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 any problems of selectivity and / or possible color change, when several direct dyes are used, and even 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 and geometric isomers, their solvates such as hydrates, and their mixtures: (I) (H)p formula (I) in which: - Z represents a multivalent hydrocarbon radical in C2 to C40, in particular in C3 to C36, linear or branched, saturated or unsaturated, conjugated or not, acyclic or cyclic, aromatic or not, Z possibly being interrupted by one or more groups or heteroatoms chosen from -O-, -N(Ra)-, -S-, -C(O)-, (hetero)cycles, and their combinations; - AK1 represents a linear or branched divalent hydrocarbon chain saturated or unsaturated in C1-C12, preferably in CrC6, more preferably saturated in Ci-C6; - AK2 represents a linear or branched, saturated or unsaturated monovalent hydrocarbon chain of CrC4O, optionally substituted by one or more identical or different radicals chosen from -OR, -X-AK3-(OC(O)-C(Ra)(Rb)-C(O)-R4)v; and / or said chain optionally being interrupted by one or more heteroatoms or groups chosen from -O-, -S-, -C(O)-, (hetero)cycle(s), and their combinations, in particular -OC(O)-, -C(O)-O- and / or -(hetero)cycle-O-(hetero)cycle-; - AK3 represents a linear or branched divalent hydrocarbon chain saturated or unsaturated in C1-C12, preferably in CrC6, more preferentially saturated in Ci-C6, even more preferentially in C1-C4; - R represents a hydrogen atom, a linear or branched alkyl radical saturated or unsaturated in Ci-C6, preferably in CrC4, in particular methyl, or a -C(O)-C(Ra)(Rb)-C(O)-R4 radical; - X represents -O-, -S-, -OC(O)- or -C(O)-O-; - Y represents -OC(O)- or -C(O)-O-; - R4 represents a monovalent hydrocarbon radical in C1 to C6, linear or branched, saturated or unsaturated, preferably a (C1-C4)alkyl group, in particular methyl or tert-butyl, more preferably methyl; - Ra and Rb, whether identical or different, represent a hydrogen atom or a (Ci-C4)alkyl group, preferably a hydrogen atom; - p denotes an integer equal to 0 or 1; - m denotes an integer equal to 0, 1, 2, 3 or 4; it being understood that when m is greater than 1, then the radicals -Y-AK2 are identical or different; - n denotes an integer equal to 0, 1, 2, 3 or 4; it being understood that when n is greater than 1, then the radicals -(0)t-(AKi)q-(0-C(0)-C(Ra)(Rb)-C(0)-R4)u are identical or different; -1 denotes an integer equal to 0 or 1; - q denotes an integer equal to 0 or 1; - u denotes an integer equal to 1, 2 or 3; - v denotes an integer equal to 1, 2 or 3; it being understood that if q is equal to 0 then t is equal to 0, that (m + n) is greater than or equal to 1, and that the compounds of formula (I) contain at least two -C(O)-C(Ra)(Rb)-C(O)-R4 groups; 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 such as hair, body hair, eyelashes, eyebrows, wool, angora, cashmere or fur. According to the present invention, the keratin fibers are preferably human keratin fibers, more preferably hair;

[0015] ■ by "(hetero)aryl" means the aryl or heteroaryl groups.

[0016] ■ by "(hetero)cycloalkyl" means cycloalkyl or heterocycloalkyl groups.

[0017] ■ the “aryl” or “heteroaryl” radicals or the aryl or heteroaryl part of a radicals can be substituted by at least one substituent attached to a carbon atom, chosen from: - a (poly)(hydroxy)alkyl radical in CrC6, 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 Ci-C4 and the radical R' is an alkyl radical in C1-C4; a carbamoyl radical ((R)2N-C(O)-) in which the R radicals, 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, an alkyl radical in CrC4 and the radical R' represents an alkyl radical in CrC4, a phenyl radical; - an aminosulfonyl radical ((R)2N-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).

[0018] ■ the cyclic or heterocyclic part of a non-aromatic radical can be substituted by at least one substituent on 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 CrC2, 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 CrC 4, amino substituted by one or two identical or different alkyl groups in CrC 4; - alkoxycarbonyl ((ROC(O)-) in which the radical R is an alkyl radical in Ci-C4, amino substituted by one or two identical or different alkyl groups 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.

[0021] ■ 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.

[0022] ■ a "heteroaryl" radical represents a mono- or polycyclic group, condensed or non-condensed, comprising 5 to 14 bonds, 1 to 6 heteroatoms chosen from nitrogen, oxygen, sulfur and selenium atoms, and of which at least one The cycle 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.

[0023] ■ A "cyclic" or "cycloalkyl" radical is a non-cyclic hydrocarbon radical aromatic, mono- or polycyclic, condensed or non-condensed, containing from 5 to 14 carbon atoms, which may have from 1 to several unsaturations, preferably the cycloalkyl is a cyclohexyl group.

[0024] ■ 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.

[0025] ■ an "alkyl" radical is a saturated hydrocarbon radical, linear or branched, in particularly in Ci-C6, preferably in CrC4.

[0026] ■ an "alkoxy" radical is an alkyl-oxy radical for which the alkyl radical is a hydrocarbon radical, linear or branched, in Ci-C6 preferentially in CrC4.

[0027] ■ 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.

[0028] ■ 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) triflic acid CF3SO3H and x) tetrafluoroboric acid HBF4; xi) organic carboxylic 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 that 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 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 polycarboxylic acids are chosen from tartaric acid, succinic acid, fumaric acid, citric acid and mixtures thereof; and xii) amino acids having more carboxylic acid radicals than amino groups such as gamma-carboxyglutamic acid, aspartic acid, glutamic acid, 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, lysine, addition salts with possibly hydroxylated amines; .

[0029] ■ 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) alkoxysulfates: Alk-OS(O)2O such as methoxysulfate and ethoxysulfate; 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 with w being an integer; xiv) acetate; xv) triflate;xvi) borates such as tetrafluoroborate, xvii) disulfate (O=)2S(O-)2 or SO42 and xviii) monosulfate HSO4;

[0030] ■ the "solvates" represent the hydrates as well as the association with alcohols linear or branched CrC4 such as ethanol, isopropanol, n-propanol;

[0031] '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. that it absorbs wavelengths in the visible range, i.e. preferably between 400 and 800 nm. Preferably, 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);

[0032] ■ 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.

[0033] The expressions "at least one" and "one or more" are synonymous and can be used interchangeably.

[0034] 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

[0035] According to a first aspect, the present invention relates to a method for coloring keratin fibers as defined above.

[0036] The applicant has found, surprisingly, that the coloring process according to the present invention makes it possible to obtain a good rise in the color, intense and chromatic colors, improved persistence to shampoos, in particular to at least 5 or 10 shampoos and to limit the possible problems of selectivity and / or possible color change, when several direct dyes are used, and even to provide shine. Compounds A

[0037] The compound(s) A used in the coloring process according to the present invention are chosen from compounds of formula (I), their optical isomers, geometric isomers, their solvates such as hydrates, and their mixtures.

[0038] According to a preferred embodiment, the compound(s) A are chosen from compounds of formula (I), their optical and geometric isomers, their solvates such as hydrates, and their mixtures, such that Z denotes a radical chosen from: a) divalent radicals, preferably C2-C30, possibly interrupted by one or more heteroatoms or groups chosen from -O-, -N(Ra)-, -S-, -C(O)- and / or (hetero)cycle(s), in particular the radicals -CH2-(CH2)f, in which f denotes an integer between 1 and 10, preferably between 1 and 5, or such as the radicals -(CH2)g-(heterocycle)-O-(CH2)h-(heterocycle)-(CH2)j-, in which h denotes 0, 1 or 2, preferably 0 or 1, and g and j independently denote an integer between 1 and 3, preferably 1; b) trivalent radicals, preferably C3-C6, in particular CH2-CH-CH2-; and (c) tetravalent radicals, preferably in C3-Ci2, in particular -CH2-C-CH2-CH2-CH2-, or -CH2-C-CH2- or radicals -(CH2)a-CH-CH-(CH2)b-, in which a and b independently denote an integer equal to 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10, preferably a is greater than b.

[0039] According to a preferred embodiment, a (hetero)cycle designates a heterocyclic divalent radical (i.e. a heterocycle), preferably a heterocycloalkyl radical, more particularly a heterocycloalkyl divalent radical comprising 3, 5 or 6 links such as an epoxide divalent radical, a tetrahydrofuran divalent radical or a tetrahydropyran divalent radical, said (hetero)cycle being optionally substituted by one or more radicals chosen from -OR with R as defined above, and in particular -OH or -OC(O)-C(Ra)(Rb)-C(O)-R4).

[0040] According to a preferred embodiment, AK2 represents a linear or branched monovalent hydrocarbon chain, saturated or unsaturated, in Ci2-C28, optionally substituted by one or more identical or different radicals chosen from -OR, -X-AK3-(OC(O)-C(Ra)(Rb)-C(O)-R4)v, and / or said chain being optionally interrupted by -OC(O)- or -C(O)-O-.

[0041] According to a first preferred embodiment, the compound(s) A are chosen from compounds of formula (I), their optical and geometric isomers, their solvates such as hydrates, and their mixtures, such as: - Z represents the trivalent radical -CH2-CH-CH2-; - p is equal to 0; - n is equal to 0; - m is equal to 3; - AK2 represents a linear or branched monovalent hydrocarbon chain, saturated or unsaturated, in Ci2-C24 possibly substituted by one or more identical or different radicals chosen from -OR, -X-AK3-(OC(O)-C(Ra)(Rb)-C(O)-R4)v, and / or said chain possibly being interrupted by one or more heteroatoms or groups chosen from -O-, -S-, -C(O)-, epoxides, and their combinations, in particular -O(CO)- or -C(O)-O-; - Y, AK3, v, R, X, R4, Ra and Rb being such as defined previously for formula (i); it being understood that the compounds of formula (I) contain at least 2 radicals -C(O)-C(Ra)(Rb)-C(O)-R4.

[0042] According to a preferred embodiment, AK2 represents a linear or branched, saturated or unsaturated monovalent hydrocarbon chain, in the form Ci2-C24j, optionally substituted by one or more identical or different radicals selected from -OR, -X-AK3-(OC(O)-C(Ra)(Rb)-C(O)-R4)v, and / or said chain being optionally interrupted by one or more heteroatoms or groups chosen from -O-, -S-, -C(O)-, and their combinations, in particular -OC(O)- or -C(O)-O-.

[0043] According to this first preferred embodiment, the compound(s) A are preferably chosen from the following compounds (1), (2), (3), (4), (7), (8), (9), (11) and (16), their optical isomers, geometric isomers, their solvates such as hydrates, and their mixtures: (1) (11)

[0044] According to this first preferred embodiment, the compound(s) A are more preferably chosen from among the compounds (3), (16), their optical isomers, geometric isomers, their solvates such as hydrates, and their mixtures.

[0045] According to a second embodiment, the compound(s) A are chosen from compounds of formula (I), their optical and geometric isomers, their solvates such as hydrates, and their mixtures, such as: - p is equal to 0; - Z represents a multivalent hydrocarbon radical in C4 to C24, particularly in C6 to C2oplus particularly in CM to C20, in particular Cp, linear or branched, saturated or unsaturated preferably saturated, acyclic, Z being further possibly substituted by one or more radicals -[(O)t-(AKl)q- (OC(O)-C(Ra)(Rb)-C(O)-R4)u]n; - n denotes an integer equal to 0, 1, 2, 3 or 4; it being understood that when n is greater than 1, then the radicals -(0)t-(AKi)q-(0-C(0)-C(Ra)(Rb)-C(0)-R4)u are identical or different; preferably n is non-zero; - m is equal to 1; - AK2 represents a linear or branched monovalent hydrocarbon chain, saturated or unsaturated, preferably saturated, in C3-C8, in particular C4 or C6, substituted by one or more identical or different radicals chosen from -OR, -X-AK3-(OC(O)-C(Ra)(Rb)-C(O)-R4)v, preferably substituted by one or more -OR radicals; and / or said chain being optionally interrupted by one or more heteroatoms or groups chosen from -O-, -S-, -C(O)-, (hetero)cycle(s), and their combinations, in particular -OC(O)-, -C(O)-O-, -(hetero)cycle-O-(hetero)cycle-, and preferably being uninterrupted; - Y, AK1, AK3, t, q, u, v, R, X, R4, Ra and Rb being such as defined previously for formula (I);

[0046] it being understood that the compounds of formula (I) contain at least 2 radicals -C(O)-C(Ra)(Rb)-C(O)-R4. According to this second embodiment, the compound(s) A are preferably chosen from compounds (5) and (6) below, their optical and geometric isomers, their solvates such as hydrates, and their mixtures: (6).

