Composition for simultaneous bleaching and dyeing of keratin fibers, comprising particular heterocyclic salt, and process using this composition

Abstract

To provide a composition for simultaneous bleaching and dyeing of keratin fibers, comprising one or more particular heterocyclic salts, and a process for simultaneous bleaching and dyeing of keratin fibers using this composition.SOLUTION: The present invention provides a composition comprising: a) one or more chemical oxidizing agents selected from hydrogen peroxide, hydrogen peroxide-generating agents other than peroxygenated salts, and mixtures thereof; b) one or more direct dyes; and c) one or more heterocyclic salts of a formula (A).SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to compositions comprising one or more specific heterocyclic salts for simultaneously bleaching and dyeing keratinous fibers and to a method for simultaneously bleaching and dyeing keratinous fibers using the compositions. [Background technology]

[0002] If you want to change your hair color to a completely different color, especially if you want to go lighter than your original color, you will often need to bleach your hair before dyeing it. There are several ways to do this.

[0003] The first method consists in using a lightening product based on aqueous ammonia and hydrogen peroxide, which may optionally contain a dye, thereby allowing the lightening and dyeing of the hair to be carried out at the same time. However, the lightening effect obtained by applying this product remains limited, especially on natural and / or darkly dyed hair.

[0004] The second method consists in applying a hair lightening composition based on peroxide salts, such as persulfates, and alkaline agents, with the extemporaneous addition of hydrogen peroxide, which aims to increase the degree of lightening. This composition can also contain a direct dye for simultaneous dyeing and bleaching of the hair. However, the range of direct dyes that can be used in this composition is still limited, since only stable direct dyes can be used to obtain strong chromatic colors with good color build-up under these conditions. In an attempt to remedy this stability problem, it was envisaged to carry out a two-stage process: in a first stage, the hair is bleached using a lightening composition, and then in a second stage, the hair is dyed using a composition containing a direct dye. However, the two-stage process is not satisfactory, since, in addition to the large number of operations, it also has the disadvantage of being relatively time-consuming.

[0005] There is therefore a strong need to develop a composition for bleaching and dyeing keratin fibers, comprising a direct dye, which exhibits both good lightening and dyeing properties, especially when applied to dark hair, and in particular is capable of obtaining intense chromatic colors in addition to good color build-up. Furthermore, this type of composition can contain a wide variety of direct dyes, allowing the user to obtain the desired shade. Finally, this type of composition can be used in a one-step process for simultaneously bleaching and dyeing keratin fibers.

[0006] Surprisingly, the Applicant has found that all these objectives are achieved by using the composition according to the invention. Summary of the Invention [Means for solving the problem]

[0007] According to a first aspect, the subject of the present invention is a method for producing a method for manufacturing a semiconductor device comprising: a) one or more chemical oxidizing agents selected from hydrogen peroxide, hydrogen peroxide generators other than peroxide salts, and mixtures thereof; b) one or more direct dyes; c) one or more compounds of formula (A): [ka] □ Het is: - 5 to 10 ring members, preferably 5 or 6 ring members; and - in addition to the ammonium to which R1 is attached, 1 or 2 atoms selected from nitrogen or oxygen atoms, preferably nitrogen atoms; represents a cationic aromatic unsaturated heterocyclic group comprising The heterocyclic group is optionally substituted with one or more R'1 or R2 groups; R1 and R'1 may be the same or different and may be selected from linear or branched, saturated or unsaturated C1-C alkyl groups, optionally substituted with one or more groups selected from, in particular, hydroxyl, amino, (C1-C6)dialkylamino, (C1-C6)alkylamino, carboxyl, carboxylate, carbamido, (C1-C4)alkoxy, -SO3H, sulfonate, and phenyl. 12 represents a hydrocarbon group; □ R2 is a hydroxyl group; an amino group; optionally, in particular, a linear or branched, saturated or unsaturated C1-C alkyl group substituted with one or more groups selected from hydroxyl, amino, (C1-C6)dialkylamino, (C1-C6)alkylamino, carboxyl, carboxylate, carbamido, (C1-C4)alkoxy, -SO3H, sulfonate, and phenyl. 12 represents a hydrocarbon group; □ Y - represents an anionic counterion; however, - if one of the hydrocarbon-based groups of R1, R'1 or R2 is substituted by a carboxylate or sulfonate group, Y is preferably substituted by a carboxylate or sulfonate group, so that the electroneutrality of the salt of formula (A) is maintained; - is understood to be absent) and The composition comprises:

[0008] According to a second aspect, the subject of the invention is also a method for simultaneously bleaching and dyeing keratinous fibers, comprising applying to the keratinous fibers a composition as defined above.

[0009] According to a third aspect, the subject of the present invention is a device or kit comprising several compartments, comprising: a first compartment containing a composition comprising one or more chemical oxidizers selected from hydrogen peroxide, hydrogen peroxide generators other than peroxide salts, and mixtures thereof; □ A second section: b) one or more direct dyes; and c) a second compartment containing a composition comprising one or more salts of formula (A) as defined above; Have or a first compartment containing a composition comprising one or more chemical oxidizers selected from hydrogen peroxide, hydrogen peroxide generators other than peroxide salts, and mixtures thereof; a second compartment, b) containing a composition comprising one or more direct dyes; a third compartment, c) containing a composition comprising one or more salts of formula (A) as defined above; The device or kit comprises: DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] With respect to the subject matter of the present invention, unless otherwise specified, it is as follows: The term "keratin fibres" is intended to mean fibres of human or animal origin, such as hair, body hair, eyelashes, eyebrows, wool, Angora goat hair, cashmere or fur. According to the invention, the keratin fibres are preferably human keratin fibres, more preferentially hair. □ The term "direct dyes" is intended to mean natural and / or synthetic dyes, including forms of extracts, other than oxidation dyes. These are dyes that will spread on the surface of the fibre. They may be ionic or non-ionic, i.e. anionic, cationic, neutral or non-ionic. Direct dyes may be of the same ionic nature or may be mixtures. Direct dyes have one or more chromophores that emit light at wavelengths λ abs It can absorb light in the range of 400nm to 700nm. Fluorescent direct dyes are dyes that contain at least one fluorescent chromophore, and these dyes emit light at wavelengths λ in the visible range of 400 nm to 800 nm. abs and absorbs light with wavelengths in the visible region λ in the range of 400 nm to 800 nm, which is longer than the absorbed wavelength. emThe difference between the absorption and emission wavelengths, also known as the Stokes shift, is between 1 nm and 100 nm. Preferably, the fluorescent direct dye has a wavelength λ in the range of 420 nm to 550 nm. abs and absorbs light with wavelengths λ in the visible range of 470 nm to 600 nm. em It is a dye that can be re-released. □ The term "chemical oxidant" is intended to mean an oxidant other than atmospheric oxygen. The term "alkyl group" is intended to mean a linear or branched saturated hydrocarbon-based group. □ "(C x ~C y The term "alkyl group" is intended to mean an alkyl group containing x to y carbon atoms. □ "Hydroxy (C x ~C y The term "alkyl group" refers to a group having at least one of its hydrogen atoms replaced by a hydroxyl (-OH) group (C x ~C y ) alkyl group. □ "(Hydroxy)(C x ~C y The term "hydroxy(C) alkyl group" refers to a x ~C y ) alkyl group or (C x ~C y ) alkyl group. The term "alkoxy group" is intended to mean an alkyl group that is bonded to an oxygen atom. □ "(C x ~C y The term "alkoxy group" is intended to mean an alkoxy group containing from x to y carbon atoms. □ "Hydroxy (C x ~C y The term "alkoxy group" refers to an alkoxy group having at least one of its hydrogen atoms replaced by a hydroxyl (-OH) group (C x ~C y ) alkoxy groups. □ The expression "optionally substituted" applied to an alkyl or alkoxy group means that the alkyl or alkoxy group may be substituted with one or more groups selected from the following groups: i) hydroxyl; ii) (C1-C4) alkoxy; iii) acylamino; iv) amino optionally substituted with one or two identical or different (hydroxy)(C1-C4) alkyl groups, said alkyl groups together with the nitrogen atom to which they are attached may form a heterocycle containing 5 to 7 ring members, said heterocycle optionally containing other nitrogen or non-nitrogen heteroatoms; v) a quaternary ammonium group -N + R'R''R''',M - (In the formula, R', R'', and R''' may be the same or different and represent a hydrogen atom or a (C1-C4) alkyl group, or R', R'', and R''' may represent N + together form a heteroaryl, such as an imidazolium, optionally substituted with a (C1-C4) alkyl group; M - represents an anion or mixture of anions such that electroneutrality is maintained). □ The term "alkylene" group refers to: i) hydroxyl, ii) (C1-C2) alkoxyl, iii) (poly)hydroxy(C2-C4) alkoxy(di)(C1-C2) (alkyl)amino, iv) (poly)hydroxy(di)(C1-C2) (alkyl)amino, v) R a -Z a -C(Z b )-Z c -,vi)R a '-C(Z b )-Z a - and vii) R a -Z a -S(O) t -Z c -(in the formula, Z a , Z b may be the same or different, and each represents an oxygen or sulfur atom or NR a ' represents a group, Z c is a bond, an oxygen or sulfur atom, or NR a ' represents a group, and R arepresents an alkali metal, a hydrogen atom, an alkyl group, or is absent if the rest of the molecule is cationic. R a ' represents a hydrogen atom or an alkyl group, and t is 1 or 2). 10 , in particular a divalent acyclic hydrocarbon chain of C1 to C6, more particularly C1 to C2; preferably, the "alkylene" group is -(CH2) p -group (wherein p is an integer of 1 to 6, preferably 1 to 4). The term "(hetero)aryl group" is intended to mean an aryl group or a heteroaryl group. □ The term "aryl group" is intended to mean a monocyclic or fused or non-fused polycyclic carbon-based group containing 6 to 22 carbon atoms, at least one ring of which is aromatic, preferentially an aryl group is phenyl, biphenyl, naphthyl, indenyl, anthracenyl or tetrahydronaphthyl. □ "Heteroaryl group" is intended to mean a 5-22 membered monocyclic or fused or non-fused polycyclic group, optionally cationic, containing 1 to 6 heteroatoms selected from nitrogen, oxygen, sulfur and selenium atoms, at least one ring of which is aromatic, preferentially heteroaryl groups being acridinyl, benzimidazolyl, benzobistriazolyl, benzopyrazolyl, benzopyridazinyl, benzoquinolyl, benzothiazolyl, benzotriazolyl, benzoxazolyl, pyridinyl, tetrazolyl, dihydrothiazolyl, and is selected from azolyl, imidazopyridyl, imidazolyl, indolyl, isoquinolyl, naphthimidazolyl, naphthoxazolyl, naphthopyrazolyl, oxadiazolyl, oxazolyl, oxazolopyridyl, phenazinyl, phenoxazolyl, pyrazinyl, pyrazolyl, pyrrylyl, pyrazoyltriazyl, pyridyl, pyridinoimidazolyl, pyrrolyl, quinolyl, tetrazolyl, thiadiazolyl, thiazolyl, thiazolopyridyl, thiazoylimidazolyl, thiopyrylyl, triazolyl, xanthinyl, and ammonium salts thereof. The (hetero)aryl group or the aryl or heteroaryl portion of any group may be optionally substituted with at least one group attached to a carbon atom selected from the following groups: - optionally substituted with at least one group selected from the following: 10 ) alkyl, preferably (C1-C4) alkyl: hydroxyl; (C1-C2) alkoxy; hydroxy (C2-C4) alkoxy; acylamino; amino optionally substituted with one or two (C1-C4) alkyl groups, which may be the same or different, optionally bearing at least one hydroxyl group (alternatively, the two (C1-C4) alkyl groups together with the nitrogen atom to which they are attached may form a 5-7 membered, preferably 5 or 6 membered, heterocyclic ring, which may be saturated or unsaturated, optionally substituted and optionally containing other nitrogen or non-nitrogen heteroatoms); - halogen atoms; - hydroxyl group; - (C1-C2)alkoxy group; - (hydroxyl) (C2-C4) alkoxy group; - amino group; - 5- or 6-membered heterocycloalkyl groups; - an optionally cationic 5- or 6-membered heteroaryl group, preferentially imidazolium, optionally substituted with a (C1-C4)alkyl group, preferentially methyl; - an amino group substituted with one or two identical or different (C1-C6) alkyl groups, optionally comprising at least i) hydroxyl groups; ii) an amino group optionally substituted with one or two optionally substituted (C1-C3) alkyl groups, which together with the nitrogen atom to which they are attached may form a saturated or unsaturated, optionally substituted, 5- to 7-membered heterocycle optionally containing at least one other nitrogen or non-nitrogen heteroatom; iii) Quaternary ammonium group -N+ R'R''R''',M - (In the formula, R', R'', and R''' may be the same or different and represent a hydrogen atom or a (C1-C4) alkyl group; M - represents an anionic counterion); iv) an optionally cationic 5- or 6-membered heteroaryl group, preferentially imidazolium, optionally substituted with a (C1-C4) alkyl group, preferentially methyl; v) an acylamino (-N(R)-C(O)-R') group (wherein R represents a hydrogen atom or a (hydroxy)(C1-C4)alkyl group, and R' represents a (C1-C2)alkyl group); having an amino group; - an acylamino (-N(R)-C(O)-R') group (wherein R represents a hydrogen atom or a (hydroxy)(C1-C4)alkyl group, and R' represents a (C1-C2)alkyl group); - a carbamoyl ((R)2N-C(O)-) group (wherein R may be the same or different and represent a hydrogen atom or a (hydroxy)(C1-C4)alkyl group); - an alkylsulfonylamino (R'-S(O)2-N(R)-) group (wherein R represents a hydrogen atom or a (hydroxy)(C1-C4)alkyl group, and R' represents a (C1-C4)alkyl group or a phenyl group); - an aminosulfonyl ((R)2N-S(O)2-) group (wherein R may be the same or different and represent a hydrogen atom or a (hydroxy)(C1-C4)alkyl group); a carboxyl group in acid or salt form (preferably in the form of a salt with an alkali metal or a substituted or unsubstituted ammonium salt); - cyano group; - nitro or nitroso groups; - polyhaloalkyl radicals, preferentially trifluoromethyl; - Ester groups. The term "cationic heteroaryl group" is intended to mean a heteroaryl group as defined above that contains an endocyclic or exocyclic quaternized cationic group; - if the cationic charge is in the ring, this is involved in the delocalization of electrons due to the mesomeric effect, for example this is the case in pyridinium, imidazolium or indolinium groups: [ka] where R and R' are substituents of heteroaryl as defined above, in particular (hydroxy)(C1-C8)alkyl groups, e.g. methyl; - when the charge is exocyclic, for example this is the ammonium substituent R such as trimethylammonium, which is exocyclic to the corresponding heteroaryl such as pyridyl, indolyl, imidazolyl, naphthalimidyl, etc. + or phosphonium: [ka] where R is a heteroaryl substituent as defined above, and R + Ammonium R a R b R c N + -, phosphonium R a R b R c P + - or ammonium R a R b R c N + -(C1-C6) alkylamino group, R a , R b , and R c may be the same or different and represent a hydrogen atom or a (C1-C8) alkyl group such as methyl). The term "cationic aryl group with an exocyclic charge" is intended to mean an aryl ring in which a quaternized cationic group is outside said ring; this is particularly the case for an ammonium substituent R, such as trimethylammonium, outside an aryl, such as a phenyl or naphthyl. + or phosphonium: [ka] . The term "(hetero)cyclic group" is intended to mean a heterocyclic group or a carbocyclic group. □ The term "heterocyclic group" is intended to mean a 5- to 22-membered monocyclic or fused or non-fused polycyclic group containing from 1 to 6 heteroatoms selected from nitrogen, oxygen, sulfur and selenium atoms, which may contain one or two unsaturations but is non-aromatic. The term "heterocycloalkyl group" is intended to mean a saturated heterocyclic group, such as morpholinyl, piperazinyl, or piperidinyl. □ The term "carbocyclic group" is intended to mean a 5- to 22-membered monocyclic or fused or non-fused polycyclic group which may contain one or two unsaturations but is non-aromatic, for example cyclobutyl, cyclopentyl, or cyclohexyl. The carbocyclic or heterocyclic portion of the non-aromatic group may be optionally substituted with at least one group selected from the following groups: - hydroxyl group; - (C1-C4)alkoxy or hydroxy(C2-C4)alkoxy groups; - (C1-C4) alkyl group; - alkylcarbonylamino (RC(O)-N(R')-) group, where R' is a hydrogen atom or a (hydroxy)(C1-C4)alkyl group, R is a (C1-C2)alkyl group or an amino group optionally substituted with one or two identical or different (hydroxy)(C1-C4)alkyl groups, which (hydroxy)(C1-C4)alkyl groups together with the nitrogen atom to which they are bonded may form a saturated or unsaturated, optionally substituted, 5- to 7-membered heterocycle optionally containing at least one other nitrogen or non-nitrogen heteroatom; - alkylcarbonyloxy (RC(O)-O-) groups, in which the R groups are (C1-C4)alkyl groups or amino groups optionally substituted with one or two identical or different (hydroxy)(C1-C4)alkyl groups, which (hydroxy)(C1-C4)alkyl groups together with the nitrogen atom to which they are attached may form a saturated or unsaturated, optionally substituted, 5- to 7-membered heterocycle, optionally containing at least one other nitrogen or non-nitrogen heteroatom; - an alkoxycarbonyl (RGC(O)-) group, where R is a (C1-C4) alkyl group and G is an oxygen atom or an amino group optionally substituted with a (hydroxy)(C1-C4) alkyl group. □ The cyclic or heterocyclic group or the non-aromatic portion of the aryl or heteroaryl group may also be substituted with at least one oxo group. □ If the hydrocarbon chain contains one or more double bonds and / or one or more triple bonds, it is an unsaturated chain.

