluated according to the protocol described above. The process according to the invention is compared to the same process implementing only step 1, referred to as "comparative process 1".

[0256] The results of the measurements are shown in the table below:

[0257] [Tables5] Process Number of Shampoos L* a* b* AE Example 1 0 54.42 -2.39 22.85 2.89 10 56.08 -2.39 20.49 Comparative Process 1 0 61.87 -3.24 31.36 18.30 10 64.13 -0.01 13.49

[0258] The yellow colour obtained using the process according to the invention has a better residual colour at 10 shampoos than that obtained using the comparative process 1. Example 2

[0259] The process implemented in Example 2 is a one-step process.

[0260] At the time of use, compositions P2 and N2 were mixed together in a 1:1 weight ratio. The resulting mixture was then applied to a strand of dry, natural, 90% white hair at a rate of 1 g of mixture per gram of hair. The hair was then left to rest for 5 minutes and finally dried with a hairdryer.

[0261] Residual effect of shampoos was evaluated according to the protocol described above. The process according to the invention is compared to the same process using composition D4 instead of the P2+N2 mixture.

[0262] The results of the measurements are shown in the table below:

[0263] [Tableauxô] Process Number of Shampoos L* a* b* AE Example 2 0 33.73 37.51 1.35 7.95 5 41.03 35.13 -0.72 Comparative Process 2 0 37.45 32.94 6.73 25.59 5 51.04 11.38 4.46

[0264] The red colour obtained using the process according to the invention has a better residual colour at 5 shampoos than that obtained using the comparative process 2. Example 3

[0265] The process implemented in Example 3 is a one-step process.

[0266] At the time of use, compositions P3 and N3 were mixed together in a 1:1 weight ratio. The resulting mixture was then applied to a strand of dry, 90% white natural hair at a rate of 1 g of mixture per gram of hair. The hair was then left to rest for 5 minutes and finally dried with a hairdryer.

[0267] Residual effect of shampoos was evaluated according to the protocol described above. The process according to the invention is compared to the same process using composition D2 instead of the P3+N3 mixture.

[0268] The results of the measurements are shown in the table below:

[0269] [Tables?] Process Number of Shampoos L* a* b* AE Example 3 0 44.88 -14.8 15.7 8.47 5 44.82 -17.12 7.55 Comparative Process 3 0 38.87 -7.99 -18.87 22.52 5 52.26 -10.06 -0.88

[0270] The blue colour obtained using the process according to the invention has a better residual colour at 5 shampoos than that obtained using the comparative process 3. Example 4

[0271] The process implemented in Example 4 is a one-step process.

[0272] At the time of use, compositions P4 and N4 were mixed together in a 1:1 weight ratio. The resulting mixture was then applied to a strand of dry, 90% white natural hair at a rate of 1 g of mixture per gram of hair. The hair was then left to rest for 5 minutes and finally dried with a hairdryer.

[0273] Residual effect of shampoos was evaluated according to the protocol described above. The process according to the invention is compared to the same process using composition D3 instead of the P4+N4 mixture.

[0274] The results of the measurements are shown in the table below:

[0275] [Tables8] Process Number of Shampoos L* a* b* AE Example 4 0 25.87 0.22 -23.2 21.30 5 43 -8.11 -13.66 Comparative Process 4 0 27.54 3.24 -23.8 34.27 5 51.93 -8.14 -2.59

[0276] The blue colour obtained using the process according to the invention has a better residual colour at 5 shampoos than that obtained using the comparative process 4. Example 5

[0277] The process implemented in Example 5 is a one-step process.

[0278] At the time of use, compositions P5 and N5 were mixed together in a 1:1 weight ratio. The resulting mixture was then applied to a wick of natural dry hair, 90% white, at a ratio of 1g of mixture per gram of strand. The strand was then left to rest for 5 minutes and finally dried with a hairdryer.

[0279] Residual effect of shampoos was evaluated according to the protocol described above. The process according to the invention is compared to the same process using composition D5 instead of the P5+N5 mixture.

[0280] The results of the measurements are shown in the table below:

[0281] [Tables9] Process Number of Shampoos L* a* b* AE Example 5 0 30.51 15.25 -13.32 6.79 5 34.62 11.69 -9.26 Comparative Process 5 0 42.23 8.11 -4.48 22.05 5 58.4 1.24 8.85

[0282] The violet colour obtained using the process according to the invention has a better residual colour at 5 shampoos than that obtained using the comparative process 5.