[0047] According to a third embodiment, the compound(s) A are chosen from the compounds of formula (I), their optical and geometric isomers, their solvates such as hydrates, and their mixtures, such as: - p is equal to 0; - n + m is equal to 4, m being non-zero; - Z represents a tetravalent radical, hydrocarbon in C2 to C24, particularly in C3 to C10, especially C3, unsubstituted and uninterrupted, linear or branched, saturated or unsaturated, preferably saturated and acyclic; - AK2 independently represent a linear or branched monovalent hydrocarbon chain, saturated or unsaturated, preferably saturated, in Ci2-C24, preferably in Ci6-C20, in particular Ci8, optionally substituted by one or more identical or different radicals chosen from -OR and -X-AK3-(OC(O)-C(Ra)(Rb)-C(O)-R4)v, preferably substituted by one or more radicals -X-AK3-(OC(O)-C(Ra)(Rb)- C(O)-R4)v ; and / or said chain being possibly interrupted by one or more heteroatoms or groups chosen from -O-, -S-, -C(O)-, (hetero)cycle(s), and their combinations, in particular -OC(O)-, -C(O)-O-, -(hetero)cycle-O-(hetero)cycle-, and preferably being uninterrupted; - AK3 represents a linear or branched divalent hydrocarbon chain saturated or unsaturated in C1-C12, preferably in Ci-C6, more preferentially saturated in Ci-C6, even more preferentially in C2-C4, better in C3; - v is such as defined previously for formula (I); preferably v is equal to 2; - X is as defined previously for formula (I); preferably X denotes a sulfur atom; - Y, AK1, u, t, q, R, R4, Ra and Rb are as defined previously for formula (i); it being understood that the compounds of formula (I) contain at least 2 radicals -C(O)-C(Ra)(Rb)-C(O)-R4.

[0048] According to a preferred embodiment, m is equal to 3, n is equal to 1 and u is equal to 1.

[0049] According to a preferred embodiment, t is equal to 0.

[0050] According to a preferred embodiment, q is equal to 0.

[0051] According to a preferred embodiment, Y denotes -C(O)-O.

[0052] According to a preferred embodiment, none of the AK2 radicals are interrupted.

[0053] According to a preferred embodiment, the AK2 radicals are saturated.

[0054] According to a preferred embodiment, the AK2 radicals are not substituted by - GOLD.

[0055] According to a preferred embodiment, AK3 represents a linear or branched divalent hydrocarbon chain saturated or unsaturated in Ci-C6, more preferably saturated in Ci-C6, even more preferably saturated in C1-C4, better saturated in C3.

[0056] According to this third embodiment, the compound(s) A are in particular chosen from the compounds (10) below, their optical and geometric isomers, their solvates such as hydrates, and their mixtures:

[0057] According to a fourth embodiment, the compound(s) A are chosen from compounds of formula (I), their optical and geometric isomers, their solvates such as hydrates, and their mixtures, such as: - p is equal to 1; - Z represents a multivalent hydrocarbon radical in C2 to C24, particularly in C4 to C20, preferably in C5 or Cp, linear or branched, saturated or unsaturated, preferably saturated and acyclic; Z being further optionally substituted by one or more radicals -[(O)t-(AKl)q-(OC(O)-C(Ra)(Rb)-C(O)-R4)u]n, preferably being unsubstituted; - AK2 represents a linear or branched monovalent hydrocarbon chain, saturated or unsaturated, preferably saturated, in C8-C30, preferably in C10-C29, substituted by one or more identical or different radicals selected from -OR, -X-AK3-(OC(O)-C(Ra)(Rb)-C(O)-R4)v, preferably substituted by one or more -OR radicals; and / or said chain being optionally interrupted by one or more heteroatoms or groups selected from -O-, -S-, -C(O)-, (hetero)cycle(s), and their combinations, in particular -OC(O)-, -C(O)-O-, -(hetero)cycle-O-(hetero)cycle-, preferably being interrupted by -OC(O)- or -C(O)-O-; - X is as defined previously for formula (I), preferably X denotes a sulfur atom; - Y, AK1, AK3, n, m, v, t, q, u, R, R4, Ra and Rb being such as defined previously for formula (I); it being understood that the compounds of formula (I) contain at least 2 radicals C(O)-C(Ra)(Rb)-C(O)-R4.

[0058] According to a preferred embodiment, n is equal to 0 and m is equal to 1.

[0059] According to a preferred embodiment, Z is a divalent radical.

[0060] According to a preferred embodiment, if Z is an unsaturated chain, AK2 is a unsaturated chain, and if Z is a saturated chain, AK2 is a saturated chain.

[0061] According to this fourth embodiment, the compound(s) A are in particular chosen from the compounds of formula (lie), their optical and geometric isomers, their solvates such as hydrates, and their mixtures: HZY-AK4-Y'-ZH (lie) formula (lie) in which: - Y is such as defined previously for formula (I); - Z represents a divalent hydrocarbon radical in C2 to C24, in particular in C4 to C20, preferably in C5 or Cp, linear or branched, saturated or unsaturated, preferably saturated; - Y' represents -C(O)-O- or -OC(O)- it being understood that if Y represents -OC(O)-, Y' represents -C(O)-O-, and if Y represents -C(O)-O-, Y' represents -OC(O)-; - AK4 designates a saturated divalent hydrocarbon radical of 5 or 6 carbon atoms, substituted by at least two -OR radicals with R being as defined previously in formula (I); it being understood that the compounds of formula (lie) contain at least 2 radicals -C(O)-C(Ra)(Rb)-C(O)-R4, and preferably 4 radicals -C(O)-C(Ra)(Rb)-C(O)-R4.

[0062] According to this fourth embodiment, the compound(s) A are in particular chosen from compounds (12) and (15) below, their optical and geometric isomers, their solvates such as hydrates, and their mixtures: (12)

[0063] According to a fifth embodiment, the compound(s) A are chosen from compounds of formula (I), their optical and geometric isomers, their solvates such as hydrates, and their mixtures, such as: - p is equal to 0; - Z represents a tetravalent hydrocarbon radical in C2 to C24, in particular in C3 to C10, preferably in C4 or C5, linear or branched, saturated or unsaturated, preferably saturated and acyclic, Z being further substituted by one or more radicals —[(O)t-(AKl)q-(OC(O)-C(Ra)(Rb)-C(O)-R4)u]n, preferably n being equal to 1; - n + m equals 4, preferably m equals 3; - AK2 independently represents a linear or branched hydrocarbon chain, saturated or unsaturated, preferably saturated, in CM to C30, preferably from Ci6 to C24, preferably in Cp, said chain being optionally substituted by one or more identical or different radicals chosen from -OR, -X-AK3-(OC(O)-C(Ra)(Rb)-C(O)-R4)v, preferably substituted by one or more -OR radicals; and / or said chain being optionally interrupted by one or more heteroatoms or groups chosen from -O-, -S-, -C(O)-, (hetero)cycle(s), and their combinations, in particular -OC(O)- or -C(O)-O-, -(hetero)cycle-O-(hetero)cycle-, preferably being uninterrupted; - X is as defined previously for formula (I), and preferably X denotes a sulfur atom; - Y, AK1, AK3, u, t, q, v, n, m R, R4, Ra and Rb being such as defined previously for formula (I); it being understood that the compounds of formula (I) contain at least 2 radicals C(O)-C(Ra)(Rb)-C(O)-R4.

[0064] According to a preferred embodiment, t is equal to 0 and u is equal to 1.

[0065] According to a preferred embodiment, all AK2 radicals are identical, and Preference is given that all Y radicals are identical.

[0066] According to a preferred embodiment, Y denotes -OC(O)-.

[0067] According to a particular embodiment, the compounds according to this fifth variant are in particular chosen from the compounds of formula (lid), their optical and geometric isomers, their solvates such as hydrates, and their mixtures: [AK'2-OCO-CH2]3-C-CH2-OC(O)-C(Ra)(Rb)-C(O)-R4 (lid) formula (lid) in which: - AK'2 represents a linear or branched monovalent hydrocarbon chain, preferably linear, saturated or unsaturated, preferably saturated, in C14-C30, preferably in C16-C24, preferably in Cp, said chain being substituted by one or several identical or different radicals chosen from -OR, -S-AK3-(OC(O)-C(Ra) (Rb)-C(O)-R4)v, preferably substituted by one or more -OR radicals; - AK3, v, R, R4, Ra and Rb being such as defined previously for formula (I); it being understood that the said compounds contain at least 2 C(O)-C(Ra)(Rb)-C(O)-R4 radicals.

[0068] According to a sixth embodiment, the compound(s) A are chosen from compounds of formula (I), their optical and geometric isomers, their solvates such as hydrates, and their mixtures, such as: - p is equal to 0; - m is non-zero; - Z represents a divalent hydrocarbon radical in C2 to C24, in particular in C3 to C[2 , linear or branched, saturated or unsaturated, conjugated or not, preferably not conjugated, acyclic or cyclic, aromatic or not, preferably not aromatic, said radical Z being further interrupted by one or more heteroatoms or groups chosen from -O-, -N(Ra)-, -S-, -C(O)-, heterocycloalkyl(s) comprising 5 or 6 links, and their combinations; - AK2 represents a linear or branched monovalent hydrocarbon chain, saturated or unsaturated, preferably saturated, in Ci4-C30, preferably in C[4-C24, preferably in C15, said chain being optionally substituted by one or more identical or different radicals chosen from -OR and -X-AK3-(OC(O)-C(Ra)(Rb)-C(O)-R4)v, preferably unsubstituted; and / or said chain being optionally interrupted by one or more heteroatoms or groups chosen from -O-, -S-, -C(O)-, (hetero)cycles, and their combinations, in particular -OC(O)-, -C(O)-O- or -(hetero)cycle-O-(hetero)cycle-, preferably possibly interrupted by -OC(O)- or -C(O)-O-, and more preferably being uninterrupted; - X is as defined previously for formula (I), and preferably X denotes a sulfur atom; - Y, AK1, AK3, v, t, q, u, R, R4, Ra and Rb being such as defined previously for formula (I), it being understood that the compounds of formula (I) contain at least 2 C(O)-C(Ra)(Rb)-C(O)-R4 radicals.

[0069] According to a preferred embodiment, in this variant, Z denotes a divalent radical -(CH2)g-(heterocycle)-O-(CH2)h-(heterocycle)-(CH2)j- in which h is equal to 0, 1, or 2, preferably is equal to 0 or 1, g and j independently denote an integer between 1 and 3, preferably 1, (heterocycle) denotes a heterocycloalkyl divalent radical having 5 or 6 members, in particular a divalent radical of tetrahydrofuran or a divalent radical of tetrahydropyran, said heterocycle being possibly substituted by one or more radicals chosen from -OR, with R as defined previously for formula (I), and in particular -OH or -OC(O)-C(Ra)(Rb )-C(O)-R4).

[0070] According to this sixth embodiment, the compound(s) A are in particular chosen from the compounds of formula (link), their optical and geometric isomers, their solvates such as hydrates, and their mixtures: AK”2-C(O)-O-(CH2)g-(heterocycle)-O-(CH2)h-(heterocycle)-(CH2)jO-CO-AK”2(Iie) formula (link) in which: - h is equal to 0, 1 or 2, preferably is equal to 0 or 1; - g and j independently denote an integer between 1 and 3, preferably 1; - (heterocycle) designates a heterocycloalkyl divalent radical comprising 5 or 6 substituted links by one or more identical or different radicals chosen from -OR, with R as defined previously for formula (I), and in particular -OH or -OC(O)-C(Ra)(Rb)-C(O)-R4); - AK” 2 represents a linear or branched monovalent hydrocarbon chain, saturated or unsaturated, preferably saturated, in Ci4-C30, preferably in Ci4-C24, preferably in Ci5, said chain being optionally substituted by one or more identical or different radicals selected from -OH, -OC(O)-C(Ra)(Rb)-C(O)-R 4) and -S-AK3-(OC(O)-C(Ra)(Rb)-C(O)-R4)v, preferably unsubstituted; and / or said chain being optionally interrupted by one or more heteroatoms or groups selected from -O-, -S-, -C(O)-, (hetero)cycle(s), and their combinations, in particular -OC(O)-, -C(O)-O- or -(hetero)cycle-O-(hetero)cycle-, preferably optionally interrupted by -OC(O)- or -C(O)-O-, and more preferably being uninterrupted; it being understood that the compounds of formula (lie) contain at least 2 radicals -C(O)-C(Ra)(Rb)-C(O)-R4.