[0011] Unless otherwise specified, when a compound is referred to in this application, this also includes its optical isomers, its geometric isomers, its tautomers, its salts, or its solvates, either alone or in mixtures.

[0012] "At least one" and "one or more" are synonymous and may be used interchangeably.

[0013] composition According to a first aspect, the subject of the invention is a composition as defined above.

[0014] Surprisingly, the Applicant has found that the addition of one or more heterocyclic salts of formula (A) to a composition comprising one or more oxidizing agents stabilizes the direct dyes and makes it possible to achieve a satisfactory level of lightening while also obtaining good colour build-up and strong chromatic colours.

[0015] Chemical oxidants a) The compositions according to the present invention comprise: a) one or more chemical oxidizing agents selected from hydrogen peroxide, hydrogen peroxide generators other than peroxide salts, and mixtures thereof.

[0016] The hydrogen peroxide generator other than a peroxide salt may be selected from urea peroxide, a polymer complex capable of releasing hydrogen peroxide, an oxidase, and mixtures thereof.

[0017] Examples of polymer complexes capable of releasing hydrogen peroxide include polyvinylpyrrolidone / H2O2, especially in powder form, and other polymer complexes described in U.S. Pat. Nos. 5,008,093, 3,376,110, and 5,183,901.

[0018] Oxidases can generate hydrogen peroxide in the presence of an appropriate substrate (eg, glucose in the case of glucose oxidase, or uric acid in the case of uricase).

[0019] Particularly preferably, the composition according to the invention comprises hydrogen peroxide as the chemical oxidizing agent.

[0020] According to one particular embodiment, a hydrogen peroxide generator other than hydrogen peroxide and / or a peroxide salt can be added immediately before applying the composition according to the invention to the keratin fibers. The intermediate composition comprising hydrogen peroxide and / or a hydrogen peroxide generator other than a peroxide salt can be referred to as an oxidizing composition and can also contain various additional compounds or various adjuvants conventionally used in hair lightening compositions.

[0021] The chemical oxidizing agents may be present in the composition in a total content ranging from 0.1% to 40% by weight, preferably ranging from 1% to 20% by weight and more preferentially ranging from 2% to 15% by weight relative to the total weight of the composition.

[0022] direct dyeb) The composition according to the invention comprises b) one or more direct dyes.

[0023] The direct dyes b) can be neutral, cationic or anionic direct dyes.

[0024] Direct dyes b) are: acridines; acridones; anthranthrones; anthrapyrimidines; anthraquinones; azines; (poly)azo or azo, hydrazono or hydrazones, in particular arylhydrazones; azomethines; benzanthrones; benzimidazoles; benzimidazolones; benzindoles; benzoxazoles; benzopyrans; benzothiazoles; benzoquinones; bis-isoindolines; carboxamides. Nilides; Coumarins; Cyanines such as (di)azacarbocyanines, (di)azahemicyanines, hemicyanines, or tetraazacarbocyanines; (di)azines; Bis-azines; (di)oxazines; (di)thiazines; (di)phenylamines; (di)phenylmethanes; (di)ketopyrrolopyrroles; Flavonoids such as flavanthrones and flavones; Fluorindins; Formasans; Indamines; Indanthrones; Indigoids, thioindigoids and may be neutral, cationic or anionic direct dyes selected from pseudoindigoids; indophenols; indoanilines; isoindolines; isoindolinones; isoviolanthrones; lactones; (poly)methines such as dimethines of the stilbene or styryl type; naphthalimides; naphthanilides; naphtholactams; naphthoquinones; nitro, especially nitro(hetero)aromatics; oxadiazoles; oxazines; perilones; perinones; perylenes; phenazines; phenoxazines; phenothiazines; phthalocyanines; polyenes / carotenoids; porphyrins; pyranthrones; pyrazoloanthrones; pyrazolones; pyrimidinoanthrones; pyronines; quinacridones; quinolines; quinophthalones; squalanes; tetrazolines; thiazines; thiopyronines; triarylmethanes; or xanthenes; and natural direct dyes. Preferably, the direct dyes b) are chosen from anthraquinones, (poly)azos, azomethines and stilbenes, more preferentially from anthraquinones.

[0025] The direct dyes b) may in particular be selected from neutral, cationic or anionic nitrobenzene direct dyes, neutral, cationic or anionic azo direct dyes, neutral, cationic or anionic tetraazapentamethine dyes, cationic or anionic quinone dyes, in particular neutral, cationic or anionic anthraquinone dyes, neutral, cationic or anionic azine direct dyes, neutral, cationic or anionic triarylmethane direct dyes, neutral, cationic or anionic azomethine direct dyes and natural direct dyes. Preferably, the direct dyes are selected from neutral or anionic anthraquinone dyes and stilbenes.