Claims

1. Demands A process for coloring keratin fibers using the following technique: (i) one or more compounds A chosen from among the compounds of formula (I), their optical isomers, their geometric isomers, their salts, their solvates such as hydrates, and their mixtures: Formula (I) in which: - R1 represents a versatile hydrocarbon radical in C2 to CM, linear or branched, saturated or unsaturated, conjugated or not, acyclic or cyclic, aromatic or not, R1 being further: a) possibly substituted by one or more hydroxy groups OH, dialkylamino-N(R)2 with R representing a (Ci-C4)alkyl group, carboxy-C(O)-OH, a vinyl group, and / or b) possibly interrupted by one or more heteroatoms or groups selected from O, S, carbonyl -C(O)-, amine -N(R'), or their combinations, in which R' represents a hydrogen atom, a linear or branched alkyl group having from 1 to 4 carbon atoms possibly substituted by at least one hydroxy group (OH) or possibly substituted by -XC(O)-C(Ra)(Rb)-C(O)-R2; - R2 represents a monovalent hydrocarbon radical in C1 to C6, linear or branched, saturated or unsaturated; - Ra, and Rb, identical or different, represent a hydrogen atom or a (Ci-C4)alkyl group; - X is a heteroatom or group chosen from O, S, N(R') or , -S-CH2-C(O)-O-, -OC(O)-CH2-S-, -OC(O)-N(R')-, -N(R')-C(O)-O-, -N(R')-C(O)-N(R')-, R' being as defined previously; - n denotes an integer ranging from 2 to 10, particularly from 3 to 9; and ii) one or more (poly)amine compounds; and iii) one or more direct dyes.

2. A method according to the preceding claim, wherein the compound(s) A are selected from the compounds of formula (la), their optical isomers, their geometric isomers, their salts, their solvates such as hydrates, and their mixtures: (there) | OO Formula (the) in which: - R1 is as defined in the preceding claim, particularly represents a versatile hydrocarbon radical in the range C2 to C14, preferably C3-Ci2, preferably C4-C10, linear or branched, saturated or unsaturated, conjugated or not, acyclic or cyclic, aromatic or not, R1 further being: a) possibly substituted by one or more hydroxyl groups OH, and / or b) optionally interrupted by one or more heteroatoms or groups selected from O, S, -N(R'), preferably interrupted by one or more oxygen atoms in which R' is as defined in the preceding claim; - R2 is as defined in the preceding claim, preferably R2 represents a (Ci-C6)alkyl group, linear or branched, preferably a (Ci-C4)alkyl group, more preferably methyl or tert-butyl such as methyl; and - n is as defined in the preceding claim, preferably n denotes an integer from 2 to 9.

3. A method according to any one of the preceding claims, wherein the compounds of formula (I) or (la) are such that: R1 represents a C6-C8 multipurpose hydrocarbon radical, linear or branched, unsaturated monocyclic or bicyclic, preferably monocyclic, possibly aromatic such as phenyl; or R1 represents a C5-C[2] multipurpose hydrocarbon radical, saturated monocyclic or bicyclic, possibly interrupted by one or more heteroatoms or groups selected from O, S, -N(R'), in which R' represents a hydrogen atom, an alkyl group having from 1 to 4 carbon atoms, preferably interrupted by a or several oxygen atony; preferably R1 represents a monosaccharide or polysaccharide motif, in particular a disaccharide on which n hydroxy groups have been substituted by n -OC(O)-CH2-C(O)-R2 groups with R2 and n as defined in any one of the preceding claims; or R1 represents a C2 to Ci2, preferably C3-C10, linear or branched, saturated or unsaturated, preferably saturated, acyclic hydrocarbon polyvalent radical.

4. A method according to any one of the preceding claims, wherein the compounds of formula (I) or (la) are such that n denotes an integer from 2 to 9, more particularly n denotes an integer from 3 to 9, even more particularly n denotes an integer from 4 to 9.