[0071] According to this sixth embodiment, the compound(s) A are in particular chosen from the compounds (14) below, their optical and geometric isomers, their solvates such as hydrates, and their mixtures: (14) with W being a hydrogen atony or -C(O)-C(Ra)(Rb)-C(O)-R4, and said compound containing at least two -C(O)-C(Ra)(Rb)-C(O)-R4 groups.

[0072] Preferably, the compound(s) A are chosen from the compounds of formula (la), their optical isomers, geometric isomers, their solvates such as hydrates, and their mixtures: Z-(Y-AK2)3 (la) formula (the) in which: - Z represents -CH2-CH-CH2- ; - AK2 independently designates a linear or branched monovalent hydrocarbon chain, saturated or unsaturated, in Ci2-C24, possibly substituted by one or more identical or different radicals chosen from -OR and -X-AK3-(OC(O)-C(Ra)(Rb)-C(O)-R4)v; and / or said chain being possibly interrupted by one or more heteroatoms or groups chosen from -O-, -S-, -C(O)-, epoxides, and their combinations, in particular -OC(O)- and -C(O)-O-; - Y, AK3, v, R, X, R4, Ra and Rb being such as defined previously for formula (I), preferably Y denotes -OC(O); it being understood that the compounds of formula (la) contain at least 2 radicals C(O)-C(Ra)(Rb)-C(O)-R4.

[0073] Preferably, the compound(s) A are chosen from compounds of formula (Ib), their optical and geometric isomers, their solvates such as hydrates, and mixtures thereof: m(AK2 -Y) - Z - [(O)t-(AKl)q-(OC(O)-C(Ra)(Rb)-C(O)-R4)u]n (Ib) formula (Ib) in which: - n + m is equal to 4, m being non-zero; m and n being such as defined previously for formula (I); - Z represents a tetravalent hydrocarbon radical in C2 to C24, in particular in C3 to C10, preferably in C3, unsubstituted and uninterrupted, linear or branched, saturated or unsaturated, preferably saturated and acyclic; - AK2 independently represent a linear or branched monovalent hydrocarbon chain, saturated or unsaturated, preferably saturated, in Ci2-C24, preferably in Ci6-C20, preferably in Ci8, optionally substituted by one or more identical or different radicals chosen from -OR, -X-AK3-(OC(O)-C(Ra)(Rb)-C(O)-R4)v, preferably substituted by one or more radicals -X-AK3-(O-C(O)-C(Ra)(Rb)-C(O)-R4)v; and / or said chain being optionally interrupted by one or more heteroatoms or groups chosen from -O-, -S-, -C(O)-, (hetero)cycle(s), and their combinations, in particular -OC(O)-, -C(O)-O- or -(hetero)cycle-O-(hetero)cycle-, preferably being uninterrupted; - AK3 represents a linear or branched divalent hydrocarbon chain saturated or unsaturated in CrCi2, preferably in CrC6, more preferentially saturated in Ci-C6, even more preferentially in C2-C4, preferably in C3; - v is such as defined previously for formula (I), preferably v is equal to 2; - X is such as defined previously for formula (I), preferably X denotes a sulfur atom; - Y, AK1, t, q, u, R, R4, Ra and Rb being such as defined previously for formula (i); it being understood that the compounds of formula (Ib) contain at least 2 radicals -C(O)-C(Ra)(Rb)-C(O)-R4.

[0074] Preferably, the compound(s) A are chosen from compounds of formula (the), their optical and geometric isomers, their solvates such as hydrates, and mixtures thereof: m(AK2 -Y) - ZH - [(O)t-(AKl)q-(OC(O)-C(Ra)(Rb)-C(O)-R4)u]n (the) formula (the) in which: - Z represents a multivalent hydrocarbon radical in CM to C24, particularly in Ci6 to C20 such as Cp, linear or branched, saturated or unsaturated, preferably saturated and acyclic, Z being further possibly substituted by one or more radicals -[(O) t-(AKl)q-(O-C(O)-C(Ra)(Rb)-C(O)-R4)u]n, preferably unsubstituted; - AK2 represents a linear or branched monovalent hydrocarbon chain, saturated or unsaturated, preferably saturated, in Ci4-C30, preferably in C2o-C29, substituted by one or more identical or different radicals chosen from -OR and -X-AK3-(OC(O)-C(Ra)(Rb)-C(O)-R4)v, preferably substituted by one or more -OR radicals; and / or said chain being optionally interrupted by one or more heteroatoms or groups chosen from -O-, -S-, -C(O)-, (hetero)cycle(s), and their combinations, in particular -OC(O)-, -C(O)-O- or (hetero)cycle-O-(hetero)cycle, preferably interrupted by -OC(O)- or -C(O)-O-; - X is as defined previously for formula (I), and preferably X denotes a sulfur atom; - Y, AK1, AK3, n, m, v, t, q, u, R, R4, Ra and Rb being such as defined previously for formula (I); it being understood that the compounds of formula (le) contain at least 2 radicals -C(O)-C(Ra)(Rb)-C(O)-R4.

[0075] Preferably, the compound(s) A are chosen from compounds of formula (Id), their optical and geometric isomers, their solvates such as hydrates, and mixtures thereof: m(AK2 -Y) - Z - [(O)t-(AKl)q-(OC(O)-C(Ra)(Rb)-C(O)-R4)u]n (Id) formula (Id) in which: - n + m equals 4, preferably m equals 3; - Z represents a tetravalent hydrocarbon radical in C2 to C24, in particular in C3 to Cio, in particular in C4 or C5, linear or branched, saturated or unsaturated, preferably saturated or acyclic, Z being further substituted by one or more radicals -[(O)t-(AKl)q-(OC(O)-C(Ra)(Rb)-C(O)-R4)u]n, preferably n is equal to 1; - AK2 independently represents a linear or branched monovalent hydrocarbon chain, saturated or unsaturated, preferably saturated, in Ci4-C30, preferably in Ci6-C24, preferably in Cp, said chain being optionally substituted by one or more identical or different radicals chosen from -OR or -X-AK3-(OC(O)-C(Ra)(Rb)-C(O)-R4)v, preferably substituted by one or more -OR radicals; and / or said chain being optionally interrupted by one or more heteroatoms or groups chosen from -O-, -S-, -C(O)-, (hetero)cycle(s), and their combinations, in particular -OC(O)-, -C(O)-O- or (hetero)cycle-O-(hetero)cycle, preferably being uninterrupted; X is as defined previously for formula (I), preferably X designates a sulfur atom; Y, AK1, AK3, v, R, IC, Ra and Rb being as defined previously for formula (I), it being understood that the compounds of formula (Id) contain at least 2 radicals -C(O)-C(Ra)(Rb)-C(O)-R4.

[0076] Preferably, the compound(s) A are chosen from compounds of formula (the), their optical and geometric isomers, their solvates such as hydrates, and mixtures thereof: m(AK2-Y) - Z - [(O)t-(AKl)q-(OC(O)-C(Ra)(Rb)-C(O)-R4)u]n (the) formula (the) in which: - n + m is equal to 2, m being non-zero, preferably m being equal to 2; n is such as defined previously for formula (I), preferably n is zero; - Z represents a divalent hydrocarbon radical in C2 to C24, in particular in C3 to C12, linear or branched, saturated or unsaturated, conjugated or not, preferably not conjugated, acyclic or cyclic, aromatic or not, preferably not aromatic, said radical Z being further interrupted by one or more heteroatoms or groups selected from -O-, -N(Ra)-, -S-, -C(O)-, (hetero)cycle(s), and their combinations; preferably Z denotes a divalent radical -(CH2)g-(heterocycle)-O-(CH2)h-(heterocycle)-(CH2)j- in which h denotes 0, 1 or 2, preferably 0 or 1, g and j independently denote an integer between 1 and 3, preferably 1; (heterocycle) denotes a heterocyclic divalent radical (ia heterocycle), preferably a heterocycloalkyl radical, more particularly a divalent heterocycloalkyl radical comprising 5 or 6 links, in particular a divalent tetrahydrofuran radical or a divalent tetrahydropyran radical, said heterocycle being optionally substituted by one or more radicals chosen from -OR with R as defined previously for formula (I), and in particular -OH or -OC(O)-C(Ra)(Rb )-C(O)-R4); . - AK2 represents a linear or branched monovalent hydrocarbon chain, saturated or unsaturated, preferably saturated, in Ci4-C30, preferably Ci4-C24, preferably in Cp, said chain being optionally substituted by one or more identical or different radicals chosen from -OR and -X-AK3-(OC(O)-C(Ra)(Rb j-QOj-ROv, preferably unsubstituted; and / or said chain being optionally interrupted by one or more heteroatoms or groups chosen from -O-, -S-, -C(O)-, (hetero)cycle(s), and their combinations, in particular -OC(O)-, -C(O)-O- or -(hetero)cycle-O-(hetero)cycle-, preferably possibly interrupted by -OC(O)- or -C(O)-O-, and more preferably uninterrupted; - X is as defined previously for formula (I), preferably X denotes a sulfur atom; - Y, AK1, AK3, v, t, q, u, R, R4, Ra and Rb being such as defined previously for formula (I); it being understood that the compounds of formula (le) contain at least 2 radicals C(O)-C(Ra)(Rb)-C(O)-R4.

[0077] According to a preferred embodiment, the compound(s) A are selected from the following compounds (1) to (16), their optical and geometric isomers, their solvates such as hydrates, and their mixtures: (5) (16) with W being a hydrogen atony or -C(O)-C(Ra)(Rb)-C(O)-R4, and said compound containing at least two -C(O)-C(Ra)(Rb)-C(O)-R4 groups. Preparation of compounds of formula (I)

[0078] In particular, the compound(s) of formula (I), or (la), (Ib), (le), (Id), (le), (lie), (lid) or (lie), can be prepared by the following sequence of reactions: First step

[0079] In a first step, a commercial polyol, preferably natural, of formula (H)pZ(OH)m- is reacted with m equivalents of fatty derivatives R'CO-AK'2 with m' greater than or equal to m, and m being as defined above, under conditions known to the person skilled in the art to form an ester bond Y according to the scheme below: (H)pZ(OH)m+mR'CO-AK'2 -> (H)pZ(OH)m,m(YAK'2)m diagram in which: - Y represents -OC(O)- ; - R' designating in particular -OH or -Cl; preferably R' designates -OH; - AK'2 represents a linear or branched, unsaturated CrC 40 hydrocarbon chain, preferably C14-C20, said chain being optionally interrupted by one or more heteroatoms or groups selected from -O-, -S-, -C(O)-, (hetero)cycle(s), and their combinations, in particular -OC(O)-, -C(O)-O- or -(hetero)cycle-O-(hetero)cycle-, preferably interrupted by -O- or -S-, more preferably being uninterrupted.

[0080] According to a preferred embodiment, m is equal to m'.

[0081] Polyols (H)pZ(OH)m can be cyclic or acyclic.

[0082] Examples of cyclic (H)pZ(OH)m polyols include maltose, lactose, raffinose, sucrose, trehalose, melibiulose, melibiose, mannobiose, kojibiose, nigerose, isomaltose, rutinose, rutinulose, xylobiose or sorbitan.

[0083] Examples of (H)pZ(OH)macyclic polyols include ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, butanediol, glycerol, pentaerythritol, dipentaerythritol, trimethylolethan, mannitol, or trimethylolpropane.

[0084] According to a preferred embodiment, the polyol (H)pZ(OH)m is chosen from glycerol, mannitol, sucrose, ethylene glycol, sorbitan, or trimethylolpropane, more preferably the polyol (H)pZ(OH)m designates glycerol.

[0085] The R'CO-AK'2 compounds are preferably unsaturated fatty acids of 15 to 36 carbon atoms, preferably of 15 to 24 carbon atoms. They may be monounsaturated or polyunsaturated.

[0086] Monounsaturated fatty acids are in particular selected from palmitoleic acid, oleic acid, 9-eicosenoic acid, 11-eicosenoic acid, erucic acid and nervonic acid.