[0026] As neutral, anionic or cationic direct dyes which can be used in the present invention, mention may be made of the following dyes: acridines; acridones; anthranthrones; anthrapyrimidines; anthraquinones; azines; (poly)azo; hydrazonos or hydrazones, in particular arylhydrazones; azomethines; benzanthrones; benzimidazoles; benzimidazolones; benzindoles; benzoxazoles; benzopyrans; benzothiazoles; benzoquinones; bisazines; bis-isoindolines; carboxanilides; coumarins; cyanines such as azacarbocyanines, diazacarbocyanines, diazahemicyanines, hemicyanines or tetraazacarbocyanines; diazines; diketopyrrolopyrroles; dioxazines; diphenylamines; diphenylmethanes; dithiaazines; flavonoids such as flavanthrones and flavones; fumarates. fluorindines; formazans; indamines; indanthrones; indigoids and pseudoindigoids; indophenols; indoanilines; isoindolines; isoindolinones; isoviolanthrones; lactones; (poly)methines such as dimethines of the stilbene or styryl type; naphthalimides; naphthanilides; naphtholactams; naphthoquinones; nitro, especially nitro(hetero)aromatics; oxadiazoles; oxazines, perilones; perinones; perylenes; phenazines; phenoxazines; phenothiazines; phthalocyanines; polyenes / carotenoids; porphyrins; pyranthrones; pyrazoloanthrones; pyrazolones; pyrimidinoanthrones; pyronines; quinacridones; quinolines; quinophthalones; squalanes; tetrazoles; thiazines; thioindigo; thiopyronines; triarylmethanes; or xanthenes.

[0027] neutral direct dye The direct dyes b) may preferably be neutral direct dyes selected from hydrazono dyes of formulae (IIIa) and (III'a), azo and styryl dyes (IVa), diazo and distyryl dyes (IV'a) and (IV''a), anthraquinone dyes (Va), and azomethine dyes (VIa) and (VI'a), and mixtures thereof, of the formulae (IIIa) and (III'a) shown below:

[0028] [ka] (In formulas (IIIa), (III'a), (IVa), (IV'a), (IV''a), (Va), (VIa), and (VI'a), □ Ar represents an aryl group such as phenyl or naphthyl substituted with at least one electron donating group, for example i) optionally substituted (C1-C8) alkyl, ii) optionally substituted (C1-C8) alkoxy, iii) (di)(C1-C8) (alkyl) amino, wherein the alkyl group is optionally substituted with a hydroxyl group, iv) aryl(C1-C8) alkylamino, v) optionally substituted N-(C1-C8) alkyl-N-aryl(C1-C8) alkylamino, or Ar represents a julolidine group; Ar' represents an optionally substituted divalent (hetero)arylene group, such as phenylene, in particular paraphenylene, or naphthalene, optionally substituted, preferably with one or more (C1-C8)alkyl, hydroxyl, or (C1-C8)alkoxy groups; □ Ar″ represents a (hetero)aryl group, preferably optionally substituted with at least i) an electron-withdrawing group such as nitro, nitroso, -C(X)-X′-R′, or ii) a (di)(C1-C6)(alkyl)amino group, iii) hydroxyl, iv) (C1-C6)alkoxy; in particular (hetero)aryl is selected from imidazolyl, triazolyl, indolyl, or pyridyl, or phenyl optionally substituted with at least one group selected from nitro, nitroso, and amino, preferably substituting the para position of the phenyl group; □ X, X', and X'' may be the same or different and represent an oxygen or sulfur atom or an NR'' group, preferably an oxygen atom; □ R 1 , R 2 , R 3 , and R 4may be the same or different and represent a hydrogen or halogen atom, or a group selected from hydroxyl, thiol, (C1-C4) alkyl, (C1-C4) alkoxy, (di)(C1-C4) (alkyl) amino, nitro, and nitroso; □ R' and R'' represent a (C1-C4) alkyl group; □ R a and R b may be the same or different and represent a hydrogen atom or a (C1-C8) alkyl group optionally substituted, preferably with a hydroxyl group; Or, as a variation, the substituent R a is a substituent of Ar″ and / or R b is a substituent of Ar and / or R a R b together with the atom to which they are attached form a (hetero)cycloalkyl; In particular, R a and R b represents a hydrogen atom or a (C1-C4) alkyl group optionally substituted with a hydroxyl group; □ T and T' may be the same or different, and C(R a ) group or N, preferably N; L represents the divalent group -ALK-, -C(X)-ALK-, -ALK-C(X)-, or -C(X)-ALK-C(X')-, where ALK represents a linear or branched (C1-C6) alkylene group, such as methylene, and X and X' are as defined above; □ R 22 , R 23 , R 24 , R 25 , R 26 , and R 27 may be the same or different and represent a hydrogen or halogen atom or one of the following: - (C1-C6) alkyl; - hydroxyl, mercapto; - (C1-C6)alkoxy, (C1-C6)alkylthio; - aryloxy or arylthio; - aryl(C1-C6)(alkyl)amino; - (di)(C1-C6)(alkyl)amino; - (di)(hydroxy(C1-C6)alkyl)amino; is selected from □ Z' is a hydrogen atom or NR 28 R 29 group (in the formula, R 28 and R 29 may be the same or different and represent a hydrogen atom or a group shown below: - (C1-C6) alkyl; - polyhydroxy(C1-C6)alkyl, such as hydroxyethyl; - aryl optionally substituted with one or more groups, in particular i) (C1-C6) alkyl; iii) R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X''-, where R° represents a (C1-C6) alkyl group and X, X' and X'' are as defined above; iv) sulfonate; - cycloalkyl, in particular cyclohexyl; represents a group selected from □ Z is hydroxyl and NR' 28 R' 29 (In the formula, R' 28 and R' 29 may be the same or different, and are R 28 and R 29 represents the same atom or group as

[0029] The direct dye b) of formula (IV″a) preferably has the formula (IV″′a): [ka] (In formula (IV'''a), □ R 1 and R 3 may be the same or different, preferably the same, and represent a hydrogen atom, a (C1-C4) alkyl group such as methyl, or a sugar such as glucosyl, preferably a hydrogen atom; □ R 2 and R 4 may be the same or different, preferably the same, and represent a hydrogen atom, a (C1-C4) alkyl or (C1-C4) alkoxy group, or an -O-sugar group such as -O-glucosyl, preferably a (C1-C4) alkoxy such as methoxy; □ X may be the same or different, preferably the same, and represents an oxygen or sulfur atom or NR, where R represents a hydrogen atom or any group, preferably an oxygen atom; □ ALK represents a (C1-C4) alkylene group such as methylene or ethylene, preferably methylene.

[0030] The direct dyes of formula (IV''a) can be derived from curcumin, demethoxycurcumin, and bisdemethoxycurcumin.

[0031] Preferably, the direct dyes b) are selected from the direct dyes of formulae (IV''a) and (IV'''a) defined above, and mixtures thereof.

[0032] According to a particularly preferred embodiment, the direct dye b) is a neutral direct dye selected from the following compounds (A) to (G) and mixtures thereof:

[0033] [ka] Preference is given to neutral direct dyes selected from compounds (E), (F) and (G) and mixtures thereof, and more preferentially from compounds (E) and (G) and mixtures thereof.

[0034] Cationic Direct Dyes The direct dyes b) can be selected from those direct dyes which are generally called "basic dyes" because they are cationic or have an affinity for acidic substances, in particular those which contain at least one endocyclic or exocyclic cationic or cationizable group in their structure.

[0035] As cationic azo dyes that can be used in the present invention, mention may be made in particular of the cationic dyes described in Kirk-Othmer's Encyclopedia of Chemical Technology, "Dyes, Azo", J. Wiley & Sons, revised on April 19, 2010.

[0036] Mention may also be made of the cationic azo dyes described in patent applications WO 95 / 15144, WO 95 / 01772 and EP 714954.

[0037] Mention may also be made of the cationic azo dyes described in the Colour Index International, 3rd edition, in particular the following compounds: Basic Red 22; Basic Red 76; Basic Yellow 57; Basic Brown 16; Basic Brown 17.

[0038] Among the cationic quinone dyes, those mentioned in the Colour Index International, 3rd edition are suitable, among which the following dyes may be mentioned in particular: Basic Blue 22; Basic Blue 99.

[0039] Among suitable azine dyes, mention may be made of those listed in the Color Index International, 3rd edition, such as the following dyes: Basic Blue 17, Basic Red 2.

[0040] Among the cationic triarylmethane dyes which can be used according to the invention, in addition to those listed in the Color Index International, 3rd edition, mention may be made of the following dyes: Basic Green 1, Basic Violet 3, Basic Violet 14, Basic Blue 7, Basic Blue 26.

[0041] Mention may also be made of the direct dyes described in documents U.S. Pat. No. 5,888,252, EP 1,133,975, WO 03 / 029359, EP 860,636, WO 95 / 01772, WO 95 / 15144 and EP 714,954.

[0042] Mention may also be made of those listed in the encyclopedia "The Chemistry of Synthetic Dyes" by K. Venkataraman, 1952, Academic Press, vol. 1-7; the chapter "Dyes and Dye Intermediates" in "Kirk-Othmer's Encyclopedia of Chemical Technology", 1993, Wiley and Sons; and various chapters in "Ullmann's Encyclopedia of Industrial Chemistry", 7th edition, Wiley and Sons.

[0043] Preferably, the cationic direct dyes are chosen from those obtained from the azo and hydrazono type dyes.

[0044] Cationic direct dyes are disclosed in European Patent No. 850636, French Patent No. 2788433, European Patent No. 920856, International Publication No. WO 99 / 48465, French Patent No. 2757385, European Patent No. 850637, European Patent No. 918053, International Publication No. WO 97 / 44004, French Patent No. 2570946, French Patent No. 2285851, German Patent No. 2538363, French Patent No. 2189006, French Patent No. 1560664, French Patent No. 1540423, French Patent No. 1567219, French Patent No. 1516943, French Patent No. Japanese Patent No. 1221122, German Patent No. 4220388, German Patent No. 4137005, International Publication No. 01 / 66646, U.S. Patent No. 5708151, International Publication No. 95 / 01772, International Publication No. 515144, British Patent No. 1195386, U.S. Patent No. 3524842, U.S. Patent No. 5879413, European Patent No. 1062940, European Patent No. 1133976, British Patent No. 738585, German Patent No. 2527638, French Patent No. 2275462, British Patent Application Publication No. 1974-27645, Acta Histochem, (1978), 61(1), 48-52; Tsitologiya (1968), 10 (3), 403-5; Zh. Obshch. Khim., (1970), 40 (1), 195-202; Ann. Chim. Chemical Society(Taipei)(1998),45(1),209-211;Rev.Roum.Chim.(1988),33(4),377-83;Text.Res.J.(1984),54(2),105-7;Chim .Ind.(Milan)(1974),56(9),600-3;Khim.Tekhnol.(1979),22(5),548-53;Ger.Monatsh.Chem.(1975),106(3),643-8;MRL Bull.Res.Dev.(1992), 6(2), 21-7; Lihua Jianyan, Huaxue Fence (1993), 29(4), 233-4; Dyes Pigm. (1992), 19(1), 69-79; Dyes Pigm. (1989), 11(3), 163-72.