5. A method according to claim 1, wherein the compound(s) A are selected from the following compounds, their optical isomers, their salts, their solvates such as hydrates, and mixtures thereof: (Compound- Ndhvçhimsque- Structure chsrHtqcse w 700865-73-2 3-oxo-1.T-(1t7-heptanediyl) butanoic acid ester -C Ç (2) 632336-20-0 3-oxo-1.T-(Ç8-odànediyl) butanoic acid ester ;\x -X 13} 501426-98-8 3-oxo-1rT-(1ttO-decanediyl) butarsoic acid ester s , ..'''vA. s "s X . x (4} 174498-06-7 3-dxo-1.T-(1,3-propanedtyi} butanoic acid ■ ^x.. x : -■-'■^''x- (5) 160187-52-0 3-oxo-1 2 d:inethy• 1,2-ethanedsyl butanoic acid ester <■"' xy''" 145020-1S-5 3-oxo-2-buty1-2-ethy1-1,3-propanediyi butanoic acid ester X;' sJ (?) 87530-36-7 a-DXO-1 :.1.2:2-tetramethyi-1,2-ethanediyi butanoic acid ester- C 0 ::i \ O 0 (Compound) Chemical name Stroctorc- chemical (8| 58213-75-5 3-Dxa-lJ'-(1-r^ 1,3-propanediyl) butanoic acid ester Ç{ 0 < -yt G (S| 53213-74-4 3-oxo-l f 1'-|2r2-chmethyi-1-(1 -metbyliéthy 1)-1,3-propanediylO butanic acid ester \ (10) 39564-28-8 3-oxo-l ,1-(1,5-peotariedjyt) butanoic acid ester GG <> (11) 14276-67-6 3-oxo-l ,1-(2,2- dtmeth^-1 .3-propanediyl) acid ester butanoic 0 G 0 ''■-S. \ (12) 13Û18-41-2 3-oxo-l,4-butanediyl butanoic acid ester S (14) 5459-64-1 3-oxo-l,.2-êthaœdiyi butanoic acid ester §. s (Compound) NW sheets Structure .disc (16) 2388-18-3 a; r5 u- J qj & .a- c «3 « Ô * ; ® t- s (JJ fU 1 v -0 su i- .3? SX □ » .. Æ —- te cr 4" S « 7 x; s S | ■§ ® « w S % 8 $ % % 0J -' Tj pj Qj XJ c J ……… Ç ...... …." (16) 32818-80-3 bis{3-oxobutanoate) of 1,1--(2,2-8^((1,3-dsoxobrstoxyjmethyi]-1,3-propanediyl] 3 .-— 1 1 / ..... / .....' •'■ s"vx' <À* X0' ■ ■ / rt ....." * % (17) 51980-20-2 bs(3-oxophetanoate) de 1,1-(2,2- Bis(hydfoxyfnéthyî)“ 1,3-propanediy5 J / ...... g < y < i / * X (15) ......0 130973-05-6 3-oxo-1.3,5-benzenefcyi butapoic acid ester AÂ, 0 £> jf A - A....... (Compound-111110:11 Ndmçhimluei Chemical Structure ¢20) 139264--86-1 3-OXO-1.2,4-benzene butanoic acid ester ” ” ¢21} 22208-25-3 Triacetoacetate of trimethythiol propagates K-FLEX 7301 - V ' TT '........ ¢22) 2360524-48-5 V? 'V ¢23) 66229-33-2 3-oxo-2-buty1-2-[( 1,3-dsoxobutoxyjmethyl]-1,3-propanediyl ester of butanoic acid ¢24) 1579231-50- Y 4,4-dimethyl!-3-oxo-, 1,142,2-^3^4.4-dimethyl-1t3-dioxopentyÇoxÿlmeth yi}-1,3-propanediylI ester of pectanoic acid, \ ,À> S'""\ $ O <• \....... (Cwripose) Name Status: cbsmiqüe {25} 6079-98-7 {ns(3-oxQbutafioaieJ of 1, r,r-( 1,2,3-propanetriy!) oh {28} CT acetone of acetoa-5 , _p> Ÿ {27} 169533-29-3 sOG^copyranose, 1 ;2,3,4,6-penîakis(3-oxobulanoate) / ,.....{ l..... / \ ' / \_r'" / \....... J ■ art -5-5-271 22 [2.3,4-tns-O-{ 1,3-dioxobuty{)-0 -xyiopyranosyî Joxy]-d'ackte benzoic- (Compounded) N' CAS bfcæ chemique (29) 1236300-10- 2,3.4t6-tetrakis(3-oxobutacoste) de «-D- G1 ucopy rauoside, 1,3-4.6-teirakis-di-ox-pGbuD1,3 fructofuranosy}, .•À ! I l ' ' . . x*"' y. (30) 86481-26-4 D-Gktopyranose. peatakis(3-oxobutanoate) ç >% ' vX <x-' x- (31) 944473-12-5 D-^udtôl, 1,4:3.6- dianhydî’o-, 2.5-bis(3- oxobutanoate) <s.....i>(32} 2254710-49- X ^..X. . .J . V-''% (Compound) Chemical structure (33) sofbitol hexa-acetaacetate V' .■X. goo:' 'o î? tr" ''V"" v %> S 0 -... J ';Ç Ô {34) 21'6756-89-7 D-Gkidtd, 4-OgD-gai aetopyEanosy I-, poiyacetoacetate Ri / \ Z™" Z \ \ / \ / \ s si \ ch—»' / 7 \ ss sm with RI chosen from -C(O)-CHi-C(O)-CH3. H with at least two, RI radicals represent -Ç(O)-CHî-C(O)-CHî (35) 101655-52-1 Sucrose. polyacetoacetate 'HC « / %1 / 'V-« $ i R ■ - „ X ' 0 with Ri chosen from -C(O)-CH2-C(Ct)-CH3, H with at least two radicals R1 represent -C(O)-CH2-C(O)-CHs Eremic name Chemical structure (36) Glucose poSyacetoaceîate RI / s\„ \ ■ / S; p / ~ ' U'-Î {37} Mannose patyacetoacetaie PI y “s 'v7 / \ (38) Xy^stot pciyaceloacelate ^'x RI xx XX 1 Â '°" ï ï ::--pi preferably 6 radicals RI represent -qO^Hi-C / OÏ-CHs Chemical name / R1 0' - IX c" ri «X ' Xi So radicals RI represent -C(C'>CH2-C(O)-CHî? and three RI rafts represent a hydrogen atom {41} 1471-84-9 JL 1 JL - V - Y 1 0 OX" {42} 2552-36-5 K 1 8 X (43} 139614-56-5 X < ? OO Ç f X,.-' MH {44} 9616S-3Û-1 X <■ {45} 7563S-D1-S > ' 'Y y xv '" ï (Compound) ||)|^SâS|| Chemical structure: {46} Dipentaeryihrito! poiyacêtoacetate ' ' 'v XJ $ / .xss-.^xs-X'X''*'*,*'fc' / < <> / x preferably 5 or 6 R I radicals. more preferably 6 R I radicals represent -O(O)-CH2-C(O)-CHî in which identical or different RIs represent a hydrogen atom or a -C(O)-CH2-C(O)-CH3 group, it being understood that at least two RI radicals represent -C(O)-CH2-C(O)-CH3, preferably at least three RI radicals represent -C(O)-CH2-C(O)-CH3; preferably from compounds (16), (18), (21), (35), (36), (37), (38), (39), (40) and (46), their optical isomers, their salts, their solvates such as hydrates, and mixtures thereof; more preferably from compounds (16), (21), (35), (38), (39) and (46), their optical isomers, their salts, their solvates such as hydrates, and mixtures thereof; even more preferentially among compounds (16), (35) and (46), their optical isomers, their salts, their solvates such as hydrates, and their mixtures.