[0087] Polyunsaturated fatty acids are selected in particular from linoleic acid, α-linolenic acid, γ-linolenic acid, dihomo-γ-linolenic acid, arachidonic acid, eicosapentaenoic acid, docosahexaenoic acid, ruminic acid; monounsaturated hydroxy fatty acids selected in particular from 10-Hydroxy-cis-12-octadecenoic acid, 10-Hydroxy-trans-11-octadecenoic acid, 12-Hydroxy-cis-9-octadecenoic acid, 13-Hydroxy-cis-9-octadecenoic acid, ricinoleic acid, isoricinoleic acid; and polyunsaturated hydroxy fatty acids selected in particular from densipolic acid. auricolic acid, dimorphecolic acid.

[0088] More preferably, the unsaturated fatty acid is chosen from ricinoleic acid, oleic acid, palmitoleic acid, erucic acid and mixtures thereof. Second stage

[0089] In a second step, all or part of the unsaturation(s) of the AK'2 radical(s) are transformed a) via an epoxidation reaction into epoxide to lead to derivatives (III), such as the starting compound al illustrated in the diagram described below, or b) via a thiol-ene reaction with a (poly)hydroxylated thiol or a thiol bearing acid function(s) to lead to derivatives (IV), such as, for example, compound b3 illustrated in the diagram described after.

[0090] The thiol-ene reaction b) can be carried out from (poly)hydroxylated thiols such as linear hydroxylated thiols of formula HS-(CH2)k-OH with k being an integer from 1 to 12, preferably from 1 to 6, such as 2-mercaptoethanol, 3-mercapto-1-propanol, 6-mercapto-1-hexanol, 4-mercapto-1-butanol, or such as branched hydroxylated thiols having preferably from 1 to 6 carbon atoms, such as 3-mercapto-3-methylbutanol, 3-mercapto-2-butanol, or such as thiols polyhydroxylated, preferably comprising 1 to 6 carbon atoms such as 3-mercapto-1,2 propanediol HS-CH(OH)-CH2OH.

[0091] The compounds (IV) obtained are thus substituted by a radical -S-AK3-(OH)V with v being equal to 1 if the thiol is hydroxylated and v being greater than 1, such as 2, if the thiol is polyhydroxylated, AK3 and v being such as defined previously for the compounds of formula (I). Third stage

[0092] In a third step, all or part of the epoxide groups of the compounds of formula (III) are opened by nucleophilic compounds, in particular i) alcohols preferably in Ci-C4 such as methanol or ethanol, or a polyol to lead to compounds (Illi), such as compound b2 illustrated in the diagram below, ii) carboxylic acids, preferably in Ci-C6, such as lactic acid, pyruvic acid, benzoic acid, glycolic acid or 2,2 bishydroxymethylpropionic acid, more preferably carboxylic acids substituted by at least one hydroxyl radical such as lactic acid, to lead to compounds (Illii), such as compound bl illustrated in the diagram below.

[0093] According to a preferred embodiment, the carboxylic acid ii) is chosen from lactic acid, glycolic acid or 2,2 bis hydroxymethyl propionic acid (epoxy-acid reaction) and the reaction is carried out in the presence of a catalyst such as imidazole, 1-Methylimidazole, N,N dimethylbenzylamine or caffeine.

[0094] According to a preferred embodiment, the alcohol i) is selected from ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, butandiol, glycerol, pentaerythritol, dipentaerythritol, trimethylolethane, trimethylolpropane, more preferably butylene glycol or trimethylolethane. Fourth step

[0095] In a fourth step, all or part of the alcohol -OH functions of the compounds (Illi) or (Illii) and all or part of the alcohol functions possibly still present from the polyols (H)pZ(OH)m' used in the first step are transformed into -0-C(0)-C(Ra)(Rb)-C(0)-R4 radicals, for example via a (trans)esterification reaction with a Gp-C(0)-C(Ra)(Rb)-C(0)-R4 ester, in which Gp preferably designates a hydroxy radical or a (Ci-C4)alkoxy radical, such as methoxy, ethoxy, isobutoxy or t-butoxy.

[0096] According to a preferred embodiment, Gp-C(0)-C(Ra)(Rb)-C(0)-R4 designates an ester selected from ethyl acetoacetate, ethyl 2-methylacetoacetate, ter-butyl acetoacetate, preferably ter-butyl acetoacetate.

[0097] The structural compounds (la), (le), such as the structural compounds (lie), the structural compounds (Id) and (le) can be obtained according to this process.

[0098] By way of example, step 4 can be implemented according to the protocol described in Trevino, AS, & Trumbo, DL (2002). Acetoacetylated castor oil in coatings applications. Progress in Organic Coatings, 44(1), 49-54:

[0099] In some cases, the compounds (H)pZ(OH)mm (YAK'2) produced in the first step are commercially available, in particular certain compounds for which m' equals m, p equals 0, and Z preferably denoting -CH2-CH-CH2-, are commercially available. When p equals 0 and m' equals m, the compounds are esters of unsaturated fatty acids, possibly hydroxylated, in particular triglycerides of castor oil, soybean oil, canola oil, or linseed oil. The synthesis of compounds (la) to (le) then begins from the second step described above.

[0100] For example, starting from an unsaturated triglyceride, a thiol-ene reaction is carried out with a (poly)hydroxy thiol such as SH-(CH2)X OH with x being an integer preferably from 1 to 4, followed by a transesterification reaction (as described in Desroches, M., Caillol, S., Lapinte, V., Auvergne, R., & Boutevin, B. (2011). Synthesis of biobased polyols by thiol-ene coupling from vegetable oils. Macromolecules, 44(8), 2489-2500): Composed of 3 Compound b3

[0101] For example, starting from an unsaturated triglyceride, a total or partial epoxidation reaction is carried out, followed by the opening of the epoxide(s) formed, which generates alcohol functionalities and (trans)esterification. A commercial epoxidized triglyceride, such as the products offered by Arkema under the references Vikoflex 7170 or Vikoflex 7190, can also be used as a raw material.

[0102] By way of example, the reaction scheme below can be implemented in which all the epoxides are opened by lactic acid and then each hydroxyl group is esterified by t-Bu-OCOCH2CH3, according to the scheme below: has) Composed al Composed bi b) Compound b! Compound C1

[0103] As an example, the reaction scheme below can also be implemented in which all the epoxides are opened by an alcohol, methanol in the example, then each hydroxyl group is esterified by t-Bu-OCOCH2CH3: has) Compound a2 Compound 62 b) Compound b2 Coaxed c2

[0104] The compounds of formula (la) to (le) can further be prepared by the following series of reactions:

[0105] - In a first step, a commercial polyacid is reacted preferably natural (H)pZ(COOH)m with m equivalents of fatty alcohol HO-AK'2 with m' greater than or equal to m, and m being as defined previously, under conditions known to those skilled in the art to form an ester bond Y according to the scheme below: (H)pZ(COOH)m+mH0-AK'2 -> (H)pZ(COOH)m_m(YAK'2)m in which Y denotes -C(O)-O-, and AK'2 represents a linear or branched, unsaturated monovalent hydrocarbon chain, in Ci-C40, preferably in Ci4-C2o, said chain being optionally interrupted by one or more heteroatoms or groups chosen from -O-, -S-, -C(O)-, (hetero)cycle(s), and their combinations, in particular -OC(O)-, -C(O)-O-, -(hetero)cycle-O-(hetero)cycle-, preferably interrupted by -O- or -S-, and more preferably uninterrupted.

[0106] According to a preferred embodiment, m is equal to m'.

[0107] Polyacids (H)pZ(OH)m can be cyclic or acyclic.

[0108] Polyacids may preferably designate dicarboxylic acids possibly hydroxylated, tricarboxylic acids possibly hydroxylated, tetraboxylic acids possibly hydroxylated.

[0109] Non-hydroxylated dicarboxylic acids are selected in particular from maleic acid, propanedioic acid, butanedioic acid, pentanedioic acid, hexanedioic acid, decanedioic acid, dodecanedioic acid, cyclopropanedicarboxylic acid, cyclohexanedicarboxylic acid, cyclobutanedicarboxylic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-2,3-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, suberic acid, oxalic acid, malonic acid, succinic acid, phthalic acid, terephthalic acid, isophthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pimelic acid, sebacic acid, azelaic acid, acid glutaric acid, adipic acid, fumaric acid, itaconic acid, and preferably propanedioic acid, butanedioic acid and pentanedioic acid.

[0110] Hydroxylated dicarboxylic acids are in particular selected from tartaric acid, malic acid, aleuritic acid, 7,18-dihydroxy-tetracos-15-enoic acid, avenic acid B, and preferably malic acid and tartaric acid.

[0111] The (hydroxy) tricarboxylic acids are in particular selected from 2-oxaloglutaric acid, oxalosuccinic acid, 3-carboxymethyl muconic acid, 2-methyl citric acid, citric acid, isocitric acid, aconitic acid, transaconitic acid, 1,2,3-propanetricarboxylic acid, 1,2,5-pentanetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, 1,3,5-cyclohexanetricarboxylic acid, 3-butene-1,2,3-tricarboxylic acid, 3-butene-1,1,3-tricarboxylic acid, trimellitic acid, 1,2,3-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, agaric acid, preferably citric acid and acotinic acid.

[0112] Tetracarboxylic acids are in particular selected from 1,2,3,4-butanetetracarboxylic acid, pyromellitic acid, oxydisuccinic acid, thiodisuccinic acid, N[l,2-dicarboxyethyl]-L-aspartic acid, ethylenediamine tetraacetic acid, ethylenediamine tetrapropionic acid and N,N'-ethylene di-(L-aspartic acid).

[0113] According to a preferred embodiment, the fatty alcohols HO-AK'2 are selected from fatty alcohols comprising 15 to 36 carbon atoms, preferably 15 to 24 carbon atoms.

[0114] Fatty alcohols HO-AK'2 can be mono or polyunsaturated (presence of one or more ethylenic double bonds).

[0115] HO-AK'2 fatty alcohols may contain several alcohol functions.

[0116] Monounsaturated fatty alcohols are particularly chosen, oleyl alcohol, the Docosenol, unsaturated fatty alcohol ethers, such as polyoxyethylene monooleyl ether, preferably oleyl alcohol. Monounsaturated fatty alcohols containing multiple alcohol groups are particularly selected from 9-Octadecene-1,12-diol.

[0117] Polyunsaturated fatty alcohols are in particular selected from linoleic alcohol, 2,4-Dodecadien-l-ol, dolichols (with n being greater than or equal to 3, and less than or equal to 5).

[0118] According to a preferred embodiment, the fatty alcohol HO-AK'2 is selected from oleyl alcohol, linoleic alcohol (Linoleyl alcohol) or mixtures thereof.

[0119] The following steps are identical to those described previously:

[0120] - In a second step, all or part of the unsaturation(s) of the radical(s) AK'2 are transformed a) via an epoxidation reaction to epoxide to lead to (III') derivatives, such as compound a4 illustrated in the scheme below, or b) via a thiol-ene reaction with a (poly)hydroxylated thiol or a thiol bearing acid function(s) to lead to derivatives (IV'), such as compound b5 illustrated in the diagram below.

[0121] - In a third step, all or part of the epoxide groups of the compounds of formula (III') are opened by nucleophilic compounds, such as i) alcohols preferably in C1-C4 such as methanol or ethanol or a polyol to lead to compounds (III'i), such as compound b4 illustrated in the diagram below, ii) carboxylic acids preferably in Ci-C6 such as lactic acid, pyruvic acid, benzoic acid, more preferably carboxylic acids substituted by at least one hydroxyl radical such as lactic acid, to lead to compounds (III'ii), such as compound b6 illustrated in the diagram below.

[0122] - In a fourth step, all or part of the alcohol -OH functions of the compounds (Ill'i) or (Ill'ii) and all or part of the alcohol functions possibly still present and derived from the polyols (H)pZ(OH)m- implemented in the first step are transformed into -OC(O)-C(Ra)(Rb)-C(O)-R4 radicals, for example via a transesterification reaction with a Gp-C(O)-C(Ra)(Rb)-C(O)-R4 ester in which Gp preferably designates a hindered alkoxy radical such as tBu-O- to lead to the corresponding formula (I) compounds.

[0123] Compounds of formula (la) to (le) such that p equals 1, Y denotes -C(O)-O- and m equals 1 can also be prepared by combining steps 2, 3 and 4 described above, from an unsaturated fatty acid such as oleic acid as described in "The synthesis of Bio-based Michael donors from tall oil fatty acids for polymer development", Polymers, 2022,14, 4107.