[0045] Preferably, the cationic direct dye comprises a quaternary ammonium group; more preferentially, the cationic charge is within the ring. This cationic group can be, for example: - a cationic group having an exocyclic (di / tri)(C1-C8) alkyl ammonium charge; or - Endocyclic charges, for example: acridinium, benzimidazolium, benzobistriazolium, benzopyrazolium, benzopyridazinium, benzoquinolium, benzothiazolium, benzotriazolium, benzoxazolium, bipyridinium, bis-tetrazolium, dihydrothiazolium, imidazopyridinium, imidazolium, indolium, isoquinolium, naphthimidazolium, naphthoxazolium, naphthopyrazolium, oxadiazolium, oxazolium, o The cationic group has an intracyclic charge and comprises a cationic heteroaryl group selected from oxazolopyridinium, oxonium, phenazinium, phenoxazolium, pyrazinium, pyrazolium, pyrazoyltriazolium, pyridinium, pyridinoimidazolium, pyrrolium, pyrylium, quinolium, tetrazolium, thiadiazolium, thiazolium, thiazolopyridinium, thiazoylimidazolium, thiopyrylium, triazolium, or xanthylium.

[0046] Mention may also be made of the following hydrazonocationic direct dyes of the formulae (IIb) and (IIIb) and azo dyes of the formulae (IVb) and (Vb): Het + -C(R a )=NN(R b )-Ar,Q(IIb) - ; Het + -N(R a)-N=C(R b )-Ar,Q - (IIIb); Het + -N=N-Ar,Q(IVb); Ar + -N=N-Ar'',Q - (Vb); (In formulas (IIb)~(Vb): □ Het + represents a cationic heteroaryl group, such as imidazolium, indolium or pyridinium, optionally substituted, preferably with at least one (C1-C8) alkyl group, such as methyl, and preferentially carrying a cationic charge in the ring; □ Ar + represents an aryl group, such as phenyl or naphthyl, carrying an exocyclic cationic charge, preferentially ammonium, in particular tri(C1-C8)alkylammonium, such as trimethylammonium; □ Ar represents an aryl group, in particular phenyl, optionally substituted with one or more electron donating groups, such as i) optionally substituted (C1-C8) alkyl, ii) optionally substituted (C1-C8) alkoxy, iii) (di)(C1-C8) (alkyl) amino, in which the alkyl group is optionally substituted with a hydroxyl group, iv) aryl(C1-C8) alkylamino, v) optionally substituted N-(C1-C8) alkyl-N-aryl(C1-C8) alkylamino, or Ar represents a julolidine group; □ Ar″ represents an optionally substituted (hetero)aryl group, such as phenyl or pyrazolyl, preferentially optionally substituted with one or more (C1-C8)alkyl, hydroxyl, (di)(C1-C8)(alkyl)amino, (C1-C8)alkoxy or phenyl groups; □ R a and R b may be identical or different and represent a hydrogen atom or a (C1-C8) alkyl group optionally and preferentially substituted with a hydroxyl group; □ Or, the substituent Ra Het + and / or R b is a substituent of Ar and / or R a R b together with the atom to which they are attached form a (hetero)cycloalkyl; in particular R a and R b represents a hydrogen atom or a (C1-C4) alkyl group optionally substituted with a hydroxyl group; □ Q - represents an anionic counterion such as a halide, alkyl sulfate, or alkyl sulfonate).

[0047] Mention may in particular be made of the azo and hydrazono direct dyes of formulae (IIb) to (Vb) having an internal cationic charge in the ring as defined above, more particularly the cationic direct dyes of formulae (IIb) to (Vb) having an internal cationic charge in the ring as described in WO 95 / 15144, WO 95 / 01772 and EP 714954.

[0048] Preferably, the following direct dyes may be mentioned: [ka] (In formulas (II-1) and (IV-1), □ R 1 represents a (C1-C4) alkyl group such as methyl; □ R 2 and R 3 may be the same or different and represent a hydrogen atom or a (C1-C4) alkyl group such as methyl; □ R 4 represents a hydrogen atom or an electron donating group, such as an optionally substituted (C1-C8) alkyl, an optionally substituted (C1-C8) alkoxy, or a (di)(C1-C8) (alkyl) amino, in which the alkyl group is optionally substituted with a hydroxyl group; in particular R 4 is a hydrogen atom, □ Z represents a CH group or a nitrogen atom, preferentially CH; □ Q - is an anionic counterion as defined above, especially a halide such as chloride or an alkyl sulfate such as methyl sulfate or mesityl).

[0049] In particular, the dyes of formulae (II-1) and (IV-1) are selected from Basic Red 51, Basic Yellow 87, and Basic Orange 31, or derivatives thereof: [ka] where Q' is an anionic counterion as defined above, in particular a halide such as chloride, or an alkyl sulfate such as methyl sulfate or mesityl.

[0050] Fluorescent dyes The direct dye b) may be selected from fluorescent direct dyes.

[0051] Examples of fluorescent dyes that can be used in the present invention include neutral, anionic or cationic dyes selected from the following dyes: acridine, acridone, benzanthrone, benzimidazole, benzimidazolone, benzindole, benzoxazole, benzopyran, benzothiazole, coumarin, difluoro{2-[(2H-pyrrol-2-ylidene-kN)methyl]-1H-pyrrolato-kN}boron (BODIPY®), diketopyrrolopyrrole, fluorindine, (poly)methines (especially cyanines and styryl / hemicyanines), naphthalimides, naphthanilides, naphthylamines (such as dansyl), oxadiazoles, oxazines, perylones, perinones, perylenes, polyenes / carotenoids, squalanes, stilbenes, xanthenes.

[0052] Fluorescent dyes described in EP 1133975, WO 03 / 029359, EP 860636, WO 95 / 01772, WO 95 / 15144, and EP 714954, as well as in the encyclopedia "The Chemistry of Synthetic Dyes" by K. Venkataraman, 1952, Academic Press, vol. 1-7, the chapter "Dyes and Dye Intermediates" in "Kirk-Othmer's Encyclopedia of Chemical Technology", 1993, Wiley and Sons, various chapters in "Ullmann's Encyclopedia of Industrial Chemistry", 7th edition, Wiley and Sons, and in the handbook "A Guide to Fluorescent Probes and Labeling Technologies", 10th Ed., Molecular Chemistry, circulated on the Internet or in print. Probes / Invitrogen-Oregon 2005 may also be mentioned.

[0053] According to a preferred variant, the fluorescent dye is a cationic polymethine containing at least one quaternary ammonium group, such as that of the following formula (Vb): W + -[C(R c )=C(R d )] m’ -Ar,Q - (In formula (Vb), □ W + represents a cationic heterocyclic or heteroaryl group, in particular containing a quaternary ammonium, which is optionally substituted, in particular with one or more (C1-C8) alkyl groups, which are optionally substituted with one or more hydroxyl groups; □ Ar represents an aryl group such as phenyl or naphthyl, preferably an aryl group optionally substituted with i) one or more halogen atoms such as chlorine or fluorine; ii) one or more (C1-C8) alkyl, preferably (C1-C4) alkyl, groups such as methyl; iii) one or more hydroxyl groups; iv) one or more (C1-C8) alkoxy groups such as methoxy; v) one or more hydroxy(C1-C8) alkyl groups such as hydroxyethyl; vi) one or more (di)(C1-C8) alkylamino groups, in which one or more amino groups or the C1-C4 alkyl moieties thereof are optionally substituted, preferably with one or more hydroxyl groups, e.g. (di)hydroxyethylamino; vii) one or more acylamino groups; viii) one or more heterocycloalkyl groups, e.g. piperazinyl, piperidyl, or 5- or 6-membered heteroaryl, e.g. pyrrolidinyl, pyridyl, and imidazolinyl; m' represents an integer ranging from 1 to 4, preferably m' is 1 or 2; more preferably m'=1; □ R c and R d are the same or different and represent a hydrogen atom or an optionally substituted (C1-C8) alkyl group, preferentially a (C1-C4) alkyl group, or W + and adjacent R c and / or R adjacent to Ar d together with the atom to which they are attached form a (hetero)cycloalkyl; in particular R c W + and adjacent to each other, which form a (hetero)cycloalkyl, such as cyclohexyl; □ Q - is the anionic counterion defined above).

[0054] Anionic Dyes The direct dyes b) can be chosen from anionic direct dyes or from dyes which are generally called "acid" direct dyes due to their affinity for alkaline substances.

[0055] The term "anionic direct dye" is intended to mean any direct dye that contains in its structure at least one CO2R or SO3R substituent, where R represents a hydrogen atom or a cation or an ammonium ion derived from a metal or an amine. The anionic dye may be chosen from acid nitro direct dyes, acid azo dyes, acid azine dyes, acid triarylmethane dyes, acid indoamine dyes, acid anthraquinone dyes, indigoids and acid natural dyes.

[0056] Preferably, the anionic direct dye is an acidic anthraquinone.

[0057] The direct dye b) may be an anionic direct dye, preferably selected from the group consisting of the following formulae (III), (III'), (IV), (IV'), (V), (V'), (VI), (VI'), (VII), (VIII), (IX) and (X), and mixtures thereof:

[0058] a) Anionic diarylazo dyes of formula (III) or (III'): [ka] (In formulas (III) and (III'): □ R7, R8, R9, R 10 , R'7, R'8, R'9, and R' 10 may be the same or different and represent a hydrogen atom or one of the following groups: - (C1-C6) alkyl; - (C1-C6)alkoxy, (C1-C6)alkylthio; - hydroxyl, mercapto; - Nitro, nitroso; - R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X''- (wherein R° represents a hydrogen atom or a (C1-C6) alkyl group or an aryl group such as phenyl; X, X', and X'' may be the same or different and represent an oxygen or sulfur atom or NR (wherein R represents a hydrogen atom or a (C1-C6) alkyl group)); - (O)2S(O - )-,M + (In the formula, M + represents a hydrogen atom or a cationic counter ion); - (O)CO - -,M + (In the formula, M + is as defined above); - R"-S(O)2-, where R" represents a hydrogen atom, an alkyl group, or an aryl, (di)(C1-C6)(alkyl)amino or aryl(C1-C6)(alkyl)amino group; preferentially a phenylamino or phenyl group; - R'''-S(O)2-X'-, where R''' represents an optionally substituted (C1-C6) alkyl or aryl group, and X' is as defined above; - (di)(C1-C6)(alkyl)amino; - i) nitro; ii) nitroso; iii) (O)2S(O - )-,M + (In the formula, M + is as defined above), and iv) (C1-C6) alkoxy; aryl(C1-C6) (alkyl) amino optionally substituted with one or more groups selected from: - optionally substituted heteroaryl; preferentially a benzothiazolyl group; - cycloalkyl, in particular cyclohexyl; - Ar-N=N- (wherein Ar represents an optionally substituted aryl group; preferentially one or more alkyl, (O)S(O - )-,M + or phenyl optionally substituted with a phenylamino group; or - or two adjacent groups R7 and R8 or R8 and R9 or R9 and R 10 together form a fused benzo group A'; R'7 and R'8 or R'8 and R'9 or R'9 and R' 10 together form a fused benzo group B'; A' and B' are i) nitro; ii) nitroso; iii) (O)S(O - )-,M + iv) hydroxyl; 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) optionally substituted aryl(C1-C6)(alkyl)amino, where M + , R°, X, X′, X″, and Ar are as defined above; □ W is a sigma σ bond, an oxygen or sulfur atom, or a divalent group i) -NR- (wherein R is as defined above) or ii) methylene-C(R a )(R b )-(wherein, R a and R b may be the same or different and represent a hydrogen atom or an aryl group, or R a and R b together with the carbon atom to which they are attached form a spirocycloalkyl; preferentially, W represents a sulfur atom or R a and R b together to form cyclohexyl; With the proviso that formulas (III) and (III') have on one of rings A, A', B, B', or C: - At least one (O)S(O - )-,M' + group (in the formula, M' + represents a cationic counterion); or - at least one (O)CO - -,M' + group (in the formula, M' + represents a cationic counterion); Preferably, at least one sodium sulfonate group; (It is understood that this includes.)

