Compositions containing specific heterocyclic salts for simultaneously bleaching and staining keratin fibers and methods for using the composition.

Abstract

The present invention relates to a composition for simultaneously bleaching and dyeing keratin fibers, the composition comprising one or more specific heterocyclic salts, and also to a method for simultaneously bleaching and dyeing keratin fibers using the composition.

Description

Technical Field

[0001] The present invention relates to a composition for simultaneously bleaching and dyeing keratin fibers, the composition comprising one or more specific heterocyclic salts, and also to a method for simultaneously bleaching and dyeing keratin fibers using the composition. Background Technology

[0002] When a person wants to completely change their hair color, especially when they want a lighter shade than their original color, it is often necessary to bleach and then dye the hair. There are several ways to do this.

[0003] The first method involves using shine-enhancing products based on ammonia and hydrogen peroxide. These products may optionally contain dyes, thus enabling the simultaneous brightening and coloring of the hair. However, the brightening performance of these products remains limited, especially when applied to naturally and / or dyed dark hair.

[0004] The second method involves applying a shine-enhancing composition to the hair based on a peroxide (such as persulfate) and an alkali, to which hydrogen peroxide has been added during application to achieve greater shine. These compositions may contain direct dyes for simultaneous dyeing and bleaching of the hair. However, the range of direct dyes that can be used in these compositions remains limited, as only stable direct dyes can be used under such conditions to achieve good color build-up and intense, vibrant color. To attempt to address this stability issue, a two-step approach is envisioned: bleaching the hair with a shine-enhancing composition in the first step, and then dyeing the hair with a composition containing direct dyes in the second step. However, the two-step method is unsatisfactory due to its relatively long processing time, in addition to the numerous steps involved.

[0005] Therefore, there is a genuine need to develop a composition for bleaching and dyeing keratin fibers containing direct dyes, which simultaneously possesses excellent brightening and dyeing properties, particularly when applied to dark hair, and especially enables the achievement of good color build-up as well as strong and vibrant color. Furthermore, such a composition can contain a wide range of direct dyes, allowing for the attainment of the desired shades. Finally, such a composition can be used in a single-step process for simultaneously bleaching and dyeing keratin fibers.

[0006] The applicant has unexpectedly discovered that all these objectives can be achieved by the composition according to the invention. Summary of the Invention

[0007] According to a first aspect, the subject of the present invention is a composition comprising:

[0008] a) One or more chemical oxidants selected from hydrogen peroxide, hydrogen peroxide generating agents other than peroxide salts, and mixtures thereof;

[0009] b) One or more direct dyes;

[0010] c) One or more heterocyclic salts of formula (A):

[0011]

[0012] in:

[0013] ■Het represents cationic, aromatic, unsaturated heterocyclic groups, which include:

[0014] -5 to 10 ring members, preferably 5 or 6 ring members; and

[0015] - One or two atoms other than ammonium with R1, selected from nitrogen or oxygen atoms, preferably nitrogen atoms;

[0016] The heterocyclic group is optionally substituted with one or more R'1 or R2 groups;

[0017] ■ R1 and R'1 can be the same or different, representing straight or branched chains, saturated or unsaturated chains based on C1-C. 12 The hydrocarbon group, wherein the hydrocarbon-based group is optionally, in particular, substituted with one or more groups selected from the following: hydroxyl, amino, (C1-C6)dialkylamino, (C1-C6)alkylamino, carboxyl, carboxylate, urea, (C1-C4)alkoxy, -SO3H, sulfonate and phenyl.

[0018] ■R2 indicates a hydroxyl, amino, straight-chain or branched saturated or unsaturated C1-C group. 12 The hydrocarbon group, wherein the hydrocarbon-based group is optionally, in particular, substituted with one or more groups selected from: hydroxyl, amino, (C1-C6)dialkylamino, (C1-C6)alkylamino, carboxyl, carboxyl, urea, (C1-C4)alkoxy, -SO3H, sulfonate, and phenyl; and

[0019] ■Y - Indicates anion counterion;

[0020] It should be understood that:

[0021] - When one of the hydrocarbon-based groups of R1, R'1, or R2 is replaced by a carboxylate group or a sulfonate group, then Y - There is no salt that can ensure the electroneutrality of the salt of formula (A).

[0022] According to a second aspect, the subject of the present invention is a method for simultaneously bleaching and dyeing keratin fibers, the method comprising applying a composition as previously defined to the keratin fibers.

[0023] According to a third aspect, the subject of the present invention is a multi-compartment device or reagent kit comprising:

[0024] ■ A first compartment containing a composition comprising a) one or more chemical oxidants selected from hydrogen peroxide, hydrogen peroxide generating agents other than peroxide salts, and mixtures thereof; and

[0025] ■ Contains a second compartment comprising the following composition:

[0026] b) one or more direct dyes; and

[0027] c) One or more salts as previously defined in formula (A);

[0028] or

[0029] ■ A first compartment containing a composition comprising a) one or more chemical oxidants selected from hydrogen peroxide, hydrogen peroxide generating agents other than peroxide salts, and mixtures thereof; and

[0030] ■ A second compartment containing a composition comprising b) one or more direct dyes; and

[0031] ■ A third compartment containing a composition comprising c) one or more salts of formula (A) as previously defined. Detailed Implementation

[0032] For the purposes of this invention and unless otherwise stated:

[0033] ■ The term "keratin fiber" is intended to refer to fibers of human or animal origin, such as hair, body hair, eyelashes, eyebrows, wool, Angora goat hair, cashmere, or fur. According to the present invention, keratin fibers are preferably human keratin fibers, and more preferably hair.

[0034] ■ The term "direct dye" is intended to refer to natural and / or synthetic dyes other than oxidative dyes, including those in the form of one or more extracts. These are dyes that will spread on the surface of fibers. They can be ionic or nonionic, i.e., anionic, cationic, neutral, or nonionic. Direct dyes can have the same type of ionicity or be a mixture.

[0035] ■ Direct dyes contain one or more chromophores, and these dyes are capable of absorbing wavelengths in the range of 400 nm to 700 nm. abs The light below;

[0036] ■ Fluorescent direct dyes are dyes containing at least one fluorophore, and these dyes are luminescent in the wavelength range of 400 nm to 800 nm. abs It absorbs light within the visible light range below 400 nm, and can also absorb light at wavelengths longer than the range of 400 nm to 800 nm. em It re-emits within the visible light range. The difference between the absorption wavelength and the emission wavelength (also known as the Stokes shift) is 1 nm to 100 nm. Preferably, the fluorescent direct dye is a dye that can emit light at wavelengths in the range of 420 nm to 550 nm. abs It absorbs at low wavelengths and is capable of operating at wavelengths in the range of 470 nm to 600 nm. em Re-emit within the visible light range below;

[0037] ■ The term "chemical oxidant" is intended to refer to oxidants other than atmospheric oxygen.

[0038] ■ The term "alkyl" is intended to refer to a straight-chain or branched, saturated hydrocarbon-based group.

[0039] ■Term "(C)" x -C y "alkyl" is intended to refer to an alkyl group containing x to y carbon atoms.

[0040] ■Term "hydroxyl (C)" x -C y "alkyl" is intended to refer to an alkyl group in which at least one of its hydrogen atoms is replaced by a hydroxyl group (-OH). x -C y )alkyl.

[0041] ■Term "(hydroxyl)(C)" x -C y "alkyl" is intended to refer to hydroxyl (C) x -C y )alkyl or (C x -C y )alkyl.

[0042] ■ The term "alkoxy" is intended to refer to an alkyl group bonded to an oxygen atom.

[0043] ■Term "(C)" x -C y "Alkoxy" is intended to refer to an alkoxy group containing x to y carbon atoms.

[0044] ■Term "hydroxyl (C)" x -C y "Alkoxy" is intended to refer to a compound in which at least one of its hydrogen atoms is replaced by a hydroxyl group (-OH). x -C y )alkoxy.

[0045] ■ The expression “optionally substituted” applied to alkyl or alkoxy groups means that the alkyl or alkoxy group may be substituted by one or more groups selected from the following: i) hydroxyl, ii) (C1-C4) alkoxy, iii) amide, iv) an amino group optionally substituted by one or two identical or different (hydroxyl) (C1-C4) alkyl groups, which may form a heterocycle containing 5 to 7 ring members with their nitrogen atoms, the heterocycle optionally containing another nitrogen or non-nitrogen heteroatom; v) a quaternary ammonium group -N + R'R”R”',M - R', R”, and R”' can be the same or different, representing a hydrogen atom or a (C1-C4) alkyl group, or additionally R', R”, and R”' can be related to N. + Forming heteroaryl groups, such as imidazolium optionally substituted with (C1-C4) alkyl groups, and M - It refers to anions or mixtures of anions designed to ensure electrical neutrality.