[0124] By way of example, the reaction scheme below can be implemented in which all the epoxides are opened by methanol and then each hydroxyl group is esterified by t-Bu-OCOCH2CH3: A4 format Compound b4 Compound b4 Compound c4

[0125] By way of example, the reaction scheme below can be implemented in which an unsaturated oil reacts with a (poly)hydroxy thiol such as SH-(CH2)xOH, with x being an integer preferably from 1 to 4, followed by a transesterification reaction (as described in Desroches, M., Caillol, S., Lapinte, V., Auvergne, R., & Boutevin, B. (2011). Synthesis of biobased polyols by thiol-ene coupling from vegetable oils. Macromolecules, 44(8), 2489-2500): Compound b 5 Compound

[0126] By way of example, the reaction scheme below can be implemented in which all the epoxides are opened by lactic acid and then each hydroxyl group is esterified by t-Bu-OCOCH2CH3: Compound b6 Compound 36 Compound b6 Compound e6 (Poly)amine compounds

[0127] 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.

[0128] The (poly)amine compound(s) may be selected 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 selected 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 (C1-C4) alkyl group such as methyl, and R' representing a hydrogen atom or a (CrC4) alkyl group, preferably a hydrogen atom.

[0129] By "non-polymer compound" is meant a compound that is not directly obtained by a polymerization reaction of monomers.

[0130] 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, and 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, xylenediamine, tris(2-aminoethyl)amine, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, diaminopropanol such as 1,3-diamino-2-propane-l ol, 4,7,10-Trioxa-1,13-tridecanediamine, spermidine, lysinol and C36-alkylenediamines (respectively Priamine™ 1071, 1073, 1074, 1075 marketed by CRODA), preferably C36-alkylenediamines (respectively Priamine™ 1071, 1073, 1074, 1075 marketed by CRODA), 1,3-diamino-2-propane-l-ol, polylysine, spermidine and mixtures thereof.

[0131] 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.

[0132] 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.

[0133] 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.

[0134] 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).

[0135] 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.

[0136] 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.

[0137] 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.

[0138] 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.

[0139] In particular, the (poly)amine compound(s) are selected from 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.

[0140] Preferably, the (poly)amine compound(s) are chosen from 3-aminopropyltriethoxysilane (APTES), 3-aminoethyltriethoxysilane (AETES), 3-aminopropylmethyldiethoxysilane, and N-(2-aminoethyl)-3-aminopropyltrieth oxysilane, and more preferably 3-aminopropyltriethoxysilane (APTES), in particular that marketed by Sigma Aldrich.

[0141] The (poly)amine compound(s) may also be selected from 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.

[0142] 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 (Ci-C4)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.

[0143] 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).

[0144] 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.mol1.

[0145] 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.

[0146] The (poly)amine compound(s) which are diaminized are particularly 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.

[0147] According to a particular embodiment of the invention, the (poly)amine compound(s) are triamine, namely they contain three primary amine groups and / or secondary, preferably primary (NH2). More particularly, they are chosen from triamine polyethers especially of formula ALK'”[(O-ALK')m-NH2]3 with ALK' as defined previously and ALK”', representing a trivalent (Ci-C6)alkylene group, linear or branched, and m representing an integer greater than or equal to 0.

[0148] As (poly)amine compounds which are triamine, triamine polyethers are particularly cited, such as those sold under the name Jeffamine T-403.

[0149] 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).

[0150] 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.

[0151] 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.

[0152] According to this variant, the (poly)amine compound(s) are in particular selected 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.

[0153] 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.

[0154] 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.

[0155] 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.

[0156] According to another variant, formula (VII) is such that Ra represents a hydroxyl or (CrC4)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.

[0157] As an amino polymer, polytetrahydrofuran (or polytetramethylene glycol) α, co-diamine, and polybutadienes α, co-diamine may also be cited.

[0158] 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.

[0159] Preferably, the (poly)amine compound(s) are chosen 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 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 designates a C2-C20 hydrocarbon divalent chain, optionally substituted by a hydroxyl group (-OH) and / or optionally interrupted by one or more selected heteroatoms among -O-, -N(R)- with R denoting a hydrogen atom or a Cr C4 alkyl radical, notably spermidine, 4,7,10-Trioxa-l,13-tridecanediamine, 1,3-diamino-2-propan-l-ol and lysinol, f) the C36-alkylenediamines, g) the polydialkylsiloxanes comprising primary amine groups at the end of the chain or on side chains, in particular the polydimethylsiloxanes comprising primary amine groups, more particularly the poly(dimethoxysiloxane) terminated by bis(3-aminopropyl) (PDMS-diNH2) and the amodimethicones comprising amine groups on side chains, even more particularly the bis-cetearyl amodimethicone; and their mixtures.

[0160] More preferably, the (poly)amine compound(s) are chosen from a), c), e), f), g), and their mixtures.

[0161] 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.

[0162] Better still, the (poly)amine compound(s) are chosen from triamine polyethers, such as Jeffamine T-403, spermidine, l,3-diamino-2-propan-l-ol, and mixtures thereof. Direct dyes

[0163] 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.

[0164] 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.

[0165] 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.

[0166] As a preferred benzene nitro direct dye according to the invention, 2-Hydroxyethylamino-5-nitroanisole may be mentioned.

[0167] The process according to the present invention may employ one or more non-ionic direct dyes.

[0168] Among the non-ionic direct dyes, we can mention neutral benzene nitro direct dyes, neutral azo direct dyes, neutral anthraquinone dyes.

[0169] The process according to the present invention can employ one or more cationic direct dyes.

[0170] 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.

[0171] Cationic direct dyes contain at least one quantified cationic chromophore or at least one chromophore bearing a quantified or quantizable cationic group.

[0172] According to a particular embodiment of the invention, the cationic direct dyes comprise at least one quantified cationic chromophore.

[0173] 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, particularly (hetero)aromatic nitro; oxadiazoles; oxazines; perilones; perinones; perylenes; phenazines; phenoxazine; phenothiazines; phthalocyanine; polyenes / carotenoids; porphyrins; pyrantrones; pyrazolantrones; pyrazolones; pyrimidineantrones; pyronins; quinacridones; quinolines; quinophthalones; squaranes; tetrazoliums; thiazines, thioindigo; thiopyronines; triarylmethanes, or xanthenes.

[0174] 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.

[0175] 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.

[0176] 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.

[0177] 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.

[0178] 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.

[0179] Among the cationic triarylmethane dyes that can be used according to the invention, the following dyes may be mentioned, in addition to those listed in the Colour Index: -Basic Green 1 -Basic Violet 3 -Basic Violet 14 -Basic Blue 7 -Basic Blue 26.

[0180] 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, vols. 1-7, in the encyclopedia "Kirk- Othmer" "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.

[0181] According to a particular embodiment, the direct dyes are cationic azoic dyes, described in EP 850636, FR 2788433, EP 920856, WO 9948465, FR 2757385, EP 850673, WO 850638, WO 9948433 9744004, FR 2570946, FR 2285851, DE 2538363, FR 2189006, FR 1560664, FR 1540423, FR 1567219, FR 1516943, FR 1212, 228 DE 4137005, WO 0166646, US 5708151, WO 9501772, WO 515144, GB 1195386, US 3524842, US 5879413, EP 1062940, EP 113938, DE 61387, DE 2527638, FR 2275462, GB 1974-27645, Acta Histochem. (1978), 61(1), 48-52 ; Cytology (1968), 10(3), 403-5 ; Zh. Obshch. Khim. (1970), 40(1), 195-202 ; Ann. Say. (Rome) (1975), 65(5-6), 305-14 ; Journal of the Chinese Chemical Society (Taipei) (1998), 45(1), 209-211 ; Rev. Rome. Say. (1988), 33(4), 377-83 ; Text. Nothing. J. (1984), 54(2), 105-7 ; Say. Ind. (Milan) (1974), 56(9), 600-3 ; Khim. Technol. (1979), 22(5), 548-53 ; Word. Monatsh. Chem. (1975), 106(3), 643-8 ; MRL Bull. Nothing. 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.

[0182] Les colorants directs cationiques comprennent par exemple un radical cationique : - à charge exocyclique (di / tri)(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.

[0183] Preferably, cationic direct dyes comprise a quaternary ammonium group, more preferably the cationic charge is endocyclic.

[0184] Examples include the following cationic hydrazono dyes of formula (C-II) and (C-III), azo dyes of formula (C-IV) and (C-V), as well as their optical, geometric, 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 (CV) 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)(CrC8)(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 else 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.

[0185] 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.

[0186] Preferably, the following direct dyes may be mentioned: R4 (C-II-1), (C-IV-1), formulas (C-II-1) and (C-IV-1) in which: - 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)(Ci-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.

[0187] 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: Basic Yellow 87,

[0188]

[0189]

[0190]

[0191] 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. 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. Examples of fluorescent dyes include radicals derived from acridine, acridone, benzantrone, benzimidazole, benzimidazolone, benzindole, benzoxazole, benzopyrane, benzothiazole, coumarin, difluoro{2-[(2H-pyrrol-2-ylidene-kN)methyl]-1H-pyrrolato-kN]bore (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, and xanthenes. We can also mention 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 encyclopedia "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 online. or in previous printed editions. 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 (Ci-C8)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 C1-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 at C1-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.

[0192] Among cationic direct dyes, triarylmethane cationic dyes may also be mentioned.

[0193] 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,

[0194] preceding formulas (C-VII) and (C-VII') in which: * Ri, R2, R3 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 Ri, attached to the same nitrogen atom, together with the nitrogen atom to which they are attached, form a heterocycloalkyl group, possibly substituted, such as morpholino, piparazino, piperidino, preferably RB. R2, R3 and Ri, whether identical or different, represent a hydrogen atom or a (Ci-C4)alkyl group, * R5, R6, R7, R8, R9, Rio, Ru, Ri2, Ri3, Ri4, Rb and R16, 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, a Ci-C4 alkyl radical possibly bearing at least one hydroxyl group and the radical R' is a CrC2 alkyl radical; viii) carbamoyl ((R)2N-C(O)-) in which the radicals R, identical or not, represent a hydrogen atom, a CrC4 alkyl radical possibly bearing at least one hydroxyl group; ix) carboxylic acid or ester, (-OC(O)R') or (-C(O)OR'), in which the radical R' is a hydrogen atom, or alkyl in CrC4 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 an atom; hydrogen, a C1-C4 alkyl radical possibly bearing at least one hydroxyl group, xiii) (Ci-C4)alkoxy, and xiv) (Ci-C4)alkylthio; * Or two radicals carried by two contiguous carbon atoms R5 and R6 and / or R7 and R8, and / or R9 and Rio and / or Ru and R[2 and / or Rn and R[4 and / or Ri5 and Ri6 together with the carbon atoms which carry them a condensed ring with 6 aryl or heteroaryl links, preferably benzo, said ring being able to be further possibly 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.

[0195] 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.

[0196] According to a preferred embodiment, the triarylmethane dyes are selected 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 a (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) group (alkyl)amino, preferably in the para position of the phenyl group.

[0197] 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.

[0198] Among cationic direct dyes, anthraquinone cationic dyes can also be mentioned.

[0199] Examples of cationic anthraquinone direct dyes include Disperse Violet 1, Hydroxyanthraquinone-aminopropyl Methyl Morpholinium Methosulfate, HC Orange No. 5 and HC Red No. 8

[0200] Preferably, the anthraquinone cationic direct dyes usable in the coloring process of the invention comprise a quaternary ammonium group.

[0201] 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.

[0202] De préférence, la charge cationique est exocyclique.

[0203] Among anthraquinone cationic direct dyes, those of formula (C-VIII) having an exocyclic cationic charge are preferred: (C-VIII) 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.

[0204] 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.

[0205] 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.

[0206] 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.

[0207] A dye of formula (C-VIII') particularly preferred is HC Blue 17.

[0208] A dye of formula (C-VIII”) particularly preferred is HC Blue 16 (l-methylamino-4-(3'-dimethylpropylammoniumpropylamino)antraquinone bromide).

[0209] Preferably, 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.

[0210] 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.

[0211] The process according to the present invention may employ one or more anionic direct dyes.

[0212] The anionic direct dyes of the invention are dyes commonly called "acid" direct dyes because of their affinity for alkali substances. Anionic direct dyes are understood to mean any direct dye having in its structure at least one CO2R or SO3R substituent, where R designates a hydrogen atom or a cation from a metal or an amine, or an ammonium ion.