[0059] Examples of dyes of formula (III) are: 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 Olefin Acid Orange 6, Acid Orange 7, Acid Orange 10, Acid Orange 19, Acid Orange 20, Acid Orange 24, Yellow 5, 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 or Sunset Yellow, Examples of dyes of formula (III') include: Acid Red 111, Acid Red 134, Acid Yellow 38.

[0060] b) Anionic pyrazolone azo dyes of formula (IV) and (IV'): [ka] (In formulas (IV) and (IV'): □ R 11 , R 12 , and R 13 may be the same or different and represent hydrogen, a halogen atom, a (C1-C6) alkyl, or -(O)2S(O - ),M + group (in the formula, M +is as defined above); □ R 14 is a hydrogen atom, a (C1-C6) alkyl group, or -C(O)O - ,M + group (in the formula, M + is as defined above); □ R 15 represents a hydrogen atom; □ R 16 represents an oxo group, in which case R' 16 does not exist, or R 15 R 16 together to form a double bond; □ R 17 and R 18 may be the same or different and represent a hydrogen atom, or: - (O)2S(O - )-,M + (In the formula, M + is as defined above); - Ar-OS(O)2-, where Ar represents an optionally substituted aryl group, preferentially a phenyl optionally substituted with one or more alkyl groups; represents a group selected from □ R 19 and R 20 taken together form either a double bond or an optionally substituted benzo group D'; □ R' 16 , R' 19 , and R' 20 may be the same or different and represent a hydrogen atom, or a (C1-C6) alkyl or hydroxyl group; □ R 21 represents a hydrogen atom, or a (C1-C6) alkyl or (C1-C6) alkoxy group; □ R a and R b may be identical or different and are as defined above; preferentially, R a represents a hydrogen atom, and R b represents an aryl group such as phenyl; □ Y represents either a hydroxyl group or an oxo group; □ [ka] represents a single bond when Y is an oxo group; represents a double bond when Y is a hydroxyl group; With the proviso that formulae (IV) and (IV') have on one of rings D or E: - At least one (O)S(O - )-,M' + group (in the formula, M' + represents a cationic counterion); or - at least one (O)CO - -,M' + group (in the formula, M' + represents a cationic counterion); Preferably, at least one sodium sulfonate group; (It is understood that this includes.)

[0061] As examples of dyes of formula (IV) there may be mentioned: Acid Red 195, Acid Yellow 23, Acid Yellow 27, Acid Yellow 76, and as examples of dyes of formula (IV'): Acid Yellow 17.

[0062] c) Anthraquinone dyes of formula (V) or (V'): [ka] (In formulas (V) and (V'): □ R 22 , R 23 , R 24 , R 25 , R 26 and R 27 may be the same or different and represent a hydrogen or halogen atom, or: - (C1-C6) alkyl; - hydroxyl, mercapto; - (C1-C6)alkoxy, (C1-C6)alkylthio; Preferentially alkyl and (O)S(O - )-,M + (In the formula, M + is as defined above); - Alkyl and (O)2S(O - )-,M + (In the formula, M + is as defined above); - (di)(C1-C6)(alkyl)amino; - (di)(hydroxy(C1-C6)alkyl)amino; - (O)2S(O - )-,M + (In the formula, M + is as defined above); is selected from □ Z' represents a hydrogen atom or NR 28 R 29 group (in the formula, R 28 and R 29 may be the same or different and represent a hydrogen atom, or - (C1-C6) alkyl; - polyhydroxy(C1-C6)alkyl, such as hydroxyethyl; - one or more groups, in particular i) (C1-C6) alkyl, such as methyl, n-dodecyl, n-butyl; ii) (O)2S(O - )-,M + (In the formula, M + is as defined above; iii) aryl optionally substituted with R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X''-, where R°, X, X', and X'' are as defined above and preferentially R° represents a (C1-C6) alkyl group; - cycloalkyl; in particular cyclohexyl; represents a group selected from □ Z is hydroxyl and NR' 28 R'29 (In the formula, R' 28 and R' 29 may be the same or different, and are R 28 and R 29 represents the same atom or group as wherein formulas (V) and (V') are: - At least one (O)S(O - )-,M' + group (in the formula, M' + represents a cationic counterion); or - at least one (O)CO - -,M' + group (in the formula, M' + represents a cationic counterion); Preferably, at least one sodium sulfonate group; (It is understood that this includes.)

[0063] Examples of dyes of formula (V) include 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 Violet No. 2; An example of the dye of formula (V') is Acid Black 48.

[0064] d) Nitro dyes of formula (VI) or (VI'): [ka] (In formulas (VI) and (VI'): □ R 30 , R 31 , and R 32 may be the same or different and represent a hydrogen or halogen atom or a group as shown below: - (C1-C6) alkyl; - (C1-C6)alkoxy optionally substituted with one or more hydroxyl groups or (C1-C6)alkylthio optionally substituted with one or more hydroxyl groups; - hydroxyl, mercapto; - Nitro, nitroso; - polyhalo(C1-C6)alkyl; - R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X''- (wherein R°, X, X', and X'' are as defined above); - (O)2S(O - )-,M + (In the formula, M + is as defined above) - (O)CO - -,M + (In the formula, M + is as defined above); - (di)(C1-C6)(alkyl)amino; - (di)(hydroxy(C1-C6)alkyl)amino; - heterocycloalkyl, such as piperidino, piperazino, or morpholino; represents a group selected from - In particular, R 30 , R 31 , and R 32 represents a hydrogen atom; □ R c and R d may be the same or different and represent a hydrogen atom or a (C1-C6) alkyl group; □ W is as defined above; in particular W represents the -N(H)- group; □ ALK represents a linear or branched divalent C1-C6 alkylene group; in particular, ALK represents a -CH2-CH2- group; □ n is 1 or 2; □ p represents an integer ranging from 1 to 5; □ q represents an integer ranging from 1 to 4; □ u is 0 or 1; □ When n is 1, J represents a nitro or nitroso group; in particular nitro; □ When n is 2, J is an oxygen or sulfur atom or a divalent group -S(O) m - (wherein m represents an integer 1 or 2); preferentially, J represents a -SO2- group; □ M″ represents a hydrogen atom or a cationic counterion; □ [ka] is optionally present and may be one or more R 30 represents a benzo group optionally substituted with a group; wherein formulas (VI) and (VI') are: - At least one (O)S(O - )-,M' + group (in the formula, M' + represents a cationic counterion); or - at least one (O)CO - -,M' + group (in the formula, M' + represents a cationic counterion); Preferably, at least one sodium sulfonate group; (It is understood that this includes.)

[0065] Examples of dyes of formula (VI) include Acid Brown 13 and Acid Orange 3; examples of dyes of formula (VI') include Acid Yellow 1, the 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)anilineethanesulfonic acid, 4-β-hydroxyethylamino-3-nitrobenzenesulfonic acid; Ext. D&C Yellow 7.

[0066] e) a triarylmethane dye of formula (VII): [ka] (In formula (VII), □ R33 , R 34 , R 35 , and R 36 may be the same or different and represent a hydrogen atom or a group selected from (C1-C6)alkyl, optionally substituted aryl and optionally substituted aryl(C1-C6)alkyl; in particular (C1-C6)alkyl groups and optionally (O) m S(O - )-,M + group (in the formula, M + and m is as defined above) represents a group selected from benzyl substituted with; □ R 37 , R 38 , R 39 , R 40 , R 41 , R 42 , R 43 , and R 44 may be the same or different and represent a hydrogen atom or one of the following groups: - (C1-C6) alkyl; - (C1-C6)alkoxy, (C1-C6)alkylthio; - (di)(C1-C6)(alkyl)amino; - hydroxyl, mercapto; - Nitro, nitroso; - R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X''- (wherein R° represents a hydrogen atom or an alkyl or aryl group; X, X', and X'' may be the same or different and represent an oxygen or sulfur atom, or NR (wherein R represents a hydrogen atom or a (C1-C6) alkyl group)); - (O)2S(O - )-,M + (In the formula, M + represents a hydrogen atom or a cationic counter ion); - (O)CO - -,M + (In the formula, M + is as defined above); or - or two adjacent groups R41 and R 42 or R 42 and R 43 or R 43 and R 44 together, i) nitro; ii) nitroso; iii) (O)2S(O - )-,M + iv) hydroxyl; v) mercapto; vi) (di)(C1-C6)(alkyl)amino; vii) R°-C(X)-X'-; viii) R°-X'-C(X)-; ix) R°-X'-C(X)-X''-, where M + , R°, X, X′, and X″ are as defined above); In particular, R 37 ~R 40 represents a hydrogen atom, R 41 ~R 44 may be the same or different and are a hydroxyl group or (O)S(O - )-,M + (In the formula, M + is as defined above); R 43 and R 44 taken together form a benzo group, this is preferentially (O)S(O - )-group; provided that at least one of rings G, H, or I is: - At least one (O)S(O - )-,M' + group (in the formula, M' + represents a cationic counterion); or - at least one (O)CO - -,M' + group (in the formula, M' + represents a cationic counterion); Preferably, at least one sodium sulfonate group; (It is understood that this includes.)

[0067] Examples of dyes of formula (VII) include Acid Blue 1; Acid Blue 3; Acid Blue 7; Acid Blue 9; Acid Violet 49; Acid Green 3; Acid Green 5; and Acid Green 50.

[0068] f) Xanthene dyes of formula (VIII): [ka] (In formula (VIII): □ R 45 , R 46 , R 47 , and R 48 may be the same or different and represent a hydrogen atom or a halogen atom; □ R 49 , R 50 , R 51 , and R 52 may be the same or different and represent a hydrogen or halogen atom or a group as shown below: - (C1-C6) alkyl; - (C1-C6)alkoxy, (C1-C6)alkylthio; - hydroxyl, mercapto; - Nitro, nitroso; - (O)2S(O - )-,M + (In the formula, M + represents a hydrogen atom or a cationic counter ion); - (O)CO - -,M + (In the formula, M + is as defined above); represents a group selected from In particular, R 53 , R 54 , R 55 , and R 48 represents a hydrogen or halogen atom; □ G is an oxygen or sulfur atom or NR e group (in the formula, R e is as defined above); in particular, G represents an oxygen atom; □ L is alkoxide O - ,M + ;Thioalkoxide S - ,M + , or NR f group (in the formula, R f represents a hydrogen atom or a (C1-C6) alkyl group, M + is as defined above; M + is in particular sodium or potassium); □ L' is an oxygen or sulfur atom or an ammonium group: N + R f R g (In the formula, R f and R g may be the same or different and represent a hydrogen atom, a (C1-C6) alkyl group, or an optionally substituted aryl group; in particular L' represents an oxygen atom or one or more alkyl or (O) m S(O - )-,M + Groups (wherein m and M + represents a phenylamino group optionally substituted with (as defined above); Q and Q' may be the same or different and represent an oxygen or sulfur atom; in particular Q and Q' represent an oxygen atom; □ M + is as defined above).

[0069] Examples of dyes of formula (VIII) include: Acid Yellow 73, Acid Red 51, Acid Red 52; Acid Red 87, Acid Red 92, Acid Red 95, and Acid Violet 9.