[0046] ■ The term "alkylene" is intended to refer to straight-chain or branched C1-C based compounds. 10 Particularly, the divalent chain of acyclic hydrocarbons of C1-C6, and more particularly C1-C2, optionally substituted by one or more groups, which may be the same or different, selected from the following: i) hydroxyl, ii) (C1-C2) alkoxy, 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 -, where Z a Z b They can be the same or different, representing oxygen or sulfur atoms or groups NR. a ', Z c Represents a bond, oxygen or sulfur atom, or group NR a ;R a It indicates an alkali metal, a hydrogen atom, or an alkyl group, or otherwise does not exist if the other part of the molecule is a cation, and R a ' represents a hydrogen atom or an alkyl group and t equals 1 or 2; preferably, "alkylene" represents -(CH2). p - group, wherein p is an integer from 1 to 6, preferably from 1 to 4.

[0047] ■ The term “(hetero)aryl” is intended to refer to aryl or heteroaryl.

[0048] ■ The term "aryl" is intended to mean a monocyclic or fused or non-fused polycyclic carbonyl group comprising 6 to 22 carbon atoms, wherein at least one ring is aromatic; preferably, the aryl group is phenyl, biphenyl, naphthyl, indenyl, anthraceneyl or tetrahydronaphthyl.

[0049] The term "heteroaryl" is intended to refer to a 5- to 22-membered monocyclic or fused or unfused polycyclic group of optional cation, comprising 1 to 6 heteroatoms selected from nitrogen, oxygen, sulfur, and selenium, and at least one ring of which is aromatic; preferably, the heteroaryl group is selected from acridine, benzimidazolyl, benzobistriazolyl, benzopyrazolyl, benzopyridazinyl, benzoquinolinyl, benzothiazolyl, benzotriazolyl, benzooxazolyl, pyridinyl, tetrazolyl, dihydrothiazolyl, imidazopyridinyl, imidazolyl, indolyl, isoquinolinyl, naphthiazolyl, etc. Azolyl, naphthooxazolyl, naphthopyrazolyl, oxadiazolyl, oxazolyl, oxazolopyridyl, phenazinyl, phenoxazolyl, pyrazinyl, pyrazolyl, pyrilyl, pyrazoyltriazolyl, pyridyl, pyridinylimidazolyl, pyrroleyl, quinolinyl, tetrazolyl, thiadiazolyl, thiazolyl, thiazopyridyl, thiazolylimidazolyl, thiopyrylyl, triazolyl, xanthylyl and their ammonium salts.

[0050] ■ (Hetero)aryl or heteroaryl moiety may optionally be replaced by at least one group attached to a carbon atom, wherein the at least one group is selected from:

[0051] -(C1-C 10 Alkyl, preferably (C1-C4)alkyl, optionally substituted with at least one group selected from: hydroxyl, (C1-C2)alkoxy, hydroxy(C2-C4)alkoxy, amide, amino optionally substituted with one or two (C1-C4)alkyl groups, which may be the same or different, optionally containing at least one hydroxyl group, or the two (C1-C4)alkyl groups may form a 5- to 7-membered, preferably 5- or 6-membered heterocycle with the nitrogen atom to which they are attached, said heterocycle being saturated or unsaturated and optionally substituted, and optionally containing another nitrogen or non-nitrogen heteroatom;

[0052] - Halogen atom;

[0053] -hydroxyl group;

[0054] -(C1-C2)alkoxy group;

[0055] -(hydroxyl)(C2-C4)alkoxy;

[0056] -amino;

[0057] -5 or 6-membered heterocyclic alkyl groups;

[0058] -Optionally, the cation is a 5- or 6-membered heteroaryl group, preferably imidazolium, and is optionally substituted with a (C1-C4) alkyl group, preferably a methyl group;

[0059] - An amino group substituted with one or two identical or different (C1-C6) alkyl groups, which optionally contain at least:

[0060] i) Hydroxyl group;

[0061] ii) an amino group optionally substituted with one or two optional (C1-C3) alkyl groups, the alkyl groups being able to form saturated or unsaturated, optionally substituted 5- to 7-membered heterocycles with the nitrogen atom to which they are attached, the heterocycles optionally containing at least one other nitrogen or non-nitrogen heteroatom;

[0062] iii) Quaternary ammonium group -N + R'R”R”',M - R', R”, and R”' can be the same or different, representing a hydrogen atom or a (C1-C4) alkyl group; and M - Indicates anion counterion;

[0063] iv) Optionally, the cation is a 5- or 6-membered heteroaryl group, preferably imidazolium, and is optionally substituted with a (C1-C4) alkyl group, preferably a methyl group;

[0064] v) Acylamino(-N(R)-C(O)-R'), where R represents a hydrogen atom or (hydroxyl) (C1-C4)alkyl and R' represents (C1-C2)alkyl;

[0065] -Acylamino(-N(R)-C(O)-R'), where R represents a hydrogen atom or (hydroxyl) (C1-C4)alkyl and R' represents (C1-C2)alkyl;

[0066] -carbamoyl((R)2N-C(O)-), where R can be the same or different, representing a hydrogen atom or (hydroxyl) (C1-C4)alkyl;

[0067] -alkylsulfonylamino(R'-S(O)2-N(R)-), where R represents a hydrogen atom or (hydroxyl) (C1-C4)alkyl and R' represents (C1-C4)alkyl or phenyl;

[0068] -aminosulfonyl((R)2N-S(O)2-), where R can be the same or different, representing a hydrogen atom or (hydroxyl) (C1-C4)alkyl;

[0069] - A carboxyl group in acid or salt form (preferably salified with an alkali metal or a substituted or unsubstituted ammonium salt);

[0070] - A cyano group;

[0071] - A nitro or nitroso group;

[0072] - A polyhaloalkyl group, preferably trifluoromethyl;

[0073] - An ester group.

[0074] [[ID=十六]]The term "cationic heteroaryl" is intended to mean a heteroaryl as previously defined, which contains a quaternized cationic group within or outside the ring,

[0075] - When the cationic charge is within the ring, it is included in the electron delocalization via the mesomeric effect; for example, it is a pyridinium, imidazolium or indolium group:

[0076]

[0077] where R and R' are heteroaryl substituents as previously defined and in particular (hydroxy)(C1-C8)alkyl, such as methyl;

[0078] - When the charge is outside the ring, for example, it is an ammonium substituent R + such as trimethylammonium or phosphonium, outside the heteroaryl such as pyridyl, indolyl, imidazolyl or naphthalenediimide group being discussed;

[0079]

[0080] where R is a heteroaryl substituent as previously defined and R + is 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, where R a , R b and R c may be the same or different and represent a hydrogen atom or a (C1-C8)alkyl such as methyl.

[0081] The term "cationic aryl with an external charge" is intended to mean an aryl ring in which its quaternized cationic group is outside the ring; it is in particular an ammonium substituent R + such as trimethylammonium or phosphonium, outside the aryl such as phenyl or naphthyl:

[0082]

[0083] ■ The term “(hetero)cyclic group” is intended to refer to a heterocyclic group or a carbocyclic group.

[0084] ■ The term "heterocyclic group" is intended to refer to a 5- to 22-membered monocyclic or fused or unfused polycyclic group, which may contain one or two non-aromatic unsaturated heteroatoms selected from nitrogen, oxygen, sulfur and selenium atoms.

[0085] ■ The term "heterocyclic alkyl" is intended to refer to saturated heterocyclic groups such as morpholino, piperazine, or piperidinyl.

[0086] ■ The term "carbocyclic group" is intended to refer to a 5- to 22-membered monocyclic or fused or unfused polycyclic group, which may contain one or two unsaturated but non-aromatic groups, such as cyclobutyl, cyclopentyl or cyclohexyl.