6. A method according to any one of the preceding claims, wherein the (poly)amine compound(s) are selected from: a) (poly)amine compounds having more than three primary and / or secondary amine groups, preferably primary (NH2), in particular chitosans such as poly(D-Glucosamine) and polylysine, b) diamine polyethers, in particular polyethylene glycol α, co-diamine, with an amine function at the chain end, c) triamine polyethers, such as Jeffamine T-403, d) aminoalkoxysilanes, in particular APTES, e) NH2-alk-NH2 polyamine compounds, in which alk denotes a C2-C20 hydrocarbon divalent chain, optionally substituted with a hydroxyl group (-OH) and / or optionally interrupted by one or more heteroatoms selected from -O-, -N(R)- with R designating a hydrogen atom or an alkyl radical in C1-C4, notably spermidine, 4,7,10-Trioxa-1,13-tri idecanediamine, the,3-Diamino-2-propan-l-ol and lysinol, f) polydialkylsiloxanes comprising primary amine groups at the end of the chain or on side chains, in particular polydimethylsiloxanes comprising primary amine groups, more particularly poly(dimethoxysiloxane) terminated by bis(3-aminopropyl) (PDMS-diNH2) and amodimethicones, comprising amine groups on side chains, more particularly bis-cetearyl amodimethicone; and mixtures thereof, preferably from a), c), e), and mixtures thereof; more preferably from polylysine, triamine polyethers, such as Jeffamine T-403, spermidine, l,3-diamino-2-prop an-l-ol, and mixtures thereof.