[0213] 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.

[0214] 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):

[0215] a) Diaryl anionic azo dyes of formula (A-II) or (A-II'): formulas (A-II) and (A-II') in which: * R7, Rs, R9, Rio, R'7, R'8, R'9 and R'10, 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 Rio 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;

[0216] 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 Blue 113, Acid Blue 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;

[0217] et à titre d’exemple de colorants de formule (A-IF), on peut citer : Acid Red 111, Acid Red 134, Acid yellow 38 ;

[0218] b) les colorants azo anioniques pyrrazolone de formule (A-III) et (A-IIF) : (A-IIF) formulas (A-III) and (A-IIF) in which: * Ru, R12 and Rn, whether identical or different, represent a hydrogen atom, a halogen atom, an alkyl group or -(O)2S(O), M+ with M+ as defined previously; * RM represents a hydrogen atom, an alkyl group or a -C(O)O group, M+ with M+ as defined previously; * R15 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'2O, whether identical or different, represent a hydrogen atom 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;

[0219] 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 R2s 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;

[0220] * 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 colorants of formula (A-IV') we can cite: Acid Black 48; d) Nitrated dyes of formula (AV), and (A-V'): (A-V') no2 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; particularly R30, R3[ 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; * 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; * - - present or absent 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;

[0221] Examples of colorants of formula (AV) include: Acid Brown 13; Acid Orange 3; examples of colorants of formula (A-V') include: Acid Yellow 1, Sodium salt of 2,4-dinitro-1-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;

[0222] e) triarylmethane dyes of formula (A-VI): 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 R^, 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 R42 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)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”-; with M+, R°, X, X', X” as defined previously; particularly R37 to R^ represent a hydrogen atom, and R4! to R^, identical or different, represent a hydroxy group or (O)2S(O )-, M+; and when R43 with R44 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;

[0223] f) xanthene-derived dyes of formula (A-VII): % (A-VII) Rs; formula (A-VII) in which: * R45, R46, R47 and R48, whether identical or different, represent a hydrogen atom or a halogen atom; * R49, 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; * The ' represents an oxygen atom, sulfur or an ammonium group: N+ RfRg, with Rf and Rg, identical or different, representing a hydrogen atom, an alkyl group, aryl possibly substituted; The ' 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.

[0224] Examples of colorants of formula (A-VII) include: Acid Yellow 73; Acid Red 51; Acid Red 52; Acid Red 87; Acid Red 92; Acid Red 95; Acid Violet 9;

[0225] g) dyes derived from indole of formula (A-VIII): 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;

[0226] As an example of colorants of formula (A-VIII), we can cite: Acid Blue 74.

[0227] h) quinoline-derived dyes of formula (A-IX): ^4 (A-IX), formula (A-IX) in which: * R6i represents a hydrogen atom, halogen or alkyl group; * R62, Res, 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.

[0228] Examples of colorants of formula (A-IX) include: Acid Yellow 2, Acid Yellow 3 and Acid Yellow 5.

[0229] 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:

[0230] [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) (CL 16250) Acid Red 44 (A-II) (Cl 17200) Acid Red 33 / Food Red 12 (A-II) (Cl 15685) Acid Red 184 (A-II) (Cl 19125) Acid Violet 3 (A-II) (Cl 18055) Sodium salt of l-hydroxy-2-(4'-acetamido) phenylazo)-8-acetamido-naphthalene-3,6-disulfonic acid / Acid Violet 7 / Food Re d 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)naphthylazo)biphenyl / Acid Red 111 (A-II) (Cl 27755) Food Black 2 (A-II) (Cl25440) 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) (Cl 14710) Sodium salt of 4-hydroxy-3((2-methoxy) phenyl)-azo)-l-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-[3-Hydroxyethylamino-3-nitrobenzene Sulfonic Acid (A-V') (CI 42640) Acid Violet 49 (A-VI) (CI 42080) Acid Blue 7 (A-VI) (CI 58005) Sodium salt of l,2-dihydroxy-3-sulfo-anthraquinone / Mordant Red 3 (A-IV) (CI 62055) Sodium salt of l-amino-9,10-dihydro-9,10-dioxo-4-(phenylamino) 2-anthracene sulfonic acid / Acid Blue 25 (A-IV) (CI 14710) Sodium salt of 4-hydroxy-3-((2-methoxyphenyl)-azo)-l-naphthalene sulfonic acid / Acid Red 4 (A-II)

[0231] 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.

[0232] 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-sulfophenyl)-methylene]-2,5-cyclohexadien-l-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. .

[0233] Compounds corresponding to the mesomeric, tautomeric forms of (A-II) to (A-IX) structures can also be used.

[0234] 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.

[0235] 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.

[0236] Preferably, the cationic direct colorant(s) are selected from Basic Red 51, HC Blue 15, HC Blue 16, Disperse Violet 1, Basic Yellow 87, and mixtures thereof.

[0237] Even more preferably, the cationic direct colorant(s) are chosen from Basic Red 51, HC Blue 15, HC Blue 16, and mixtures thereof.

[0238] Additional features of the coloring process

[0239] According to a first embodiment, the coloring process comprises applying to the keratin fibers a composition (A) comprising the direct dye(s) and optionally the compound(s) A and then a composition (B) comprising the (poly)amine compound(s) and optionally the compound(s) A, it being understood that at least one of the compositions (A) or (B) comprises the compound(s) A, preferably composition (B) comprises the compound(s) A.

[0240] Preferably, according to this first embodiment, the composition (B) does not include direct colorants.

[0241] 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).

[0242] According to another embodiment, the coloring process includes the application of compound(s) A and compound(s) (poly)amine or a composition (B) comprising compound(s) A and compound(s) (poly)amine on keratin fibers previously colored with direct dye(s) or a composition (A) comprising them.

[0243] 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.

[0244] 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.

[0245] 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.

[0246] 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).

[0247] According to the second embodiment, the keratin fibers are preferably unrinsed and dried after application of composition (C).

[0248] When dried, keratin fibers can be air-dried or dried with a drying device such as a helmet, hair dryer or climazon.

[0249] Characteristics of compositions (A), (B) (C) and (D)

[0250] Preferably, compound(s) A are present in composition (A) or (B) or (C) in a total content of 0.2% to 99% by weight, preferably of 1% to 98% by weight, more preferably of 5% to 96% by weight, relative to the total weight of the composition comprising them.

[0251] Preferably, 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 1% to 35% by weight, relative to the total weight of the composition comprising them.

[0252] Preferably, 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.

[0253] 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).

[0254] 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).

[0255] 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.

[0256] According to a preferred embodiment, compositions (A), (B), (C) and / or (D) comprise water and / or one or more solvents S selected from polar and / or protic solvents, oils distinct from compounds A, and mixtures thereof.

[0257] Polar and / or protic solvents are preferably chosen from monoalcohols having 2 to 6 carbon atoms such as ethanol, propanol, n-butanol, isopropanol, isobutanol, tert-butanol, pentanol, hexanol, and mixtures thereof, in particular n-butanol, ethanol, and mixtures thereof, esters having 3 to 8 carbon atoms such as ethyl lactate, more preferably chosen from ethanol, ethyl lactate, and mixtures thereof.

[0258] The distinct oils of compounds A are preferably chosen from hydrocarbon oils, more preferably chosen from C8-Ci6 hydrocarbon oils, even more preferably chosen from iso-alkanes, and better chosen from Ci3-Ci6 iso-paraffins, isododecane, isohexadecane, and mixtures thereof, and even better isododecane.

[0259] By "oil" is meant a non-aqueous compound, immiscible with water, liquid at room temperature (20 °C) and atmospheric pressure (760 mm Hg).

[0260] 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.

[0261] When compositions (A), (B), (C) and / or (D) include water, the water is present in a total weight content of 20% to 90% by weight, preferably of 30% to 80% by weight, relative to the total weight of the composition comprising it.

[0262] When compositions (A), (B), (C) and / or (D) comprise one or more solvents S, the solvent(s) S are present in a total weight content of 1% to 90% by weight, preferably of 20% to 80% by weight, relative to the total weight of the composition comprising it.

[0263] Compositions (A), (B), (C) and / or (D) may be presented in all galenic forms classically used for hair application. Composition (C)

[0264] According to a second aspect, the present invention relates to a composition (C) as defined above. Kit

[0265] 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 above, it being understood that at least one of the compartments includes one or more direct dyes. Use

[0266] 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

[0267] The following examples serve to illustrate the invention without, however, being limiting in nature.

[0268] 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.

[0269] Example A: Synthesis of castor oil with acetoacetate function (Compound No. 1)

[0270] The synthesis is represented by the following preparation scheme:

[0271] In a 250 mL SVL® reactor equipped with mechanical stirring, a thermometer, and a distillation column, 50 g of castor oil (commercially available from Société Interchimie) and 25.40 g of tert-butyl acetoacetate are introduced. The reaction mixture is heated to 130 °C using an oil bath. After 7 hours, the reaction mixture is cooled, transferred to a 250 mL bulb flask, and heated to 120 °C under continuous vacuum using a rotary evaporator for 1 hour. A slightly yellow oil is obtained.

[0272] Example B: Synthesis of hydroxylated castor oil with acetoacetate function (Compound No. 2)

[0273] The synthesis is represented by the following preparation scheme: Step a)#:

[0274]

[0276]

[0277]

[0278]

[0279]

[0280]

[0281] In step a), the hydroxylated castor oil is prepared: In a 250 mL round-bottom flask equipped with a magnetic stirrer and under argon, 10 g of castor oil (commercially available from Interchimie), 9 g of 3-Mercapto-1,2-propanediol (commercially available from Sigma Aldrich), and 0.7 g of 2-Hydroxy-2-methylpropiophenone (commercially available from Sigma Aldrich) are added to 20 mL of ethyl acetate and stirred for 5 minutes under argon. The reaction mixture is then irradiated under a UV lamp (100 W, 365 nm) for 4 hours and subsequently washed 3 times with saturated NaCl water. The organic phase is separated, dried over MgSO4, and then concentrated under vacuum. Finally, the solvent, traces of thiol, and photoinitiator (2-Hydroxy 2-methylpropiophenone) are removed by distillation under reduced pressure. The resulting product is used as is in the next step. In step b), the hydroxylated castor oil is functionalized with acetoacetate groups: 10 g of hydroxylated castor oil obtained in step a) and 12 g of tert-butyl acetoacetate are introduced into a 250 mL round-bottom flask equipped with a magnetic stirrer. The reaction mixture is heated to 130 °C using an oil bath. After 4 hours, the reaction mixture is placed under continuous vacuum for 1 hour. A viscous, yellow oil is obtained. Example C: Synthesis of epoxidized oil with acetoacetate function (Compound No. 3) The synthesis is represented by the following preparation diagram: Step a)#: Step b)#:

[0282]

[0283] In step a), in a 500 mL S VL® reactor equipped with mechanical stirring, an argon inlet, and a distillation column, 200 g of epoxidized oil (Vikoflex 7170 marketed by Arkema), 50.4 g of lactic acid, and 6.52 g of caffeine are introduced. The reaction mixture is heated at 120 °C for 5 hours. The polyhydroxylated compound is obtained. A slightly yellow, viscous oil is produced.

[0284] In step b), in a 500 mL S VL® reactor equipped with mechanical stirring, an argon inlet, and a distillation column, 165 g of the polyhydroxylated compound obtained in step a) and 116.74 g of tert-butylacetoacetate are introduced. The reaction mixture is heated between 130 °C and 140 °C for 5 hours. After 5 hours of heating, the mixture is placed under vacuum at 50 mbar at 140 °C. A viscous, orange-colored oil is obtained.

[0285] The oil obtained is diluted with ethyl acetate and washed three times with a saturated sodium bicarbonate solution, then twice with water. The organic phase is filtered through MgSO4, and then the ethyl acetate is distilled using a rotary evaporator at 100 °C under reduced pressure. A slightly orange, viscous oil is obtained.