[0087] ■ The carbocyclic or heterocyclic portion of the non-aromatic group may optionally be replaced by at least one group selected from the following groups:

[0088] -hydroxyl group;

[0089] -(C1-C4)alkoxy or hydroxy(C2-C4)alkoxy;

[0090] -(C1-C4)alkyl;

[0091] -alkylcarbonylamino (RC(O)-N(R')-), wherein R' is a hydrogen atom or a (hydroxy)(C1-C4)alkyl, and R is a (C1-C2)alkyl or an amino group optionally substituted with one or two identical or different (hydroxy)(C1-C4)alkyl groups, the (hydroxy)(C1-C4)alkyl groups being able to form saturated or unsaturated, optionally substituted 5- to 7-membered heterocycles with the nitrogen atoms to which they are attached, the heterocycles optionally containing at least one other nitrogen or non-nitrogen heteroatom;

[0092] -alkylcarbonyloxy (RC(O)-O-), wherein R is a (C1-C4)alkyl or an amino group optionally substituted with one or two identical or different (hydroxy)(C1-C4)alkyl groups, the (hydroxy)(C1-C4)alkyl groups being able to form saturated or unsaturated, optionally substituted 5- to 7-membered heterocycles with the nitrogen atoms to which they are attached, the heterocycles optionally containing at least one other nitrogen or non-nitrogen heteroatom.

[0093] -alkoxycarbonyl (RGC(O)-), where R is a (C1-C4) alkyl group and G is an oxygen atom or an amino group optionally substituted with a (hydroxyl) (C1-C4) alkyl group.

[0094] ■The cyclic or heterocyclic group, or the non-aromatic portion of the aryl or heteroaryl group, may also be replaced by at least one oxo group.

[0095] ■ When a hydrocarbon-based chain includes one or more double bonds and / or one or more triple bonds, the chain is unsaturated.

[0096] Unless otherwise stated, when referring to a compound in this application, this also includes its optical isomers, its geometric isomers, its tautomers, its salts or solvates, alone or as mixtures.

[0097] The expressions "at least one / kind" and "one / kind or more / kinds" are synonyms and can be used interchangeably.

[0098] Composition

[0099] According to a first aspect, the subject matter of the present invention is a composition as previously defined.

[0100] The applicant has unexpectedly noted that adding one or more heterocyclic salts of formula (A) to a composition containing one or more oxidizing agents enables the stabilization of direct dyes and achieves satisfactory brightening levels, as well as better color accumulation and intense and vibrant colors.

[0101] Chemical oxidants a)

[0102] The compositions according to the invention comprise a) one or more chemical oxidants selected from hydrogen peroxide, hydrogen peroxide generating agents other than peroxide salts, and mixtures thereof.

[0103] Hydrogen peroxide generators other than peroxide salts can be selected from urea peroxide, polymeric complexes that release hydrogen peroxide, oxidases, and mixtures thereof.

[0104] Examples of polymeric complexes that can release hydrogen peroxide include, in particular, polyvinylpyrrolidone / H2O2 in powder form and other polymeric complexes described in US 5008093, US 3376110 and US 5183901.

[0105] Oxidases can produce hydrogen peroxide in the presence of suitable substrates, such as glucose in the case of glucose oxidase or uric acid in the case of uricase.

[0106] Particularly preferably, the composition according to the invention comprises hydrogen peroxide as a chemical oxidant.

[0107] According to one specific embodiment, hydrogen peroxide and / or a hydrogen peroxide-generating agent other than peroxide salts may be added to the composition according to the invention just before the composition is applied to keratin fibers. An intermediate composition containing hydrogen peroxide and / or a hydrogen peroxide-generating agent other than peroxide salts may be referred to as an oxidizing composition, and may also contain various other compounds or various auxiliaries conventionally used in hair brightening compositions.

[0108] The chemical oxidant may be present in the composition in a total amount ranging from 0.1% to 40% by weight, preferably from 1% to 20% by weight, and more preferably from 2% to 15% by weight relative to the total weight of the composition.

[0109] Direct dyes (b)

[0110] The compositions according to the invention comprise b) one or more direct dyes.

[0111] Direct dyes (b) can be neutral, cationic, or anionic direct dyes.

[0112] Direct dyes (b) may be neutral, cationic, or anionic direct dyes selected from the following: acridine; acridine ketone; anthraquinone; anthraquinone; anthraquinone; acridine; (poly)azo or azo, hydrazine or hydrazone, especially aryl hydrazone; methylimine; benzoanthrone; benzimidazole; benzimidazolone; benzoindole; benzoxazole; benzopyran; benzothiazole; benzoquinone; bis-isodihydroindole; carboxylaniline; coumarin; cyanines, such as (di)azacarbonyl cyanines, (di)azahemicyanines, hemicyanines or tetraazacarbonyl cyanines; (di) acridines; bis-acridines; (di) oxazines; (di) thiazines; (di) aniline; (di) phenylmethane; (di) ketopyrrolopyrroles; flavonoids, such as flavanones and yellow Ketones; fluoroidines; formazan; indamine; indanone; indigo derivatives, thio-indigo derivatives, and pseudo-indigo derivatives; indophenol; indoaniline; isodihydroindole; isodihydroindoleone; isoviolanthrone; lactones; (poly)methimides, such as piracetam or styryl dimethyl derivatives; naphthiadicarboximide; naphthiadicarboximide; naphthoquinone; nitro, especially nitro(hetero)aromatic compounds; oxadiazoles; oxazines; perillone; violetone; perylene; phenazines; phenoxazines; phenothiazines; phthalocyanines; polyenes / carotenoids; porphyrins; pinanthrones; pyrazothrones; pyrazolones; pyrimidinthrones; pyrimidinthrones; pyridine; quinacridones; quinoline; quinophthalones; squalane; tetrazoline derivatives; thiazides; thiopyridines; triarylmethanes or xanthones and natural direct dyes. Preferably, the direct dye b) is selected from anthraquinone, (poly)azo, methylimine, and zirconia, and more preferably from anthraquinone.

[0113] Direct dyes (b) may be particularly selected from neutral, cationic, or anionic nitrobenzene direct dyes, neutral, cationic, or anionic azo direct dyes, neutral, cationic, or anionic tetraazapentamethyne cyanine dyes, cationic or anionic quinone dyes, and especially neutral, cationic, or anionic anthraquinone dyes, neutral, cationic, or anionic azazine direct dyes, neutral, cationic, or anionic triarylmethane direct dyes, neutral, cationic, or anionic methylimine direct dyes, and natural direct dyes. Preferably, the direct dyes are selected from neutral or anionic anthraquinone dyes and violet.

[0114] Examples of neutral, anionic, or cationic direct dyes that can be used in this invention include the following dyes: acridine; acridine ketone; anthraquinone; anthraquinone; anthraquinone; acridine; (poly)azo, hydrazino, or hydrazone, especially aryl hydrazone; methylimine; benzoanthrone; benzimidazole; benzimidazolone; benzoindole; benzoxazole; benzopyran; benzothiazole; benzoquinone; biacrazine; bis-isodihydroindole; carboxylaniline; coumarin; anthocyanins, such as azacarbonyl anthocyanins, diazacarbonyl anthocyanins, diazaheptan anthocyanins, heptan anthocyanins, or tetraazacarbonyl anthocyanins; diazine; diketopyrrolopyrrole; dioxazine; diphenylamine; diphenylmethane; dithiazine; flavonoids, such as flavanones and Flavonoids; fluridines; formazan; indamine; indanone; indigo and pseudoindigo compounds; indophenol; indigoaniline; isodihydroindole; isodihydroindoleone; isoviolanthrone; lactones; (poly)methimides, such as piracetam or styryl-type dimethyl compounds; naphthodicarboximide; naphthoaniline; naphtholide; naphthoquinone; nitro, especially nitro(he)aromatic compounds; oxadiazoles; oxazines; perillone; violetones; perylene; phenazines; phenoxazines; phenothiazines; phthalocyanines; polyenes / carotenoids; porphyrins; pinanthrones; pyrazothrones; pyrazolones; pyrimidinthrones; pyrimidinthrones; pyridine; quinacridones; quinoline; quinophthalones; squalane; tetrazolides; thiazides; thioindole; thiopyridines; triarylmethanes or xanthones.