[0070] g) Indole dyes of formula (IX): [ka] (In formula (IX), □ R 53 , R 54 , R 55 , R 56 , R 57 , R58 , R 59 , and R 60 may be the same or different and represent a hydrogen atom or a group as shown below: - (C1-C6) alkyl; - (C1-C6)alkoxy, (C1-C6)alkylthio; - hydroxyl, mercapto; - Nitro, nitroso; - R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X''- (wherein R° represents a hydrogen atom or an alkyl or aryl group; X, X', and X'' may be the same or different and represent an oxygen or sulfur atom, or NR (wherein R represents a hydrogen atom or a (C1-C6) alkyl group)); - (O)2S(O - )-,M + (In the formula, M + represents a hydrogen atom or a cationic counter ion); - (O)CO - -,M + (In the formula, M + is as defined above); represents a group selected from □ G is an oxygen or sulfur atom or NR e group (in the formula, R e is as defined above); in particular, G represents an oxygen atom; □ R i and R h may be the same or different and represent a hydrogen atom or a (C1-C6) alkyl group; However, formula (IX) is: - At least one (O)S(O - )-,M' + group (in the formula, M' + represents a cationic counterion); or - at least one (O)CO - -,M' + group (in the formula, M' + represents a cationic counterion); Preferably, at least one sodium sulfonate group; (It is understood that this includes.)

[0071] An example of a dye of formula (IX) is Acid Blue 74.

[0072] h) Quinoline dyes of formula (X): [ka] (In formula (X): □ R 61 represents a hydrogen atom, a halogen atom, or a (C1-C6) alkyl group; □ R 62 , R 63 , and R 64 may be the same or different, and are a hydrogen atom or (O)S(O - )-,M + group (in the formula, M + represents a hydrogen atom or a cationic counterion; or R 61 and R 62 or R 61 and R 64 together form one or more (O)S(O - )-,M + group (in the formula, M + represents a hydrogen atom or a cationic counterion), forming a benzo group optionally substituted with However, the formula (X) contains at least one (O)S(O - )-,M' + group (in the formula, M' + represents a cationic counterion), which is understood to preferably contain at least one sodium sulfonate group).

[0073] Examples of dyes of formula (X) include Acid Yellow 2, Acid Yellow 3, and Acid Yellow 5.

[0074] More specifically, the dyes of formulae (III)-(VIII) useful in the present invention are selected from the following: Acid Red 87 (VIII) (CI 45380); the sodium salt of 2,4-dinitro-1-naphthol-7-sulfonic acid (VI') (CI 10316); Acid Orange 3 (VI) (CI 10383); Acid Yellow 9 / Food Yellow 2 (III) (CI 13015); Direct Red 45 / Food Red 13 (III) (CI 14780); Acid Black 52 (II I) (CI13711); Acid Yellow 36 (III) (CI13065); 1-Hydroxy-2-(2',4'-xylyl-5-sulfonatoazo)naphthalene-4-sulfonic acid, sodium salt / Food Red 1 (III) (CI14700); Acid Red 14 / Food Red 3 / Mordant Blue 79 (III) (CI14720); 4-Hydroxy-3-[(2-methoxy-5-nitrophenyl)diaza]-6-(phenylamino)naphthalene-2-sulfonic acid, sodium salt / Acid Brown 4(III)(CI14805);Acid Orange 7 / Pigment Orange 17 / Solvent Orange 49(III)(CI15510);Food Yellow 3 / Pigment Yellow 104(III)(CI15985);Acid Red 27 / Food Red 9(III)(CI16185);Acid Orange 10 / Food Orange 4(III)(CI16230);Acid Red 44(III)(CI16250);Acid Red 33 / Food Red 12(III)(CI172 00;Acid Red 184(III)(CI15685);Acid Violet 3(III)(CI19125);1-Hydroxy-2-(4'-acetamidophenylazo)-8-acetamidonaphthalene-3,6-disulfonic acid, sodium salt / Acid Violet 7 / Food Red 11(III)(CI18055);Acid Red 135(III)(CI18130);Acid Yellow 27(IV)(CI19130);Acid Yellow 23 / Food Yellow 4(IV)(CI19140;4'-(sulfonato-2",4"-dimethyl)-bis-(2,6-phenylazo)-1,3-dihydroxybenzene / Acid Orange 24(III)(CI20170);1-amino-2-(4'-nitrophenylazo)-7-phenylazo-8-hydroxynaphthalene-3,6-disulfonic acid sodium salt / Acid Black 1(III)(CI20470);(4-((4-methylphenyl)sulfonyloxy)phenylazo)-2,2'-dimethyl-4-((2-hydroxy-5,8-disulfonic acid) 1-(4'-sulfonatophenylazo)-4-((2”-hydroxy-3”-acetylamino-6”,8”-disulfonato)naphthylazo)-6-sulfonatonaphthalene (tetrasodium salt) / Food Black 1(III)(CI25440);Acid Blue 9(VII)(CI42090);Acid Violet 43(V)(CI60730);Acid Green 25(V)(CI61570);1-amino-4-cyclohexylamino-9,10-anthraquinone-2-sulfonic acid, sodium salt / Acid Blue 62(V)(CI62045);Acid Blue 78(V)(CI62105);4-hydroxy-3-((2-methoxyphenyl)azo)-1-naphthalenesulfonic acid, sodium salt / Acid Red 4(III)(CI14710);2-piperidino-5-nitrobenzenesulfonic acid(VI');2(4'-N,N(2"-hydroxyethyl)amino-2'-ni 4-β-Hydroxyethylamino-3-nitrobenzenesulfonic acid (VI'); Acid Violet 49 (VII) (CI 42640); Acid Blue 7 (VII) (CI 42080); 1,2-Dihydroxy-3-sulfoanthraquinone sodium salt / Mordant Red 3 (V) (CI 58005); 1-Amino-9,10-dihydro-9,10-dioxo-4-(phenylamino) 2-anthracenesulfonic acid sodium salt / Acid Blue 25 (V) (CI62055);4-hydroxy-3-((2-methoxyphenyl)azo)-1-naphthalenesulfonic acid, sodium salt / Acid Red 4(III)(CI14710).

[0075] Most of these dyes are described in particular in the Colour Index published by the Society of Dyers and Colourists, PO Box 244, Perkin House, 82 Grattan Road, Bradford, Yorkshire, BD1 2JBN England.

[0076] Particularly the most preferred anionic dyes are those designated in the Color Index by the numbers 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-1-anthracenyl)amino]-5-methylbenzenesulfonic acid), CI 15510 (monosodium salt of 4-[(2-hydroxy-1-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 ... It is a dye designated by the following formulas: CI 20470 (1-amino-2-(4'-nitrophenylazo)-7-phenylazo-8-hydroxy-3,6-naphthalenedisulfonic acid, disodium salt), CI 42090 (N-ethyl-N-[4-[[4-[ethyl(3-sulfophenyl)methyl]amino]phenyl](2-sulfophenyl)methylene]-2,5-cyclohexadien-1-ylidene]-3-sulfobenzenemethanaminium hydroxide, disodium salt, inner salt), and CI 61570 (2,2'-[(9,10-dihydro-9,10-dioxo-1,4-anthracenediyl)diimino]bis[5-methyl]benzenesulfonic acid, disodium salt).

[0077] Compounds corresponding to the mesomeric or tautomeric forms of structures (III)-(X) can also be used.

[0078] natural dyes The direct dyes may be selected from natural direct dyes.

[0079] Among the natural direct dyes which may be used according to the invention, mention may be made of lawsone, juglone, alizarin, purpurin, carminic acid, kermesic acid, purpurogallin, protocatechualdehyde, indigo, isatin, curcumin, spinulosin, apigenidin, orcein, brazilin, brazilein, hematein and hematoxylin. Extracts or decoctions containing these natural dyes may also be used, in particular henna-based poultices or extracts.

[0080] According to a preferred embodiment, the direct dye b) is selected from the triarylmethane direct dyes of formulae (IIa1) and (IIa2) and mixtures thereof:

[0081] [ka] (In the formula, R1, R2, R3 and R4 may be the same or different and represent a hydrogen atom or one of the following groups: (C1-C6) alkyl, preferably optionally substituted with a hydroxyl group; aryl, such as phenyl; aryl(C1-C4) alkyl, such as benzyl; heteroaryl; heteroaryl(C1-C4) alkyl; or two groups R1 and R2 and / or R3 and R4, bound to the same nitrogen atom, together with the nitrogen atom to which they are bound, form an optionally substituted heterocycloalkyl group, such as morpholino, piperazino or piperidino, preferably R1, R2, R3 and R4 may be the same or different and represent a hydrogen atom or a (C1-C4) alkyl group; □ R5, R6, R7, R8, R9, R 10 , R11 , R 12 , R 13 , R 14 , R 15 , and R 16 are the same or different and represent a hydrogen or halogen atom or are the following groups: i) hydroxyl; ii) thiol; iii) amino; iv) (di)(C1-C4)(alkyl)amino; v) (di)arylamino, such as (di)phenylamino; vi) nitro; vii) acylamino (-NR-C(O)R'), where the R groups are hydrogen atoms, C1-C4 alkyl groups optionally carrying at least one hydroxyl group and the R' groups are C1-C2 alkyl groups; viii) carbamoyl ((R)2N-C(O)-), where the R groups are the same or different and represent a hydrogen atom or a C1-C4 alkyl group optionally carrying at least one hydroxyl group; ix) carboxylic acids or esters (-OC(O)R') or (-C(O)OR'), where the R' group is a hydrogen atom or a C1-C4 alkyl group optionally carrying at least one hydroxyl group, the R' group being a C1-C2 alkyl group; x) an alkyl optionally substituted, in particular with a hydroxyl group; xi) an alkylsulfonylamino (R'SO2-NR-), in which the R group represents a hydrogen atom or a C1-C4 alkyl group optionally carrying at least one hydroxyl group, the R' group represents a C1-C4 alkyl group, a phenyl group; xii) an aminosulfonyl ((R)2N-SO2-), in which the R groups, which may be identical or different, represent a hydrogen atom or a C1-C4 alkyl group optionally carrying at least one hydroxyl group; xiii) a (C1-C4)alkoxy; and xiv) a (C1-C4)alkylthio; □ Or, two groups R5 and R6 and / or R7 and R8 and / or R9 and R 10 and / or R 11 and R 12 and / or R 13 and R 14 and / or R 15 and R 16together with the carbon atom to which they are attached form a 6-membered fused ring which is aryl or heteroaryl, preferably benzo, which may be an optionally substituted, preferably unsubstituted, benzo ring; □ Q - represents an anionic counterion, preferably selected from halides, such as chloride or bromide, and phosphate, to achieve electroneutrality.

[0082] The direct dyes b) may preferably be selected 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, and HC Blue 15, and mixtures thereof.

[0083] More preferentially, the direct dye b) is HC Blue 15.

[0084] The direct dyes b) may be present in the composition in a total content ranging from 0.001% to 10% by weight, preferably in the range from 0.05% to 5% by weight and more preferentially in the range from 0.1% to 3% by weight relative to the total weight of the composition.