[0286] Example D: Synthesis of soybean oil with acetoacetate function (Compound No. 4)

[0287] The synthesis is represented by the following preparation scheme: Step a)#:

[0289] Step b)#:

[0290] In step a), in a 250 mL flask equipped with a magnetic stirrer, 10 g of soybean oil (Henry Lamotte Oils), 10 g of 3-Mercapto-1,2-propanediol (marketed by Sigma Aldrich) and 0.8 g of 2-Hydroxy 2-methylpropiophenone (marketed by Sigma Aldrich) are added to 25 mL of ethyl acetate and stirred for 5 minutes under argon. The reaction mixture

[0291]

[0292]

[0293]

[0294] The sample is then irradiated under a UV lamp (100 W, 365 nm) for 4 hours, and then washed 3 times with saturated NaCl water. The organic phase is separated, dried over MgSO4, and then concentrated under vacuum. The solvent, traces of thiol, and photoinitiator are removed by distillation under reduced pressure. In step b), 10 g of hydroxylated soybean oil obtained in step a) and 14 g of tert-butyl acetoacetate are introduced into a 250 mL round-bottom flask equipped with a magnetic stirrer. The reaction mixture is then heated to 130 °C using an oil bath. After 4 hours, the reaction mixture is cooled and placed under continuous vacuum for 1 hour to remove the excess tert-butyl acetoacetate. A viscous, yellow oil is obtained. Example E: Synthesis of an "acidic" oil with acetoacetate function (Compound n Z5) The synthesis is represented by the following preparation diagram: Step a)#:

[0295] Step b)#: Step c)#:

[0296]

[0297] In step a), 100 g of citric acid and 419 g of oleic alcohol are introduced into a 500 mL S VL® reactor equipped with mechanical stirring and a distillation column. The reaction mixture is heated to 190 °C using a heating mantle. for 7 hours, then at 220 °C for 5 hours. The reaction is monitored by acid number. When the acid number is less than 5, the reaction is stopped.

[0298] In step b), in a 250 mL flask equipped with a magnetic stirrer, 100 g of the acidic oil obtained in a), 70 g of 3-Mercapto-1,2-propanediol (commercially available from Sigma Aldrich) and 5 g of 2-Hydroxy-2-methylpropiophenone (commercially available from Sigma Aldrich) are added to 15 mL of ethyl acetate and stirred for 5 minutes under argon. The reaction mixture is then irradiated under a UV lamp (100 W, 365 nm) for 4 hours and subsequently washed 3 times with saturated NaCl water. The organic phase is separated, dried over MgSO4, and then concentrated under vacuum. The solvent, traces of thiol, and photoinitiator (2-Hydroxy-2-methylpropiophenone) are removed by distillation under reduced pressure.

[0299] In step c), 100 g of the hydroxylated acid oil obtained in step b) and 100 g of tert-butyl acetoacetate are introduced into a 250 mL round-bottom flask equipped with a magnetic stirrer. The reaction mixture is heated to 130 °C using an oil bath. After 4 hours of reaction, the reaction mixture is placed under continuous vacuum for 1 hour. A viscous, brown-colored oil is obtained.

[0300] Example F: Synthesis of a castor oil with acetoacetate function (Compound n 6)

[0301] The synthesis is represented by the following preparation scheme: Step a)#:

[0302]

[0304]

[0305]

[0306]

[0307]

[0308]

[0309]

[0310]

[0311]

[0312]

[0313] In step a), in a 250 mL flask equipped with a magnetic stirrer, 100 g of castor oil (commercially available from Interchimie), 17 g of 3-Mercapto-1,2-propanediol (commercially available from Sigma Aldrich), and 1 g of 2-Hydroxy-2-methylpropiophenone (commercially available from Sigma Aldrich) are added to 20 mL of ethyl acetate and stirred for 5 minutes under argon. The reaction mixture is then irradiated under a UV lamp (100 W, 365 nm) for 4 hours and subsequently washed 3 times with saturated NaCl water. The organic phase is separated, dried over MgSO4, and then concentrated under vacuum. The solvent, traces of thiol, and photoinitiator (2-Hydroxy-2-methylpropiophenone) are removed by distillation under reduced pressure. In step b), 100 g of hydroxylated castor oil obtained in step a) and 99 g of tert-butyl acetoacetate are introduced into a 250 mL round-bottom flask equipped with a magnetic stirrer. The reaction mixture is then heated to 130 °C using an oil bath (set to 140 °C on the oil bath). After 4 hours, the reaction mixture is placed under continuous vacuum for 1 hour. A viscous, yellow oil is obtained. Example G: Synthesis of mannitol dihexanoate with acetoacetate function (Compound No. 7) The synthesis is represented by the following preparation diagram: Step a)#: Step b)#: In step a), mannitol dihexanoate is obtained from mannitol under the conditions described in the publication Angew. Chem. Int. Ed. 2010, 49, 7695-7698. After 64 hours at 45°C, the reaction mixture was filtered and then concentrated under reduced pressure. The crude compound obtained after filtration and evaporation was then triturated in dichloromethane. In step b), 4 equivalents of 2,2,6-Trimethyl-1,3-dioxin-4-one in p-xylene are heated at 140°C for 2 hours. Purification by silica gel chromatography leads to the compound mannitol dihexanoate with an acetoacetate function. Example H: Synthesis of sucrose palmitate with acetoacetate function (Compound No. 8)

[0314]

[0315]

[0316]

[0317] In a 500 mL three-necked round-bottom flask equipped with a mechanical stirrer and a distillation column, 100 g of sucrose palmitate ester (Surfhope® SE Cosme C-1616, marketed by Mitsubishi-Kagaku Foods Corporation) and 110 g of tert-butyl acetoacetate are introduced. The mixture is heated in an oil bath at a temperature between 140°C and 150°C (as indicated on the oil bath) for 2 hours. The reaction mixture is then concentrated using a rotary evaporator at 140°C under continuous vacuum until constant weight is reached. Example I: Synthesis of a castor oil with acetoacetate function (Compound No. 9) The synthesis is represented by the following preparation diagram: Step a)#:

[0318] Step c)#:

[0319]

[0320] In step a), 451 g of castor oil (commercially available from Interchimie) and 171 g of glutaric anhydride are introduced into a 750 mL SVL® reactor equipped with a condenser, mechanical stirring, and an argon inlet. The reaction mixture is heated in an oil bath at 150°C (see oil bath instructions) for 5 hours. The reaction is monitored by NMR.

[0321] In step b), 600 g of castor oil modified with glutaric acid and 134 g of glycerol are introduced into a 500 mL SVL® reactor equipped with a distillation apparatus, mechanical stirring, and an argon supply. The reaction mixture is heated using a heating mantle for 4 hours at 190°C and then for 11 hours at 230°C. The reaction is monitored by acid value.

[0322] In step c), 600 g of glycerol-modified castor oil and 418 g of tert-butyl acetoacetate are introduced into a 1000 mL SVL® reactor equipped with a distillation apparatus, mechanical stirring, and an argon supply. The reaction mixture is heated in an oil bath at 150°C (as specified on the oil bath) for 5 hours. The reaction mixture is then placed in a rotary evaporator at 150°C under continuous vacuum to remove any unreacted tert-butyl acetoacetate.

[0323] Examples 1 to 7: Examples of application on strands

[0324] The compositions implemented in the examples were prepared from the following compositions: Compositions H1 to H6

[0325] [Tables2] Ingredients H1 H2 H3 H4 H5 H6 Compound #9 19.9 - - - - 20 Compound #2 - - - 10 19 - Compound #8 - 19.6 10 - - - Basic Red 51 - - 0.3 - - - HC Blue 15 - - - 0.1 0.2 0.2 Ethyl Lactate Qsp 100 - - Qsp 100 Qsp 100 Qsp 100 50 / 50 Isododecane / EtO H - Qsp 100 Qsp 100 - - - NI to N7 compositions

[0326] [Tables3] Ingredients NI N2 N3 N4 N5 N6 N7 Jeffamine T-403 Polyetheramine Mw = 440 g / mol AHEW = 81 g / eq CAS: 39423-51-3 Supplier: Huntsman Ann 8.6 17.6 13.4 1,3-Diamino-2-propanol CAS: 616-29-5 Supplier: Sigma-Aldrich 5.4 Priamine 1075 Supplier: Croda - - - 16.8 - - 17 Belsil ADM LOG 1 Aminated Silicone marketed by Wacker (15% MA) 100 Spermidine CAS: 124-20-9 Supplier: Sigma-Aldrich - - - 4.3 - - - Ethyl Lactate Qsp 10 0 - - - - Qsp 10 0 Qsp 10 0 50 / 50 Isododecane / EtOH - Qsp 10 0 - - - - - 50 / 50 Water / EtOH - - Qsp 10 0 Qsp 10 0 - - -

[0327] MA: Active ingredient Compositions DI to D4

[0328] [Tables4] Ingredients DI D2 D3 D4 2-Hydroxyethylamino-5-Nit roanisole 0.2 - - - HC Blue 16 - 1 - - Basic Red 51 - - 0.3 - HC Blue 15 - - - 0.1 50 / 50 Water / EtOH Qsp 100 Qsp 100 - - 50 / 50 Isododecane / EtOH [ 64-17-5] - - Qsp 100 - Ethyl Lactate - - - Qsp 100

[0329] Examples 1 to 3: Evaluation of the rise in color

[0330] In examples 1 to 3, the rise in colour was evaluated in the CIE L*a*b* system, using a Minolta Spectrophotometer CM3600A colourimeter (illuminant D65, angle 10°, specular component included).

[0331] 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.

[0332] The color uptake is assessed by the color difference AE between uncolored strands and after coloring. The higher the AE value, the more the color has uptaken the hair. The AE value is calculated according to the following equation: a s =

[0333] In this equation, L*, a* and b* represent the values ​​measured after hair coloring, and Lo*, a0* and b0* represent the values ​​measured before hair coloring. Example 1

[0334] The process implemented in Example 1 is a two-step process:

[0335] ■ Step 1

[0336] Composition D2 was applied to a strand of dry, natural hair that was 90% white, placed on a heated plate maintained at 27°C, at a rate of 1g of composition D2 per gram of hair. The hair was then left to rest for 5 minutes, rinsed with water, and finally dried with a hairdryer.

[0337] ■ Step _ 2

[0338] At the time of use, the H2 and N2 compositions were mixed together in a 1:1 weight ratio. The resulting mixture was then applied at temperature ambient temperature on the strand obtained in step 1 at a rate of 1g of mixture per gram of strand then the strand was finally dried with a hairdryer.

[0339] The color development 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".

[0340] The results of the color rise measurements are shown in the table below:

[0341] [Tables5] AF '11' method, ascent. Example 1: 25.05. Comparative method 1: 21.13.

[0342] The process according to example 1 of the invention allows for a better rise in colouring than comparative process 1. Example 2

[0343] The process implemented in Example 2 is a two-step process:

[0344] ■ Step 1

[0345] Composition H3 was applied to a strand of dry, natural hair that was 90% white, placed on a heated plate maintained at 27°C, at a rate of 1g of composition H3 per gram of hair. The hair was then left to rest for 5 minutes and then dried with a hairdryer.

[0346] ■ Step _ 2

[0347] Composition N3 was then applied to the strand obtained in step 1 at a rate of 1g of mixture per gram of strand, and then the strand was finally dried with a hairdryer.

[0348] The color development was evaluated according to the protocol described above. The process according to the invention is compared to the same process implementing only step 1 in which composition H3 is replaced by composition D3, referred to as "comparative process 2".

[0349] The results of the color rise measurements are shown in the table below:

[0350] [Tableauxô] AF '11' method, ascent Example 2 42.37 Comparative method 2 20.32

[0351] The process according to example 2 of the invention gives a better rise in colour than comparative process 2. Example 3

[0352] The process implemented in Example 3 is a two-step process:

[0353] ■ Step 1

[0354] Composition H3 was applied to a strand of dry, natural hair that was 90% white, placed on a heated plate maintained at 27°C, at a rate of 1g of composition H3 per gram of hair. The hair was then left to rest for 5 minutes and then dried with a hairdryer.

[0355] * Step 2

[0356] Composition N4 was then applied to the strand obtained in step 1 at a rate of 1g of mixture per gram of strand, and then the strand was finally dried with a hairdryer.

[0357] The color development was evaluated according to the protocol described above. The process according to the invention is compared to the same process implementing only step 1 in which composition H3 is replaced by composition D3, referred to as "comparative process 3".

[0358] The results of the color rise measurements are shown in the table below:

[0359] [Tables7] AF '11' method, ascent Example 3 46.27 Comparative method 3 21.02

[0360] The process according to example 3 of the invention allows for a better rise in colouring than comparative process 3.

[0361] Examples 4 to 7: Evaluation of the persistence of the coloring

[0362] In examples 4 to 7, the persistence of the shampooed highlights' color was evaluated in the CIE L*a*b* system, using a Minolta Spectrophotometer CM3600A colorimeter (illuminant D65, angle 10°, specular component included).