[0115] Neutral direct dyes

[0116] Direct dye b) can be a neutral direct dye, preferably selected from hydrazine dyes, azo and styryl dyes (IVa), diazo and stilbene dyes (IV'a) and (IV”a), anthraquinone dyes (Va) and methylimine dyes (VIa) and (VI'a), and mixtures thereof of the following formulas (IIIa) and (III'a):

[0117]

[0118] Equations (IIIa), (III'a), (IVa), (IV'a), (IV”a), (Va), (VIa), and (VI'a), where:

[0119] ■Ar represents an aryl group, such as phenyl or naphthyl, which is substituted with at least one electron-donating group, such as i) a optionally substituted (C1-C8) alkyl group, ii) a optionally substituted (C1-C8) alkoxy group, iii) a (di)(C1-C8)(alkyl)amino group optionally substituted with a hydroxyl group on the alkyl group, iv) an aryl(C1-C8) alkylamino group, v) an optionally substituted N-(C1-C8) alkyl-N-aryl(C1-C8) alkylamino group, or Ar represents a juuloridin group;

[0120] ■Ar' represents an optionally substituted divalent (hetero)arylene, such as phenylene, particularly p-phenylene, or naphthylene, which is optionally, preferably substituted by one or more (C1-C8)alkyl, hydroxyl, or (C1-C8)alkoxy groups;

[0121] ■Ar'' represents a (hetero)aryl group, which is optionally, preferably, substituted with at least the following: i) an electron-withdrawing group such as nitro, nitroso, -C(X)-X'-R' or ii) (di)(C1-C6)(alkyl)amino, iii) hydroxyl, iv) (C1-C6) alkoxy; the (hetero)aryl group is particularly selected from imidazolyl, triazolyl, indolyl or pyridyl or phenyl, wherein the phenyl is optionally substituted with at least one group selected from nitro, nitroso and amino, preferably substituted at the para position of the phenyl;

[0122] ■X, X', and X" can be the same or different, representing an oxygen or sulfur atom, or a group NR", preferably oxygen;

[0123] ■R 1 R 2 R 3 and R 4 They can be the same or different, representing hydrogen or halogen atoms, or groups selected from the following: hydroxyl, thiol, (C1-C4)alkyl, (C1-C4)alkoxy, (bis(C1-C4)(alkyl)amino, nitro and nitroso;

[0124] ■R' and R” represent (C1-C4) alkyl groups;

[0125] ■R a and R b They can be the same or different, representing hydrogen atoms or (C1-C8) alkyl groups, which are optionally, preferably, substituted with hydroxyl groups;

[0126] Alternatively, as a variant, the base R is replaced. a Substituents with Ar and / or R b With substituents of Ar and / or R a With R b Together with the atoms containing them, they form (hetero)cycloalkyl groups;

[0127] In particular, R a and R b Represents a hydrogen atom or a (C1-C4) alkyl group, which may optionally be substituted with a hydroxyl group;

[0128] ■T and T' can be the same or different, representing the group C(R) a ) or N, preferably N; and

[0129] ■L represents a divalent group -ALK-, -C(X)-ALK-, -ALK-C(X)- or -C(X)-ALK-C(X')-, where ALK represents a straight-chain or branched (C1-C6) alkylene group, such as methylene, and X and X' are as previously defined;

[0130] ■R 22 R 23 R 24 R 25 R 26 and R 27 These can be the same or different, representing hydrogen or halogen atoms, or groups selected from the following:

[0131] -(C1-C6)alkyl;

[0132] -hydroxyl, mercapto;

[0133] -(C1-C6)alkoxy, (C1-C6)alkylthio;

[0134] -Aryloxy or arylthio;

[0135] -Aryl(C1-C6)(alkyl)amino;

[0136] -(bi)(C1-C6)(alkyl)amino;

[0137] -(di)(hydroxy(C1-C6)alkyl)amino;

[0138] ■Z' represents a hydrogen atom or group NR 28 R 29 , where R 28 and R 29 They can be the same or different, representing hydrogen atoms or groups selected from the following:

[0139] -(C1-C6)alkyl;

[0140] - Polyhydroxy (C1-C6) alkyl groups, such as hydroxyethyl;

[0141] -Optionally substituted with one or more groups, particularly aryl groups: i) (C1-C6) alkyl; iii) R o -C(X)-X'-、R o-X'-C(X)-、R o -X'-C(X)-X”-, where R o (iv) alkyl group (C1-C6) and X, X' and X” as previously defined; ...

[0142] -Cycloalkyl; especially cyclohexyl;

[0143] ■Z indicates that it is selected from hydroxyl and NR' 28 R' 29 The group, wherein R' 28 and R' 29 They can be the same or different, indicating that they are different from R as defined above. 28 and R 29 Identical atoms or groups.

[0144] The direct dye of formula (IV”a) b) is preferably of formula (IV”'a).

[0145]

[0146] Equation (IV”'a), where:

[0147] ■R 1 and R 3 They can be the same or different, preferably the same, representing hydrogen atoms, (C1-C4) alkyl such as methyl or sugar such as glucosyl, preferably hydrogen atoms;

[0148] ■R 2 and R 4 They can be the same or different, preferably the same, representing a hydrogen atom, (C1-C4)alkyl or (C1-C4)alkoxy or -O-sugar group such as -O-glucosyl, preferably (C1-C4)alkoxy; such as methoxy;

[0149] ■X can be the same or different, preferably the same, representing an oxygen or sulfur atom or NR (where R represents a hydrogen atom or group), preferably an oxygen atom;

[0150] ■ALK represents (C1-C4) alkylene such as methylene or ethylene, preferably methylene.

[0151] The direct dyes of formula (IV”a) can be derived from curcumin, demethoxycurcumin and bis-demethoxycurcumin.

[0152] Preferably, the direct dye (b) is selected from direct dyes of formula (IV”a) and formula (Iv”'a) as previously defined, and mixtures thereof.

[0153] According to a particularly preferred embodiment, the direct dye b) is a neutral direct dye selected from compounds (A) to (G) and mixtures thereof:

[0154]

[0155] Preferably selected from compounds (E), (F) and (G) and mixtures thereof, more preferably selected from compounds (E) and (G) and mixtures thereof.

[0156] Cationic direct dyes

[0157] Direct dyes (b) may be selected from cationic or commonly referred to as “basic dyes” due to their affinity for acidic substances, and in particular, their structures contain at least one intra- or extra-cyclic, cationic or cationic group.

[0158] As cationic azo dyes that can be used in this invention, particular reference can be made to the cationic dyes described in Kirk-Othmer's Encyclopedia of Chemical Technology, "Dyes, Azo", J. Wiley & Sons, updated April 19, 2010.

[0159] Also worth mentioning are the cationic azo dyes described in patent applications WO 95 / 15144, WO 95 / 01772 and EP 714954.

[0160] Also worth mentioning are the cationic azo dyes described in the 3rd edition of the Colour Index International, particularly the following compounds: Basic Red 22; Basic Red 76; Basic Yellow 57; Basic Brown 16; and Basic Brown 17.

[0161] Among cationic quinone dyes, those mentioned in the 3rd edition of the International Color Index are appropriate, and the following dyes may be mentioned in particular: Basic Blue 22; Basic Blue 99.

[0162] Among suitable azine dyes, those listed in the International Color Index, 3rd edition, may be mentioned, such as the following dyes: Basic Blue 17, Basic Red 2.

[0163] Among the cationic triarylmethane dyes that can be used according to the present invention, in addition to those listed in the International Color Index, 3rd edition, the following dyes may be mentioned: Basic Green 1, Basic Violet 3, Basic Blue 7.

[0164] The direct dyes described in documents US 5888252, EP 1133975, WO 03 / 029359, EP 860636, WO 95 / 01772, WO 95 / 15144 and EP 714954 may also be mentioned.

[0165] Also mentioned are those listed in different chapters of K. Venkataraman's encyclopedia "The Chemistry of Synthetic Dyes," 1952, Academic Press, Volumes 1-7; the chapter "Dyes and Dye Intermediates" in "Kirk-Othmer's Encyclopedia of Chemical Technology," 1993, Wiley and Sons; and "Ullmann's Encyclopedia of Industrial Chemistry," 7th edition, Wiley and Sons.

[0166] Preferably, the cationic direct dyes are those produced from azo and hydrazine type dyes.