[0085] Heterocyclic salts of formula (A) The composition according to the invention comprises c) one or more compounds of formula (A): [ka] (In the formula, □ Het is: - 5 to 10 ring members, preferably 5 or 6 ring members; and - in addition to the ammonium to which R1 is attached, 1 or 2 atoms selected from nitrogen or oxygen atoms, preferably nitrogen atoms; represents a cationic aromatic unsaturated heterocyclic group comprising The heterocyclic group is optionally substituted with one or more R'1 or R2 groups; R1 and R'1 may be the same or different and may be selected from linear or branched, saturated or unsaturated C1-C alkyl groups, optionally substituted with one or more groups selected from, in particular, hydroxyl, amino, (C1-C6)dialkylamino, (C1-C6)alkylamino, carboxyl, carboxylate, carbamido, (C1-C4)alkoxy, -SO3H, sulfonate, and phenyl. 12 represents a hydrocarbon group; □ R2 is a hydroxyl group; an amino group; optionally, in particular, a linear or branched, saturated or unsaturated C1-C alkyl group substituted with one or more groups selected from hydroxyl, amino, (C1-C6)dialkylamino, (C1-C6)alkylamino, carboxyl, carboxylate, carbamido, (C1-C4)alkoxy, -SO3H, sulfonate, and phenyl. 12 represents a hydrocarbon group; □ Y - represents an anionic counterion; however: - if one of the hydrocarbon-based groups of R1, R'1 or R2 is substituted by a carboxylate or sulfonate group, Y is preferably substituted by a carboxylate or sulfonate group, so that the electroneutrality of the salt of formula (A) is maintained; - is not present).

[0086] Preferably, the salt of formula (A) has the following formula (I): [ka] (In formula (I), □ R1 is a linear or branched, saturated or unsaturated C1-C alkyl group optionally substituted with one or more groups selected from hydroxyl, amino, (C1-C6)dialkylamino, (C1-C6)alkylamino, carboxyl, carboxylate, carbamido, (C1-C4)alkoxy, -SO3H, sulfonate, and phenyl; 12 represents a hydrocarbon group; □ R'1 is a hydrogen atom; a linear or branched, saturated or unsaturated (C1-C) alkyl group optionally substituted with one or more groups selected from hydroxyl, amino, (C1-C6) dialkylamino, (C1-C6) alkylamino, carboxyl, carboxylate, carbamido, (C1-C4) alkoxy, -SO3H, sulfonate, and phenyl. 12 ) represents a hydrocarbon group; □ R2 is a hydroxyl group; a linear or branched, saturated or unsaturated C1-C alkyl group optionally substituted with one or more groups selected from hydroxyl, (C1-C4)alkoxy, -SO3H, sulfonate, and benzene. 12 represents a hydrocarbon group; n is 0, 1, 2, or 3; preferably, n is 0 or 1; □ Y - represents an anionic counter ion, however: - if one of the hydrocarbon-based groups of R1, R'1 or R2 is substituted by a carboxylate or sulfonate group, Y is preferably substituted by a carboxylate or sulfonate group, so that the electroneutrality of the salt of formula (A) is maintained; - does not exist, - when n is 2 or 3, the substituents are selected from:

[0087] According to one particular embodiment, the salt of formula (I) is one in which R'1 represents a hydrogen atom or is selected from the group consisting of hydroxyl, (C1-C2)alkoxy, -SO3H, -SO3 - and phenyl, preferably R'1 represents a hydrogen atom or a saturated, linear or branched, more preferentially linear C1-C6 hydrocarbon group, and even more preferentially R'1 represents a methyl group.

[0088] According to a particular embodiment, the salt of formula (I) is such that R2 represents a linear or branched saturated C1-C6 hydrocarbon-based group, such as methyl; preferably, n is 1 and R2 is in the 2-position.

[0089] According to a preferred embodiment of the present invention, the salt of formula (A) is selected from the following compounds 1 to 27 and mixtures thereof:

[0090] [ka] JPEG2024173970000024.jpg33170 (in the formula, Y - represents an anionic counter ion) Preferably, it is selected from compounds 2, 3, 4, 5 and 25 and mixtures thereof, more preferentially from compounds 2, 4, 5 and 25 and mixtures thereof, and even more preferentially from compound 4 and mixtures thereof.

[0091] According to a preferred embodiment of the invention, the salt of formula (A) is - i) halides such as chlorides or bromides, ii) hydrogen sulfates, iii) (bis)(poly)halo(C1-C2) compounds such as bis(trifluoromethylsulfonyl)imide and bis(fluorosulfonyl)imide, 12 ) (alkyl)sulfonylimides, iv) (C1-C 12 ) alkyl sulfates, v) (poly)halophosphates such as hexafluorophosphate, vi) (C1-C6) phosphates such as 12 ) (alkyl)phosphates, vii) (poly)haloborates such as tetrafluoroborate, viii) carbonates, ix) bicarbonates, x) (C1-C 12 ) alkyl carbonates, xi) dicyanamides, xii) nitrates, xiii) thiocyanates, xiv) formates, xv) their (C1-C 12 ) alkyl group may be substituted with one or more halogen atoms or groups selected from hydroxyl, (C1-C6) (di) (alkyl) amino, phenyl, imidazole, (C1-C4) alkyl carbonyl, (C1-C4) alkyl carbonyloxy, (C1-C4) alkyl carbonyl amino, guanidine, thiol, -SO3H, and (C1-C8) alkoxy; 12) alkyl carboxylates, for example trifluoroacetate; xvi) the (C1-C 20 ) the alkene group may have one or more double bonds and may be substituted with one or more hydroxyl groups; (C1-C 20 xvii) alkene carboxylates, the aryl group of which may be substituted with one or more halogen atoms or groups selected from hydroxyl, (C1-C6)(di)(alkyl)amino, phenyl, imidazole, (C1-C4)alkylcarbonyl, (C1-C4)alkylcarbonyloxy, (C1-C4)alkylcarbonylamino, guanidine, thiol, -SO3H, and (C1-C8)alkoxy; 12 ) aryl carboxylates; xviii) their (C1-C 12 ) alkyl group may be substituted with one or more halogen atoms or groups selected from hydroxyl, (C1-C6) (di) (alkyl) amino, phenyl, imidazole, (C1-C4) alkylcarbonyl, (C1-C4) alkylcarbonyloxy, (C1-C4) alkylcarbonylamino, guanidine, thiol, -SO3H, and (C1-C8) alkoxy; 12 xix) alkylsulfonates, for example (C1-C6) alkylsulfonates such as triflates, in particular methylsulfonate or mesylate; and xix) the aryl group of which may be substituted with one or more halogen atoms or groups selected from hydroxyl, (C1-C6) (di) (alkyl) amino, phenyl, imidazole, (C1-C4) alkylcarbonyl, (C1-C4) alkylcarbonyloxy, (C1-C4) alkylcarbonylamino, guanidine, thiol, -SO3H, (C1-C8) alkoxy, (C6-C6) (di) (alkyl) amino, phenyl, imidazole, (C1-C4) alkylcarbonyl, (C1-C4) alkylcarbonyloxy, (C1-C4) alkylcarbonylamino, guanidine, thiol, -SO3H, (C1-C8) alkoxy. 12 ) arylsulfonates, such as benzenesulfonates and toluenesulfonates or tosylates; preferably Y - represents an anionic counterion selected from: [ka] More preferentially, Y - represents an anionic counterion selected from: [ka] More preferentially, Y - represents an anionic counterion selected from: [ka]

[0092] According to one particularly preferred embodiment, the salt of formula (A) is selected from the following compounds 4a, 4b, 4c, and 4d, and mixtures thereof: [ka]

[0093] The salt of formula (A) may be present in the composition in a total content ranging from 1% to 99.5% by weight, preferably from 3% to 90% by weight, more preferentially from 5% to 80% by weight, even more preferentially from 5% to 60% by weight, most preferentially from 5% to 50% by weight and better still from 5% to 40% by weight, relative to the total weight of the composition.

[0094] Peroxide salt d) The composition according to the invention preferably comprises d) one or more peroxide salts, preferably chosen from alkali metal or alkaline earth metal or ammonium persulfates, perborates or percarbonates, and mixtures thereof, and more preferentially from sodium, potassium or ammonium persulfate, and mixtures thereof.

[0095] The peroxide salts d) are preferably present in the composition in a total content ranging from 0.1% to 50% by weight, preferably from 1% to 25% by weight, relative to the total weight of the composition.

[0096] Alkaline agent e) The composition according to the present invention preferably comprises e) one or more alkaline agents. The alkaline agents are preferably selected from aqueous ammonia, alkanolamines such as monoethanolamine, urea, ammonium salts such as ammonium chloride, ammonium sulfate, ammonium phosphate or ammonium nitrate, and silicates, phosphates or carbonates of alkali metals or alkaline earth metals such as lithium, sodium, potassium, magnesium, calcium and barium, and mixtures thereof. Preferably, the alkaline agents are selected from aqueous ammonia, monoethanolamine and silicates such as sodium silicate, and mixtures thereof.

[0097] The alkaline agent e) is preferably present in the composition in a total content ranging from 0.01% to 40% by weight, preferably in the range from 0.1% to 30% by weight relative to the total weight of the composition.

[0098] The composition according to the invention is a cosmetic composition, ie it is in a cosmetic medium.

[0099] The term "cosmetic medium" is intended to mean a medium suitable for dyeing keratin fibers, also known as a dye carrier, which is generally a cosmetic medium formed from water or from a mixture of water with one or more organic solvents or from a mixture of organic solvents.

[0100] The composition preferably comprises water in a content ranging from 5% to 99% by weight and more preferentially from 5% to 95% by weight relative to the total weight of the composition.

[0101] The term "organic solvent" is intended to mean an organic substance that is capable of dissolving other substances without chemically modifying them.

[0102] Examples of organic solvents include lower C2-C4 alkanols, such as ethanol and isopropanol; polyols and polyol ethers, such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol monomethyl ether, as well as aromatic alcohols, such as benzyl alcohol or phenoxyethanol, and mixtures thereof.

[0103] The organic solvent is preferably present in a proportion ranging from 0.1% to 40% by weight, more preferentially from 1% to 30% by weight, and even more preferentially from 1% to 25% by weight, relative to the total weight of the composition.

[0104] According to one preferred embodiment, the composition according to the invention comprises: a) one or more chemical oxidizing agents selected from hydrogen peroxide, hydrogen peroxide generators other than peroxide salts, and mixtures thereof; b) one or more direct dyes; c) one or more heterocyclic salts of formula (A) as defined above; d) one or more peroxide salts; e) one or more alkaline agents; Includes.

[0105] According to one particular embodiment, the composition according to the invention comprises: a) one or more chemical oxidizing agents selected from hydrogen peroxide, hydrogen peroxide generators other than peroxide salts, and mixtures thereof; b) one or more direct dyes; c) one or more heterocyclic salts of formula (A) as defined above; d) one or more peroxide salts; e) one or more alkaline agents; f) water or a mixture of water and one or more organic solvents selected from lower C2-C4 alkanols, preferably ethanol; Includes.

[0106] pH The pH of the composition according to the invention is between 3 and 12, more preferentially between 5 and 11, and even more preferentially between 8 and 10.5.

[0107] The pH of this composition can be adjusted with acidifying or alkaline agents conventionally used in cosmetics.

[0108] Among the acidifying agents, examples which may be mentioned are organic or inorganic acids.

[0109] The term "inorganic acid" is intended to mean any acid derived from an inorganic compound. Among the inorganic acids, mention may be made of hydrochloric acid, orthophosphoric acid, sulfuric acid, sulfonic acid, and nitric acid.

[0110] The term "organic acid" is intended to mean any acid derived from an organic compound. Among the organic acids, mention may be made of acetic acid, tartaric acid, citric acid, lactic acid, and sulfonic acid.

[0111] In particular, inorganic or organic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid, lactic acid, and sulfonic acids can be used.