[0363] 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.

[0364] 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:

[0365] 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 4

[0366] The process implemented in Example 4 is a two-step process:

[0367] ■ Step 1

[0368] Composition DI was applied to a strand of dry, natural hair that was 90% white, 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.

[0369] ■ Step _ 2

[0370] At the time of use, compositions H1 and NI 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.

[0371] 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 4".

[0372] The results of the measurements are shown in the table below:

[0373] [Tables8] Method Number of shampoos L* a* b* AE ^^permanence Example 4 0 63.02 -3.97 30.5 14.74 10 51.62 -2.21 21.33 Comparative method 4 0 61.87 -3.24 31.36 18.30 10 64.13 -0.01 13.49

[0374] 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 4. Example 5

[0375] The process implemented in Example 5 is a two-step process:

[0376] ■ Step 1

[0377] Composition H4 was applied to a strand of dry, natural hair that was 90% white, placed on a heated plate maintained at 27°C, at a rate of 1g of composition H4 per gram of hair. The hair was then left to rest for 5 minutes and then dried with a hairdryer.

[0378] * Step 2

[0379] Composition N5 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 then the strand was finally dried with a hairdryer.

[0380] Residual effect of shampoos was evaluated according to the protocol described above.

[0381] The process according to the invention is compared to the same process implementing only step 1 in which composition H4 is replaced by composition D4 called "comparative process 5".

[0382] The results of the measurements are shown in the table below:

[0383] [Tables9] Method Number of Shampoos L* a* b* AE ^^residuality Example 5 0 43.35 -16.43 -8.87 12.89 5 49.43 -10.71 0.95 Comparative Method 5 0 39.77 -2.54 -11.01 21.85 5 53.8 -3.65 5.71

[0384] 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 5. Example 6

[0385] The process implemented in Example 6 is a one-step process.

[0386] At the time of use, compositions H5 and N6 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.

[0387] 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 H5+N6 mixture.

[0388] The results of the measurements are shown in the table below:

[0389] [TableauxlO] Process Number of shampoos L* a* b* AE ^^residual effect Example 6 0 47.26 -16.7 6.95 4.96 5 46.5 -14.2 2.73 Comparative method 6 0 39.77 -2.54 -11.01 21.85 5 53.8 -3.65 5.71

[0390] 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 6. Example 7

[0391] The process implemented in Example 7 is a one-step process.

[0392] At the time of use, compositions H6 and N7 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.

[0393] 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 H6+N7 mixture.

[0394] The results of the measurements are shown in the table below:

[0395] [Tables II] Method Number of Shampoos L* a* b* AE ^^permanence Example 7 0 45.16 -13.36 -9.24 17.02 5 52.48 -5.65 4.05 Comparative Method 7 0 39.77 -2.54 -11.01 21.85 5 53.8 -3.65 5.71

[0396] 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 7.

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 and geometric isomers, their solvates such as hydrates, and their mixtures: (Hy.....Z - (Y-AK2>» * [(OHAKIMO-COT formula (I) in which: - Z represents a multivalent hydrocarbon radical in C2 to C40, in particular in C3 to C36, linear or branched, saturated or unsaturated, conjugated or not, acyclic or cyclic, aromatic or not, Z possibly being interrupted by one or more groups or heteroatoms chosen from -O-, -N(Ra)-, -S-, -C(O)-, (hetero)cycles, and their combinations; - AK1 represents a linear or branched divalent hydrocarbon chain saturated or unsaturated in C1-C12, preferably in Ci-C6, more preferably saturated in Ci-C6; - AK2 represents a linear or branched monovalent hydrocarbon chain, saturated or unsaturated, in C1-C40, optionally substituted by one or more identical or different radicals chosen from -OR, -X-AK3-(OC(O)-C(Ra)(Rb)-C(O)-R4)v; and / or said chain being optionally interrupted by one or more heteroatoms or groups chosen from -O-, -S-, -C(O)-, (hetero)cycle(s), and their combinations, in particular -OC(O)-, -C(O)-O- and / or -(hetero)cycle-O-(hetero)cycle-; - AK3 represents a linear or branched divalent hydrocarbon chain saturated or unsaturated at C1-C12, preferably at Ci-C6, more preferentially saturated at Ci-C6, even more preferentially at C1-C4; - R represents a hydrogen atom, a linear or branched alkyl radical saturated or unsaturated in Ci-C6, preferably in C1-C4, in particular methyl, or a -C(0)-C(Ra)(Rb)-C(0)-R4 radical; - X represents -O-, -S-, -OC(O)- or -C(O)-O-; - Y represents -OC(O)- or -C(O)-O-;

2. - R4 represents a monovalent hydrocarbon radical in C1 to C6, linear or branched, saturated or unsaturated, preferably a (Ci-C4)alkyl group, in particular methyl or tert-butyl, more preferably methyl; - Ra and Rb, whether identical or different, represent a hydrogen atom or a (Ci-C4)alkyl group, preferably a hydrogen atom; - p denotes an integer equal to 0 or 1; - m denotes an integer equal to 0, 1, 2, 3 or 4; it being understood that when m is greater than 1, then the radicals -Y-AK2 are identical or different; - n denotes an integer equal to 0, 1, 2, 3 or 4; it being understood that when n is greater than 1, then the radicals -(O)t-(AKi)q-(OC(O)-C(Ra)(Rb)-C(O)-R4)u are identical or different; -1 denotes an integer equal to 0 or 1; - q denotes an integer equal to 0 or 1; - u denotes an integer equal to 1, 2 or 3; - v denotes an integer equal to 1, 2 or 3; it being understood that if q is equal to 0 then t is equal to 0, that (m + n) is greater than or equal to 1, and that the compounds of formula (I) contain at least two -C(O)-C(Ra)(Rb)-C(O)-R4 groups; ii) one or more (poly)amine compounds; and iii) one or more direct dyes. A method according to the preceding claim, wherein the compound(s) A are selected from compounds of formula (I), their optical and geometric isomers, their solvates such as hydrates, and their mixtures, such as: - Z represents the trivalent radical -CH2-CH-CH2-; - p is equal to 0; - n is equal to 0; - m is equal to 3; - AK2 represents a linear or branched, saturated or unsaturated monovalent hydrocarbon chain, in the form C[2-C24, possibly substituted by one or more identical or different radicals chosen from -OR, -X-AK3-(OC(O)-C(Ra)(Rb)-C(O)-R4)v, and / or said chain possibly being interrupted by one or more heteroatoms or groups selected from -O-, -S-, -C(O)-, epoxides, and their combinations, in particular -O(CO)- or -C(O)-O-; - Y, AK3, v, R, X, R4, Ra and Rb being as defined in claim 1; provided that the compounds of formula (I) contain at least 2 -C(O)-C(Ra)(Rb)-C(O)-R4 radicals; preferably from the following compounds (1), (2), (3), (4), (7), (8), (9), (11) and (16), their optical isomers, geometric isomers, their solvates such as hydrates, and mixtures thereof: (1)

3. more preferentially among the compounds (3), (16), their optical isomers, geometric isomers, their solvates such as hydrates, and their mixtures. A method according to claim 1, wherein the compound(s) A are selected from compounds of formula (I), their optical isomers, geometric isomers, their solvates such as hydrates, and their mixtures, such that: - p is equal to 0; - m is non-zero; - Z represents a divalent hydrocarbon radical in C2 to C24, in particular in C3 to C,2, linear or branched, saturated or unsaturated, conjugated or not, preferably not conjugated, acyclic or cyclic, aromatic or not, preferably not aromatic, said radical Z being further interrupted by one or more heteroatoms or groups selected from -O-, -N(Ra)-, -S-, -C(O)-, heterocycloalkyl(s) comprising 5 or 6 links, and their combinations; - AK2 represents a linear or branched monovalent hydrocarbon chain, saturated or unsaturated, preferably saturated, in Ci4-C30, preferably in Ci4-C24, preferably in Ci5, said chain being optionally substituted by one or more identical or different radicals selected from -OR and -X-AK3-(OC(O)-C(Ra)(Rb)-QOj-RJv, preferably unsubstituted; and / or said chain being optionally interrupted by one or more heteroatoms or groups selected from -O-, -S-, -C(O)-, (hetero)cycles, and their combinations, in particular -OC(O)-, -C(O)-O- or -(hetero)cycle- O-(hetero)cycle-, preferably possibly interrupted by -OC(O)- or -C(O)-O-, and more preferably being uninterrupted; - X is as defined in claim 1, and preferably X designates a sulfur atom; - Y, AK1, AK3, v, t, q, u, R, R4, Ra and Rb being as defined in claim 1, it being understood that the compounds of formula (I) contain at least 2 C(O)-C(Ra)(Rb)-C(O)-R4 radicals.

4. 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 CrC4, notably spermidine, 4,7,10-Trioxa-l,13-tridecanediamine, l,3-Diamino-2-propan-l-ol and lysinol, f) C36-alkylenediamines, g) 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, even more particularly bis-cetearyl amodimethicone; and mixtures thereof, preferably from a), c), e), f), g), and mixtures thereof; more preferentially among polylysine, triamine polyethers, such as Jeffamine T-403, spermidine, l,3-diamino-2-propan-l-ol, and mixtures thereof; even more preferentially among triamine polyethers, such as Jeffamine T-403, spermidine, l,3-diamino-2-propan-l-ol, and mixtures thereof.

5. 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, most preferably selected from Basic Red 51, HC Blue 15, HC Blue 16, and mixtures thereof.

6. 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 5 and optionally the compound(s) A as defined in any one of claims 1 to 3 and then a composition (B) comprising the (poly)amine compound(s) as defined in claim 1 or 4 and optionally the compound(s) A as defined in any one of claims 1 to 3, 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 3, preferably composition (B) comprises the compound(s) A as defined in any one of claims 1 to 3.

7. A method according to any one of claims 1 to 5, 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 3, the (poly)amine compound(s) as defined in claim 1 or 4 and the direct dye(s) as defined in claim 1 or 5.

8. A method according to any one of claims 1 to 5, wherein the method comprises applying the compound(s) A as defined in any one of claims 1 to 3 and the (poly)amine compound(s) as defined in claim 1 or 4 or a composition (B) comprising the compound(s) A as defined in any one of claims 1 to 3 and the (poly)amine compound(s) as defined in claim 1 or 4 to keratin fibers previously colored using the direct dye(s) as defined in claim 1 or 5 or a composition (A) comprising them.

9. A method according to any one of claims 1 to 5, wherein the method comprises applying to keratin fibers the direct dye(s) as defined in claim 1 or 5 or a composition (D) comprising the dye(s) and then the compound(s) A as defined in any one of claims 1 to 3 or a composition (A) comprising the dye(s) and then the (poly)amine compound(s) as defined in claim 1 or 4 or a composition (B) comprising the dye(s).

10. A process according to claim 6 to 9, wherein the compound(s) A are present in the composition (A) or (B) or (C) in a total content of 0.2% to 99% by weight, preferably of 1% to 98% by weight, more preferably of 5% to 96% by weight, relative to the total weight of the composition comprising the compound(s).

11. A method according to any one of claims 6 to 10, wherein the (poly)amine compound(s) are present in composition (B) or (C) in a total content of from 0.2% to 60% by weight, preferably from 0.5% to 40% by weight, more preferably from 1% to 35% by weight, relative to the total weight of the composition comprising the compound(s)

12. A process according to any one of claims 6 to 11, 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.

13. Composition (C) as defined in any one of claims 7 or 10 to 12.

14. A device with two or three compartments comprising: - a first compartment containing a composition comprising the compound(s) A as defined in any one of claims 1 to 3 and optionally one or more direct dyes as defined in claim 1 or 5; - a second compartment separate from the first compartment containing a composition comprising the (poly)amine compound(s) as defined in claim 1 or 4 and optionally one or more direct dyes as defined in claim 1 or 5; - optionally a third compartment separate from the first and second compartments containing one or more direct dyes as defined in claim 1 or 5, it being understood that at least one of the compartments comprises one or more direct dyes as defined in claim 1 or 5.

15. Use of one or more compounds A as defined in any one of claims 1 to 3 associated with one or more (poly)amine compounds as defined in claim 1 or 4 or of a composition (B) comprising the compound(s) A as defined in any one of claims 1 to 3 and the (poly)amine compound(s) as defined in claim 1 or 4, to improve the shampoo retention of a direct dye of keratin fibers.

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