[0167] Cationic direct dyes can be cationic azo dyes, such as those described below: EP 850 636, FR 2788 433, EP 920 856, WO 99 / 48465, FR 2 757 385, EP 850 637, EP 918 053, WO 97 / 44004, FR 2 570 946, FR 2 285 851, DE 2 538 363, FR 2 189 006, FR 1 560 664, FR 1540 423, FR 1 567 219, FR 1 516 943, FR 1 221 122, DE 4 220 388, DE 4 137 005, WO01 / 66646, US 5 708 151, WO 95 / 01772, WO 515 144, GB 1 195 386, US 3524842, US5879413, EP 1062940, EP 1133976, GB 738585, DE 2527638, FR 2275462, GB 1974-27645、Acta Histochem. [Acta Histochemica Sinica] (1978), 61(1), 48-52; Tsitologiya (1968), 10(3), 403-5; Zh.Obshch.Khim., (1970), 40(1), 195-202; Ann.Chim.(Rome) [Annalen chemogastrologer (Rome)] (1975), 65(5-6), 305-14; Rev.Roum.Chim. [Romanian Chemical Review] (1988), 33(4), 377-83; Text.Res.J. [Journal of Textile Research] (1984), 54(2), 105-7; Chim.Ind. (Milan) [Chemical Industry (Milan)] (1974), 56(9), 600-3; Khim.Tekhnol. [Chemical Technology] (1979), 22(5), 548-53; Ger.Monatsh.Chem. [German Monthly Chemical Journal] (1975), 106(3), 643-8; MRL Bulletin on Research and Development of MRL (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.

[0168] Preferably, the cationic direct dye comprises a quaternary ammonium group; more preferably, the cationic charge is intracyclic. These cationic groups are, for example, the following cationic groups:

[0169] - With (di / tri) (C1-C8) alkylammonium ring external charge, or

[0170] - Possesses an in-ring charge, such as a cationic heteroaryl group selected from: acridine onion, benzimidazole onion, benzobistriazole onion, benzopyrazole onion, benzopyridazine onion, benzoquinoline onion, benzothiazolium onion, benzotriazole onion, benzooxazolium onion, bipyridinium onion, bis-tetrazole onion, dihydrothiazolium onion, imidazopyridinium onion, imidazoline onion, indoline onion, isoquinoline onion, naphthemidazole onion, naphtheoxazolium onion, naphthepyrazole onion, oxadiazole onion Onion, oxazolium, oxazolopyridinium, oxonium, phenazineonium, phenooxazolium, pyrazineonium, pyrazolium, pyrazolyltriazolium, pyridinium, pyridinium, pyridinium, pyridineimidazolium, pyrroleonium, pyranonium, quinolineonium, tetrazolium, thiadiazolium, thiazolylium, thiazolylium, thiazopyridinium, thiazolylimidazolium, thiopyrylium, triazolium, or xanthonium.

[0171] The following hydrazine cationic direct dyes of formulas (IIb) and (IIIb) and azo dyes of formulas (IVb) and (Vb) may be mentioned:

[0172] Het + -C(R a )=NN(R b )-Ar,Q(IIb) - ;

[0173] Het + -N(R a )-N=C(R b )-Ar,Q - (IIIb);

[0174] Het + -N = N - Ar,Q(IVb);

[0175] Ar + -N=N-Ar”,Q - (Vb);

[0176] Equations (IIb) to (Vb), where:

[0177] ■Het + The preferred option is a cationic heteroaryl group with an intracyclic cationic charge, such as imidazolium, indolonium, or pyridinium, which is optionally, preferably, substituted with at least one (C1-C8) alkyl group, such as methyl.

[0178] ■Ar +The aryl group, such as phenyl or naphthyl, is preferred to have an exocyclic cation charge, particularly tri(C1-C8) alkylammonium such as trimethylammonium;

[0179] ■Ar represents an aryl group, particularly a phenyl group, which is optionally and preferably 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 group which is optionally substituted with a hydroxyl group on the alkyl group, iv) aryl(C1-C8)alkylamino group, v) optionally substituted N-(C1-C8)alkyl-N-aryl(C1-C8)alkylamino group, or alternatively, Ar represents a juuloridin group;

[0180] "■Ar" indicates an optionally substituted (hetero)aryl group, such as phenyl or pyrazolyl, which is optionally, preferably, substituted by one or more (C1-C8)alkyl, hydroxyl, (di)(C1-C8)(alkyl)amino, (C1-C8)alkoxy or phenyl;

[0181] ■R a and R b They can be the same or different, representing hydrogen atoms or (C1-C8) alkyl groups, which are optionally, preferably, substituted with hydroxyl groups;

[0182] ■Or alternatively, substituent R a With Het + Substituents and / or R b With substituents of Ar and / or R a With R b Together with the atoms containing them, they form (hetero)cycloalkyl groups; in particular, R a and R b Represents a hydrogen atom or an alkyl group optionally substituted with a hydroxyl group (C1-C4);

[0183] ■Q - This indicates anion counterions, such as halide ions, alkyl sulfate ions, or alkyl sulfonate ions.

[0184] In particular, reference may be made to azo and hydrazine-based direct dyes of formulas (IIb) to (Vb) with intracyclic cationic charges as previously defined. More particularly, reference may be made to cationic direct dyes of formulas (IIb) to (Vb) with intracyclic cationic charges as described in patent applications WO 95 / 15144, WO 95 / 01772 and EP714954.

[0185] Preferably, the following direct dyes may be mentioned:

[0186]

[0187] Equations (II-1) and (IV-1), where;

[0188] ■R 1 Indicates (C1-C4) alkyl, such as methyl;

[0189] ■R 2 and R 3 These can be the same or different, representing hydrogen atoms or (C1-C4) alkyl groups, such as methyl.

[0190] ■R 4 Represents a hydrogen atom or an electron-donating group, such as an optionally substituted (C1-C8)alkyl, optionally substituted (C1-C8)alkoxy, or a (di)(C1-C8)(alkyl)amino group optionally substituted with a hydroxyl group on the alkyl group; in particular, R 4 It is a hydrogen atom.

[0191] ■Z represents a CH group or a nitrogen atom, preferably CH.

[0192] ■Q - These are anionic counterions as previously defined, particularly halide ions such as chloride ions or alkyl sulfate ions such as methyl sulfate ions or mesitylene ions.

[0193] Specifically, the dyes of formulas (II-1) and (IV-1) are selected from Basic Red 51, Basic Yellow 87, and Basic Orange 31 or their derivatives:

[0194]

[0195] Q' is an anionic counterion as previously defined, particularly a halide ion such as chloride or an alkyl sulfate such as methyl sulfate or mesitylene.

[0196] Fluorescent dyes

[0197] Direct dyes (b) can be selected from fluorescent direct dyes.

[0198] Examples of fluorescent dyes that can be used in this invention include neutral, anionic, or cationic dyes selected from the following: acridine, acridine ketone, benzanthrone, benzimazole, benzimazole ketone, benzoindole, benzoxazole, benzopyran, benzothiazole, coumarin, and difluoro{2-[(2H-pyrrolato-2-ylidene-kN)methyl]-1H-pyrrolato-kN}boron. Diketylpyrrolopyrrole, fluridine, (poly)methimide (especially cyanine and styryl / hemicyanine), naphthalenediimide, naphthylaniline, naphthylamine (such as dansyl), oxadiazole, oxazine, perillone, perylene, polyene / carotenoid, squalane, piracetam, xazolide.

[0199] Also mentioned are the fluorescent dyes described in documents EP 1133975, WO 03 / 029359, EP 860636, WO 95 / 01772, WO 95 / 15144 and EP 714954, as well as those listed below: K. Venkataraman's encyclopedia "The Chemistry of Synthetic Dyes", 1952, Academic Press, Volumes 1-7; the chapter "Dyes and Dye Intermediates" in "Kirk-Othmer's Encyclopedia of Chemical Technology", 1993, Wiley and Sons; and "Ullmann's Encyclopedia of Industrial Chemistry", 7th edition, Wiley and Sons. Different chapters from Sons, as well as "The Handbook—A Guide to Fluorescent Probes and Labeling Technologies," 10th edition, Molecular Probes / Invitrogen – Oregon 2005, available online or in previous print editions.