[0112] Among the basifying agents, for example, aqueous ammonia, alkali metal carbonates, alkanolamines such as monoethanolamine, diethanolamine, and triethanolamine and their derivatives, sodium hydroxide, potassium hydroxide, and amines of the formula (B): [ka] (In formula (B), W is a (C1-C6) alkylene group optionally substituted with one or more hydroxyl groups; R a , R b , R c , and R dmay be the same or different and represent a hydrogen atom or a (C1-C4) alkyl group optionally substituted with one or more hydroxyl groups. Preferably, the pH adjuster can be selected from an alkaline agent such as aqueous ammonia, monoethanolamine, diethanolamine, triethanolamine, 1,3-propanediamine, or an alkaline hydroxide such as 2-amino-2-methyl-1-propanol; or an acidifying agent such as phosphoric acid or hydrochloric acid.

[0113] The composition according to the invention may be in liquid form, in serum form, in thickened form, in particular in the form of a gel, cream, wax or paste, or in foam form.

[0114] The compositions according to the invention may also contain surfactants selected from nonionic, anionic, cationic or amphoteric surfactants; cationic, anionic, nonionic or amphoteric, associative or nonassociative thickening polymers of natural or synthetic origin; silicones in the form of oils, gums, resins; or non-silicone oils of vegetable, mineral or synthetic origin; UV filters; fillers such as pearlescent agents and metal oxides such as titanium dioxide, clays; fragrances; deflocculants; vitamins; and preservatives.

[0115] Process for simultaneously bleaching and dyeing keratin fibres - Patents.com According to a second aspect, the subject of the invention is also a method for simultaneously bleaching and dyeing keratinous fibers, comprising applying to the keratinous fibers a composition as defined above.

[0116] The composition can be applied to wet or dry keratinous fibers.

[0117] Preferably, the application of the composition according to the invention to the keratinous fibres is carried out at room temperature, ie at a temperature between 25°C and 30°C.

[0118] The method includes a step consisting of leaving the composition on the keratin fibers for a period ranging from 5 minutes to 60 minutes.

[0119] According to one advantageous variant of the invention, after application of the composition or after the standing time, if any, has elapsed, the keratinous fibers are rinsed, optionally shampooed and then dried naturally or at a temperature, for example above 30°C.

[0120] According to one particular embodiment, this temperature is greater than 40° C. According to one particular embodiment, this temperature is greater than 45° C. and less than 220° C.

[0121] Preferably, when the keratin fibres are dried, they are dried by using an air current in addition to the supply of heat.

[0122] During drying, the fibers can be subjected to mechanical action such as combing, brushing or hand combing, which can also be carried out after the keratin fibers have been naturally or otherwise dried.

[0123] The drying step can be carried out using a drying appliance such as a hood, hair dryer, or Climazon.

[0124] The drying step can be carried out at a drying temperature in the range of 40°C to 110°C, preferably in the range of 50°C to 90°C, using a hood-type dryer or a hair dryer.

[0125] Once drying is complete, an optional final rinse or shampoo wash may be performed.

[0126] The composition is applied to wet or dry keratinous fibres such that the mass ratio of the amount of composition applied to the amount of hair is preferably in the range of 0.1 to 10, more particularly in the range of 0.2 to 7.5.

[0127] kit According to a third aspect, the subject of the present invention is a device or kit comprising several compartments, comprising: a first compartment containing a composition comprising one or more chemical oxidizers selected from hydrogen peroxide, hydrogen peroxide generators other than peroxide salts, and mixtures thereof; □ A second section: b) one or more direct dyes; and c) a second compartment containing a composition comprising one or more salts of formula (A) as defined above; Have or a first compartment containing a composition comprising one or more chemical oxidizers selected from hydrogen peroxide, hydrogen peroxide generators other than peroxide salts, and mixtures thereof; a second compartment, b) containing a composition comprising one or more direct dyes; a third compartment, c) containing a composition comprising one or more salts of formula (A) as defined above; The device or kit comprises:

[0128] In embodiments of the compositions of the invention that include d) one or more peroxide salts and / or e) one or more alkaline agents, these may be present in the composition contained in the second or third compartment.

[0129] The technical characteristics defined above for the various components of the composition according to the invention also apply to the components of the kit. EXAMPLES

[0130] The following examples will enable the present invention to be more clearly understood, but are not intended to limit the nature of the present invention.

[0131] Example 1 The following compositions were prepared and then applied according to the application procedures described below.

[0132] [Table 1]

[0133] Application steps: 10 g of composition 1, 2 or 3 is applied to 1 g of Caucasian hair tress of tone depth 4 (TD4) in a trough for 50 minutes at a temperature of 33° C. The tress is then rinsed, shampooed and dried.

[0134] Color Difference Measurement Using a Minolta spectrophotometer CM3610A colorimeter (illuminant D65), CIE L * a * b * Color accumulation in the system (ΔE * ) was evaluated. * a * b * In the system, L * represents the lightness of the color, and a * represents the hue along the green / red axis, and b * represents the hue along the blue / yellow axis. * The lower the value of a, the darker or more intense the color. * The higher the value of b, the more reddish the color will be. * The higher the value, the more blue the color.

[0135] ΔE in the table below * is expressed as follows: * a * b * This value is calculated from the value of

number

[0136] In the formula, L * , a * , and b * represents the value measured on the hair bundle after treatment with the above procedure, and L0 * , a0 * , and b0 * represents the value measured on a control tress treated with composition 1.

[0137] ΔE* The higher the value, the better the dye accumulation.

[0138] result The measurement results are shown in the following table.

[0139] [Table 2]

[0140] The above results show that the presence of the salt of formula (A) according to the present invention significantly improves color build-up.

[0141] Example 2 The following compositions were prepared and then applied according to the application procedures described below.

[0142] [Table 3]

[0143] Application steps: 10 g of composition 4, 5 or 6 are applied to 1 g of a TD4 Caucasian hair tress in a water bath for 50 minutes at a temperature of 33° C. The tress is then rinsed, shampooed and dried.

[0144] Color Difference Measurement Using a Minolta spectrophotometer CM3610A colorimeter (illuminant D65), CIE L * a * b * Color accumulation in the system (ΔE * ) was evaluated. * a * b * In the system, L * represents the lightness of the color, and a * represents the hue along the green / red axis, and b * represents the hue along the blue / yellow axis. * The lower the value of a, the darker or more intense the color. * The higher the value of b, the more reddish the color will be. * The higher the value, the more blue the color.

[0145] ΔE in the table below * is expressed as follows: * a * b * This value is calculated from the value of

number

[0146] In the formula, L * , a * , and b * represents the value measured on the hair bundle after treatment with the above procedure, and L0 * , a0 * , and b0 * represents the value measured on a control tress treated with composition 4.

[0147] ΔE * The higher the value, the better the dye accumulation.

[0148] result The measurement results are shown in the following table.

[0149] [Table 4]

[0150] The above results show that the presence of the salt of formula (A) according to the present invention significantly improves color build-up.

[0151] Example 3 The following compositions were prepared and then applied according to the application procedures described below.

[0152] [Table 5]

[0153] Application steps: 10 g of composition 7, 8 or 9 is applied to 1 g of a tress of natural white hair, 90% of which is white, in a water bath for 50 minutes at a temperature of 33° C. The tress is then rinsed, shampooed and dried.

[0154] Color Difference Measurement Using a Minolta spectrophotometer CM3610A colorimeter (illuminant D65), CIE L * a * b * Color accumulation in the system (ΔE * ) was evaluated. * a * b * In the system, L * represents the lightness of the color, and a * represents the hue along the green / red axis, and b * represents the hue along the blue / yellow axis. * The lower the value of a, the darker or more intense the color. * The higher the value of b, the more reddish the color will be. * The higher the value, the more blue the color.

[0155] ΔE in the table below * is expressed as follows: * a * b * This value is calculated from the value of

number

[0156] In the formula, L * , a * , and b * represents the value measured on the hair bundle after treatment with the above procedure, and L0 * , a0 * , and b0 * represents the value measured on a control tress treated with composition 7.

[0157] ΔE * The higher the value, the better the dye accumulation.

[0158] result The measurement results are shown in the following table.

[0159] [Table 6]

[0160] The above results show that the presence of the salt of formula (A) according to the present invention significantly improves color build-up.

[0161] Example 4 The following compositions were prepared and then applied according to the application procedures described below.

[0162] [Table 7]

[0163] Application steps: 10 g of composition 10, 11 or 12 is applied to 1 g of a tress of natural white hair, 90% of which is white, in a water bath for 50 minutes at a temperature of 33° C. The tress is then rinsed, shampooed and dried.

[0164] Color Difference Measurement Using a Minolta spectrophotometer CM3610A colorimeter (illuminant D65), CIE L * a * b * Color accumulation in the system (ΔE * ) was evaluated. * a * b * In the system, L * represents the lightness of the color, and a * represents the hue along the green / red axis, and b * represents the hue along the blue / yellow axis. * The lower the value of a, the darker or more intense the color. * The higher the value of b, the more reddish the color will be. * The higher the value, the more blue the color.

[0165] ΔE in the table below * is expressed as follows: * a * b* This value is calculated from the value of

number

[0166] In the formula, L * , a * , and b * represents the value measured on the hair bundle after treatment with the above procedure, and L0 * , a0 * , and b0 * represents the value measured on a control tress treated with composition 10.

[0167] ΔE * The higher the value, the better the dye accumulation.

[0168] result The measurement results are shown in the following table.

[0169] [Table 8]

[0170] The above results show that the presence of the salt of formula (A) according to the present invention significantly improves color build-up.

Claims

[Claim 1] 1. A composition comprising: a) one or more chemical oxidizing agents selected from hydrogen peroxide, hydrogen peroxide generators other than peroxide salts, and mixtures thereof; b) one or more direct dyes; c) one or more compounds of formula (A): 【Chemistry 1】 (In the formula, □ Het is: - 5 to 10 ring members, preferably 5 or 6 ring members; and - R １ in addition to the ammonium to which is attached, one or two atoms selected from nitrogen or oxygen atoms, preferably nitrogen atoms; represents a cationic aromatic unsaturated heterocyclic group comprising The heterocyclic group may optionally include one or more R' １ Or R ２ is substituted with a group; □ R １ and R' １ may be the same or different and may optionally be selected from the group consisting of, in particular, hydroxyl, amino, (C １ ~C ６ ) dialkylamino, (C １ ~C ６ ) alkylamino, carboxyl, carboxylate, carbamide, (C １ ~C ４ ) Alkoxy, —SO ３ Linear or branched, saturated or unsaturated, substituted with one or more groups selected from H, sulfonate, and phenyl. １ ~C １２ represents a hydrocarbon group; □ R ２ is a hydroxyl group; an amino group; optionally, in particular, hydroxyl, amino, (C １ ~C ６ ) dialkylamino, (C １ ~C ６ ) alkylamino, carboxyl, carboxylate, carbamide, (C １ ~C ４ ) Alkoxy, —SO ３ Linear or branched, saturated or unsaturated, substituted with one or more groups selected from H, sulfonate, and phenyl; １ ~C １２ represents a hydrocarbon group; □ Y － represents an anionic counterion; however: - R １ , R' １ , or R ２ In the case where one of the hydrocarbon groups is substituted with a carboxylate group or a sulfonate group, Y is preferably substituted with a carboxylate group or a sulfonate group so as to maintain the electrical neutrality of the salt of the formula (A). － (it is understood that R is not present); A composition comprising:

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