7. A method according to any one of the preceding claims, wherein the direct dye(s) are selected from cationic direct dyes, amphoteric direct dyes, nonionic direct dyes, and mixtures thereof, preferably selected from cationic direct dyes, more preferably selected from azo cationic direct dyes, hydrazono cationic direct dyes, anthraquinone cationic direct dyes, triarylmethane cationic direct dyes, and mixtures thereof, even more preferably selected from Basic Red 51, HC Blue 15, HC Blue 16, Disperse Violet 1, Basic Yellow 87, and mixtures thereof, and better selected from Basic Red 51, HC Blue 15, HC Blue 16, Disperse Violet 1, and mixtures thereof.

8. A method according to any one of the preceding claims, wherein the method comprises applying to keratin fibers a composition (A) comprising the direct dye(s) as defined in claim 1 or 7 and optionally the compound(s) A as defined in any one of claims 1 to 5 and then a composition (B) comprising the (poly)amine compound(s) as defined in claim 1 or 6 and optionally the compound(s) A as defined in any one of claims 1 to 5, it being understood that at least one of the compositions (A) or (B) comprises the compound(s) A as defined in any one of claims 1 to 5, preferably composition (B) comprises the compound(s) A as defined in any one of claims 1 to 5.

9. A method according to any one of claims 1 to 7, wherein the method comprises applying to keratin fibers a composition (C) comprising the compound(s) A as defined in any one of claims 1 to 5, the (poly)amine compound(s) as defined in claim 1 or 6 and the direct dye(s) as defined in claim 1 or 7.

10. A method according to any one of claims 1 to 7, wherein the method comprises applying the compound(s) A as defined in any one of claims 1 to 5 and the (poly)amine compound(s) as defined in claim 1 or 6 or a composition (B) comprising the compound(s) A as defined in any one of claims 1 to 5 and the (poly)amine compound(s) as defined in claim 1 or 6 to keratin fibers previously colored using the direct dye(s) as defined in claim 1 or 7 or a composition (A) comprising them.

11. A method according to any one of claims 1 to 7, wherein the method comprises applying to keratin fibers the direct dye(s) as defined in claim 1 or 7 or a composition (D) comprising the dye(s) and then the compound(s) A as defined in any one of claims 1 to 5 or a composition (A) comprising the dye(s) and then the (poly)amine compound(s) as defined in claim 1 or 6 or a composition (B) comprising the dye(s).

12. A method according to any one of claims 8 to 11, wherein the compound(s) A are present in the composition (A) or (B) or (C) in a total content of 0.2% to 80% by weight, preferably of 0.5% to 50% by weight, more preferably of 2% to 35% by weight, relative to the total weight of the composition comprising the compound(s).

13. A method according to any one of claims 8 to 12, wherein the (poly)amine compound(s) are present in composition (B) or (C) in a total content of 0.2% to 60% by weight, preferably of 0.5% to 40% by weight, more preferably of 5% to 40% by weight, relative to the total weight of the composition comprising them.

14. A process according to any one of claims 8 to 13, wherein the direct colorant(s) are present in composition (A) or (C) or (D) in a total content of 0.001% to 20% by weight, preferably of 0.005% to 15% by weight, more preferably of 0.01% to 10% by weight, even more preferably of 0.05% to 5% by weight, most preferably of 0.1% to 3% by weight, relative to the total weight of the composition comprising them.

15. Composition (C) as defined in any one of claims 9 or 12 to 14.

16. A device with two or three compartments comprising: - a first compartment containing a composition comprising one or more compounds A as defined in any one of claims 1 to 5 and optionally one or more direct dyes as defined in claim 1 or 7; - a second compartment, separate from the first compartment, containing a composition comprising one or more (poly)amine compounds as defined in claim 1 or 6 and optionally one or more direct dyes as defined in claim 1 or 7; - optionally a third compartment, separate from the first and second compartments, containing one or more direct dyes as defined in claim 1 or 7, it being understood that at least one of the compartments comprises one or more direct dyes as defined in claim 1 or 7.

17. Use of one or more compounds A as defined in any one of claims 1 to 5 associated with one or more (poly)amine compounds as defined in claim 1 or 6 or of a composition (B) comprising the compound(s) A as defined in any one of claims 1 to 5 and the (poly)amine compound(s) as defined in claim 1 or 6, to improve the shampoo retention of a direct dye of keratin fibers.