[0200] According to preferred variants, the fluorescent dye is a cationic polymethyl group and contains at least one quaternary ammonium group, such as those of the following formula (Vb): W + -[C(R c )=C(R d )] m’ -Ar,Q -

[0201] Equation (Vb), where:

[0202] ■W + The group represents a cationic heterocyclic group or heteroaryl group, which in particular comprises a quaternary ammonium group optionally substituted with one or more (C1-C8) alkyl groups, which are optionally, in particular, substituted with one or more hydroxyl groups;

[0203] ■Ar represents an aryl group such as phenyl or naphthyl, which is optionally preferably substituted with: i) one or more halogen atoms, such as chlorine or fluorine; ii) one or more (C1-C8) alkyl, preferably (C1-C4) alkyl 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 amino or (di) (C1-C8) alkylamino groups, preferably having a C1-C4 alkyl moiety optionally substituted with one or more hydroxyl groups, such as (di) hydroxyethylamino; vii) one or more amide groups; viiii) one or more heterocyclic alkyl groups such as piperazine, piperidinyl or 5- or 6-membered heteroaryl groups such as pyrrolidinyl, pyridinyl and imidazolinyl;

[0204] ■m' represents an integer ranging from 1 to 4, preferably m' equals 1 or 2; more preferably m' = 1;

[0205] ■R c and R d They can be the same or different, representing hydrogen atoms or optionally substituted (C1-C8) alkyl groups, preferably optionally substituted (C1-C4) alkyl groups, or additionally, R c With W + Adjacency and / or R d Ar adjacent to and with atoms containing them to form (hetero)cycloalkyl groups; in particular, R c With W + They are adjacent to each other and form (hetero)cycloalkyl groups such as cyclohexyl;

[0206] ■Q - It is an anion counterion as previously defined.

[0207] Anionic dyes

[0208] Direct dyes (b) can be selected from anionic direct dyes or dyes that are commonly referred to as "acidic" direct dyes due to their affinity for basic substances.

[0209] The term "anionic direct dye" is intended to refer to any direct dye whose structure contains at least one CO2R or SO3R substituent, where R indicates a hydrogen atom or a cation derived from a metal or amine, or an ammonium ion. Anionic dyes can be selected from acidic nitro direct dyes, acidic azo dyes, acidic azazine dyes, acidic triarylmethane dyes, acidic indoamine dyes, acidic anthraquinone dyes, indigo dyes, and acidic natural dyes.

[0210] Preferably, the anionic direct dye is acidic anthraquinone.

[0211] Direct dye b) can be anionic direct dye, preferably selected from dyes of formulas (III), (III'), (IV), (IV'), (V), (V'), (VI), (VI'), (VII), (VIII), (IX) and (X), and mixtures thereof:

[0212] a) Diaryl anionic azo dyes of formula (III) or (III') :

[0213]

[0214] Equations (III) and (III'), where:

[0215] ■R7, R8, R9, R 10 R'7, R'8, R'9 and R' 10 They can be the same or different, representing hydrogen atoms or groups selected from the following:

[0216] -(C1-C6)alkyl;

[0217] -(C1-C6)alkoxy, (C1-C6)alkylthio;

[0218] -hydroxyl, mercapto;

[0219] - Nitro, nitroso;

[0220] -R o -C(X)-X'-、R o -X'-C(X)-、R o -X'-C(X)-X”-, where R o It represents a hydrogen atom or a (C1-C6) alkyl or aryl such as phenyl; X, X' and X" can be the same or different, representing an oxygen or sulfur atom, or NR, where R represents a hydrogen atom or a (C1-C6) alkyl;

[0221] -(O)2S(O - )-,M + M + Indicates a hydrogen atom or cation as a counter ion;

[0222] -(O)CO - -,M + M + As previously defined;

[0223] -R”-S(O)2-, where R” represents a hydrogen atom, alkyl, or aryl, (di)(C1-C6)(alkyl)amino or aryl(C1-C6)(alkyl)amino; preferably phenylamino or phenyl;

[0224] -R”'-S(O)2-X’-, where R”' represents an optionally substituted (C1-C6) alkyl or aryl group, and X' is as previously defined;

[0225] -(bi)(C1-C6)(alkyl)amino;

[0226] -aryl (C1-C6) (alkyl)amino, optionally substituted by one or more groups selected from: i) nitro; ii) nitroso; iii) (O)2S(O - )-,M + and iv)(C1-C6)alkoxy, wherein M + As previously defined;

[0227] -Optionally substituted heteroaryl groups; preferably benzothiazolyl;

[0228] -Cycloalkyl; especially cyclohexyl;

[0229] -Ar-N=N-, where Ar represents an optionally substituted aryl group; preferably optionally substituted with one or more alkyl groups, (O)2S(O - )-,M + Or phenylamino-substituted phenyl;

[0230] -Or two other adjacent groups R7 and R8, or R8 and R9, or R9 and R 10 Together they form a fused benzo[a] group A'; and R'7 with R'8 or R'8 with R'9 or R'9 with R' 10 Together they form a fused benzo[a] group B'; wherein A' and B' are optionally substituted by one or more groups selected from: i) nitro; ii) nitroso; iii) (O)2S(O - )-,M + ;iv) hydroxyl group;v) mercapto group;vi) (di) (alkyl) amino group;vii) R o -C(X)-X'-;viii)R o -X'-C(X)-;ix)R o -X'-C(X)-X”-; x)Ar-N=N- and xi) optionally substituted aryl (C1-C6) (alkyl)amino; wherein M + R o X, X', X” and Ar are as previously defined;

[0231] ■W represents a sigma σ bond, an oxygen or sulfur atom, or a divalent group i) –NR-, where R is as previously defined, or ii) methylene-C(R a (R) b )-, where R a and R bThey can be the same or different, representing a hydrogen atom or an aryl group, or alternatively, R a and R b Together with the carbon atoms containing them, they form spirocycloalkyl groups; preferably, W represents a sulfur atom or R a and R b Together they form a cyclohexyl group;

[0232] It should be understood that equations (III) and (III') contain the following over one of the rings A, A', B, B', or C:

[0233] -At least one group (O)2S(O) - )-,M' + , where M' + Indicates a cation counterion; or

[0234] -At least one group (O)CO - -,M' + , where M' + Indicates a cation counterion;

[0235] Preferably, at least one sodium sulfonate group is used.

[0236] Examples of dyes according to formula (III) include: 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 135, and Acid Red 1 38. Acid Red 184. Food Red 13. Acid Orange 7. Acid Orange 10. Acid Orange 19. Acid Orange 20. 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 Yellow 3 or Sunset Yellow;

[0237] Examples of dyes of formula (III') include: Acid Red 111, Acid Red 134, and Acid Yellow 38.

[0238] b) Pyrazolone anionic azo dyes of formula (IV) or (IV') :

[0239]

[0240] Equations (IV) and (IV'), where:

[0241] ■R 11 R 12 and R 13They can be the same or different, representing hydrogen or halogen atoms, or (C1-C6) alkyl groups or -(O)2S(O - ),M + Group, wherein M + As previously defined;

[0242] ■R 14 Represents a hydrogen atom, (C1-C6)alkyl group, or -C(O)O - M + Group, wherein M + As previously defined;

[0243] ■R 15 Represents a hydrogen atom;

[0244] ■R 16 R' represents an oxo group. 16 It does not exist, or there is another R. 15 With R 16 Together they form a double bond;

[0245] ■R 17 and R 18 They can be the same or different, representing hydrogen atoms or groups selected from the following:

[0246] -(O)2S(O - )-,M + M + As previously defined;

[0247] -Ar-OS(O)2-, where Ar represents an optionally substituted aryl group; preferably a phenyl group optionally substituted with one or more alkyl groups;

[0248] ■R 19 and R 20 Together they form a double bond, or optionally a benzo[D] group;

[0249] ■R' 16 、R' 19 and R' 20 They can be the same or different, representing hydrogen atoms or (C1-C6) alkyl or hydroxyl groups;

[0250] ■R 21 Represents a hydrogen atom or a (C1-C6) alkyl or (C1-C6) alkoxy group;

[0251] ■R a and R b They can be the same or different, as previously defined; preferably, R a Represents a hydrogen atom and R b Indicates aryl groups such as phenyl;

[0252] ■Y represents a hydroxyl or oxo group;

[0253] ■ When Y is an oxo group, it represents a single bond; and when Y represents a hydroxyl group, it represents a double bond.

[0254] It should be understood that equations (IV) and (IV') contain the following on either ring D or E:

[0255] -At least one group (O)2S(O) - )-,M' + , where M' + Indicates a cation counterion; or

[0256] -At least one group (O)CO - -,M' + , where M' + Indicates a cation counterion;

[0257] Preferably, at least one sodium sulfonate group is used.

[0258] Examples of dyes of formula (IV) include: Acid Red 195, Acid Yellow 23, Acid Yellow 27, and Acid Yellow 76; and examples of dyes of formula (IV') include: Acid Yellow 17.

[0259] c) Anthraquinone dyes of formula (V) or (V'):

[0260]

[0261] Equations (V) and (V'), where:

[0262] ■R 22 R 23 R 24 R 25 R 26 and R 27 These can be the same or different, representing hydrogen or halogen atoms, or groups selected from the following:

[0263] -(C1-C6)alkyl;

[0264] -hydroxyl, mercapto;

[0265] -(C1-C6)alkoxy, (C1-C6)alkylthio;

[0266] -Optionally substituted aryloxy or arylthio groups, preferably selected from one or more alkyl groups and (O)2S(O - )-,M + Group substitution, wherein M + As previously defined;

[0267] -aryl(C1-C6)(alkyl)amino, which is optionally composed of one or more radicals selected from alkyl and (O)2S(O - )-,M + The group is substituted, wherein M is a group that is substituted. + As previously defined;

[0268] -(bi)(C1-C6)(alkyl)amino;

[0269] -(di)(hydroxy(C1-C6)alkyl)amino;

[0270] -(O)2S(O - )-,M + M + As previously defined;

[0271] ■Z' represents a hydrogen atom or group NR 28 R 29 , where R 28 and R 29 They can be the same or different, representing hydrogen atoms or groups selected from the following:

[0272] -(C1-C6)alkyl;

[0273] - Polyhydroxy (C1-C6) alkyl groups, such as hydroxyethyl;

[0274] -Optionally substituted with one or more groups, particularly aryl groups: i) (C1-C6) alkyl, such as methyl, n-dodecyl, n-butyl; ii) (O)2S(O - )-,M+, where M + As previously defined; iii)R o -C(X)-X'-、R o -X'-C(X)-、R o -X'-C(X)-X”-, where R o X, X', and X" are as previously defined; preferably R o Indicates (C1-C6) alkyl;

[0275] -Cycloalkyl, especially cyclohexyl;

[0276] ■Z indicates that it is selected from hydroxyl and NR' 28 R' 29 The group, wherein R' 28 and R' 29 They can be the same or different, indicating that they are different from R as previously defined. 28 and R 29 Identical atoms or groups;

[0277] It should be understood that equations (V) and (V') contain:

[0278] -At least one group (O)2S(O) - )-,M' + , where M' + Indicates a cation counterion; or

[0279] -At least one group (O)CO - -,M' + , where M' + Indicates a cation counterion;

[0280] Preferably, at least one sodium sulfonate group is used.

[0281] 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;

[0282] And as an example of a dye of formula (V'), Acid Black 48 can be mentioned;

[0283] d) Nitro dyes of formula (VI) or (VI'):

[0284]

[0285] Equations (VI) and (VI'), where:

[0286] ■R 30 R 31 and R 32 These can be the same or different, representing hydrogen or halogen atoms, or groups selected from the following:

[0287] -(C1-C6)alkyl;

[0288] - An (C1-C6) alkoxy group optionally substituted with one or more hydroxyl groups, or an (C1-C6) alkylthio group optionally substituted with one or more hydroxyl groups;

[0289] -hydroxyl, mercapto;

[0290] - Nitro, nitroso;

[0291] - Polyhalogenated (C1-C6) alkyl groups;

[0292] -R o -C(X)-X'-、R o -X'-C(X)-、R o -X'-C(X)-X”-, where R oX, X', and X" are as previously defined;

[0293] -(O)2S(O - )-,M + M + As previously defined;

[0294] -(O)CO - -,M + M + As previously defined;

[0295] -(bi)(C1-C6)(alkyl)amino;

[0296] -(di)(hydroxy(C1-C6)alkyl)amino;

[0297] - Heterocyclic alkyl groups, such as piperidino, piperazino, or morpholino;

[0298] - Specifically, R 30 R 31 and R 32 Represents a hydrogen atom;

[0299] ■R c and R d They can be the same or different, representing hydrogen atoms or (C1-C6) alkyl groups;

[0300] ■W is as previously defined; W specifically represents the N(H)- group;

[0301] ■ALK represents a straight-chain or branched divalent C1-C6 alkylene group; in particular, ALK represents a -CH2-CH2- group;

[0302] ■n is 1 or 2;

[0303] ■p represents an integer ranging from 1 to 5;

[0304] ■q represents an integer ranging from 1 to 4;

[0305] ■u is 0 or 1;

[0306] ■ When n is 1, J represents nitro or nitroso; especially nitro;

[0307] ■ When n is 2, J represents an oxygen or sulfur atom, or a divalent group -S(O). m - where m represents an integer 1 or 2; preferably, J represents a -SO2- group;

[0308] "■M" indicates a hydrogen atom or a cation counter ion;

[0309] ■ The presence or absence of the group indicates that it may be optionally occupied by one or more groups R as previously defined. 30 Substituted benzo[a] group;

[0310] It should be understood that equations (VI) and (VI') contain:

[0311] -At least one group (O)2S(O) - )-,M' + , where M' + Indicates a cation counterion; or

[0312] -At least one group (O)CO - -,M' + , where M' + Indicates a cation counterion;

[0313] Preferably, at least one sodium sulfonate group is used.

[0314] Examples of dyes of formula (VI) include: Acid Brown 13 and Acid Orange 3; examples of dyes of formula (VI') include: Acid Yellow 1, sodium salts of the following acids: 2,4-dinitro-1-naphthol-7-sulfonic acid, 2-piperidinyl-5-nitrobenzenesulfonic acid, 2-(4'-N,N-(2”-hydroxyethyl)amino-2'-nitro)aniline ethanesulfonic acid, 4-β-hydroxyethylamino-3-nitrobenzenesulfonic acid; and Ext. D&C Yellow 7.

[0315] e) Triarylmethane dyes of formula (VII) :

[0316]

[0317] Equation (VII), where:

[0318] ■R 33 R 34 R 35 and R 36 These can be the same or different, representing a hydrogen atom or a group selected from: (C1-C6)alkyl, optionally substituted aryl, and optionally substituted aryl(C1-C6)alkyl; particularly (C1-C6)alkyl and optionally (O) m S(O - )-,M + A group-substituted benzyl group, wherein M + and m as previously defined;

[0319] ■R 37 R 38 R 39 R 40 R41 R 42 R 43 and R 44 They can be the same or different, representing hydrogen atoms or groups selected from the following:

[0320] -(C1-C6)alkyl;

[0321] -(C1-C6)alkoxy, (C1-C6)alkylthio;

[0322] -(bi)(C1-C6)(alkyl)amino;

[0323] -hydroxyl, mercapto;

[0324] - Nitro, nitroso;

[0325] -R o -C(X)-X'-、R o -X'-C(X)-、R o -X'-C(X)-X”-, where R o X represents a hydrogen atom or an alkyl or aryl group; X, X', and X" can be the same or different, representing an oxygen or sulfur atom, or NR, where R represents a hydrogen atom or a (C1-C6) alkyl group;

[0326] -(O)2S(O - )-,M + M + Indicates a hydrogen atom or cation as a counter ion;

[0327] -(O)CO - -,M + M + As previously defined;

[0328] -or two other adjacent groups R 41 With R 42 Or R 42 With R 43 Or R 43 With R 44 Together they form a fused benzo[a] group, which is optionally substituted by one or more groups selected from: i) nitro; ii) nitroso; iii) (O)2S(O - )-,M + ;iv) hydroxyl group;v) mercapto group;vi) (di) (C1-C6) (alkyl)amino group;vii) R o -C(X)-X'-;viii)R o -X'-C(X)-;ix)R o -X'-C(X)-X”-; where M + R oX, X', and X" are as previously defined;

[0329] In particular, R 37 To R 40 Represents a hydrogen atom, and R 41 To R 44 They can be the same or different, representing hydroxyl groups or (O)2S(O - )-,M + M + As previously defined; and when R 43 With R 44 When they form a benzo[a] group together, it is preferably (O)2S(O - )- group substitution;

[0330] It should be understood that at least one of the rings G, H, or I contains:

[0331] -At least one group (O)2S(O) - )-,M' + , where M' + Indicates a cation counterion; or

[0332] -At least one group (O)CO - -,M' + , where M' + Indicates a cation counterion;

[0333] Preferably, at least one sodium sulfonate group is used.

[0334] Examples of dyes of formula (VII) include: Acid Blue 3, Acid Blue 7, Acid Blue 9, Acid Violet 49, Acid Green 3, Acid Green 5 and Acid Green 50.

[0335] f) Xanton-based dyes of formula (VIII) :

[0336]

[0337] Equation (VIII) in which:

[0338] ■R 45 R 46 R 47 and R 48 These can be the same or different, representing hydrogen atoms or halogen atoms;

[0339] ■R 49 R 50 R 51 and R 52 These can be the same or different, representing hydrogen or halogen atoms or groups selected from the following:

[0340] -(C1-C6)alkyl;

[0341] -(C1-C6)alkoxy, (C1-C6)alkylthio;

[0342] -hydroxyl, mercapto;

[0343] - Nitro, nitroso;

[0344] -(O)2S(O - )-,M + M + Indicates a hydrogen atom or cation as a counter ion;

[0345] -(O)CO - -,M + M + As previously defined;

[0346] In particular, R 53 R 54 R 55 and R 48 Represents a hydrogen or halogen atom;

[0347] ■G represents an oxygen or sulfur atom or group. NR e , where R e As previously defined; in particular, G represents the oxygen atom;

[0348] ■L represents alkoxide O - M + Thiol salt S - M + or group NR f , where R f It represents a hydrogen atom or a (C1-C6) alkyl group, and M + As previously defined; M + Specifically, sodium or potassium;

[0349] ■L' represents an oxygen or sulfur atom or an ammonium group: N + R f R g , where R f and R g They can be the same or different, representing a hydrogen atom, a (C1-C6) alkyl group, or an optionally substituted aryl group; L' specifically represents an oxygen atom or optionally an oxygen atom surrounded by one or more alkyl groups or (O). m S(O - )-,M + phenylamino groups substituted with groups, wherein m and M + As previously defined;

[0350] ■Q and Q' can be the same or different, representing oxygen or sulfur atoms; in particular, Q and Q' represent oxygen atoms;

[0351] ■M + It is as previously defined.

[0352] Examples of dyes of formula (VIII) include: Acid Yellow 73, Acid Red 51, Acid Red 52, and Acid Red 92.

[0353] g) Indole-based dyes of formula (IX) :

[0354]

[0355] Equation (IX), where:

[0356] ■R 53 R 54 R 55 R 56 R 57 R 58 R 59 and R 60 They can be the same or different, representing hydrogen atoms or groups selected from the following:

[0357] -(C1-C6)alkyl;

[0358] -(C1-C6)alkoxy, (C1-C6)alkylthio;

[0359] -hydroxyl, mercapto;

[0360] - Nitro, nitroso;

[0361] -R o -C(X)-X'-、R o -X'-C(X)-、R o -X'-C(X)-X”-, where R o X represents a hydrogen atom or an alkyl or aryl group; X, X', and X" can be the same or different, representing an oxygen or sulfur atom, or NR, where R represents a hydrogen atom or a (C1-C6) alkyl group;

[0362] -(O)2S(O - )-,M + M + Indicates a hydrogen atom or cation as a counter ion;

[0363] -(O)CO - -,M + M + As previously defined;

[0364] ■G represents an oxygen or sulfur atom or group. NRe , where R e As previously defined; in particular, G represents the oxygen atom;

[0365] ■R i and R h They can be the same or different, representing hydrogen atoms or (C1-C6) alkyl groups;

[0366] It should be understood that equation (IX) includes:

[0367] -At least one group (O)2S(O) - )-,M' + , where M' + Indicates a cation counterion; or

[0368] -At least one group (O)CO - -,M' + , where M' + Indicates a cation counterion;

[0369] Preferably, at least one sodium sulfonate group is used.

[0370] As an example of a dye of formula (IX), Acid Blue 74 can be mentioned.

[0371] h) Quinoline-based dyes of formula (X) :

[0372]

[0373] Equation (X), where:

[0374] ■R 61 Indicates a hydrogen or halogen atom or a (C1-C6) alkyl group;

[0375] ■R 62 R 63 and R 64 They can be the same or different, representing hydrogen atoms or groups (O)2S(O) - )-,M + M + Indicates a hydrogen atom or a cation counter ion; or alternatively, R 61 With R 62 、or R 61 With R 64 Together they form a benzo[a] group, which is optionally surrounded by one or more groups (O)2S(O) - )-,M + Replacement, where M + Indicates a hydrogen atom or cation as a counter ion;

[0376] It should be understood that formula (X) contains at least one group (O)2S(O)- )-,M' + (where M') + (representing a cationic counterion), preferably at least one sodium sulfonate group.

[0377] Examples of dyes of formula (X) include: Acid Yellow 2, Acid Yellow 3 and Acid Yellow 5.

[0378] More specifically, the dyes used in formulas (III) to (VIII) of the present invention are selected from: Acid Orange 3 (VI) (CI10383); Acid Yellow 9 / Food Yellow 2 (III) (CI13015); Direct Red 45 / Food Red 13 (III) (CI14780); Acid Black 52 (III) (CI13711); Acid Yellow 36 (III) (CI13065); Sodium salt of 1-hydroxy-2-(2',4'-dimethyl-5-sulfonyl azo)naphthalene-4-sulfonic acid / Food Red 1 (III) (CI14700); Acid Red 14 / Food Red 3 / Modal Blue 79 (III) (CI14720); 4-hydroxy-3-[(2 Sodium salt of 1-methoxy-5-nitrophenyl)diaza-6-(phenylamino)naphthalene-2-sulfonic acid / Acid Brown 4(III) (CI 14805); Acid Orange 7 / Pigment Orange 17 / Solvent Orange 49(III) (CI 15510); Food Yellow 3 / Pigment Yellow 104(III) (CI 15985); Acid Red 27 / Food Red 9(III) (CI 16185); Acid Orange 10 / Food Orange 4(III) (CI 16230); Acid Red 44(III) (CI 16250); Acid Red 33 / Food Red 12(III) (CI 17200); Acid Red 184(III) (CI 15685); Acid Violet 3(III) (CI19125); Sodium salt of 1-hydroxy-2-(4'-acetamidophenylazo)-8-acetamidonaphthalene-3,6-disulfonic acid / Acid Purple 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'-(sulfonyl-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 salts of sulfonic acid / Acid Black 1(III) (CI20470); (4-((4-methylphenyl)sulfonyloxy)phenylazo)-2,2'-dimethyl-4-((2-hydroxy-5,8-disulfonic)naphthylazo)biphenyl / Acid Red 111(III') (CI23266); Food Black 2(III) (CI27755); 1-(4'-sulfonicophenylazo)-4-((2"-hydroxy-3"-acetylamino-6",8"-disulfonic)naphthylazo)-6-sulfoniconaphthalene (tetrasodium salt) / Food Black 1(III) (CI25440); Acid Blue 9(VII) (CI42090); Acid Violet 43(V) (CI60730); Acid Green 25(V) (CI61570); Sodium salt of 1-amino-4-cyclohexylamino-9,10-anthraquinone-2-sulfonic acid / Acid Blue 62(V) (CI62045); Acid Blue 78(V) (CI62105); Sodium salt of 4-hydroxy-3-((2-methoxyphenyl)azo)-1-naphthalenesulfonic acid / Acid Red 4(III) (CI14710); 2-piperidinyl5-nitrobenzenesulfonic acid (VI'); 2(4'-N,N(2"-hydroxyethyl)amino-2'-nitro)anilineethanesulfonic acid (VI'); 4-β- Hydroxyethylamino-3-nitrobenzenesulfonic acid (VI'); Acid Violet 49 (VII) (CI42640); Acid Blue 7 (VII) (CI42080); Sodium salt of 1,2-dihydroxy-3-sulfoanthraquinone / Modifier Red 3 (V) (CI58005); Sodium salt of 1-amino-9,10-dihydro-9,10-dioxo-4-(phenylamino)2-anthrasulfonic acid / Acid Blue 25 (V) (CI62055); Sodium salt of 4-hydroxy-3-((2-methoxyphenyl)azo)-1-naphthalenesulfonic acid / Acid Red 4 (III) (CI14710).

[0379] Most of these dyes are specifically described in the Color Index, published by The Society of Dyers and Colorists, PO Box 244, Perkin House, 82 Grattan Road, Bradford, Yorkshire, BD12JBN, England.

[0380] The most particularly preferred anionic dyes are those named in the color index with the following codes: CI58005 (monosodium salt of 1,2-dihydroxy-9,10-anthraquinone-3-sulfonic acid), CI60730 (monosodium salt of 2-[(9,10-dihydro-4-hydroxy-9,10-dioxo-1-anthrayl)amino]-5-methylbenzenesulfonic acid), CI15510 (monosodium salt of 4-[(2-hydroxy-1-naphthyl)azo]benzenesulfonic acid), CI15985 (disodium salt of 6-hydroxy-5-[(4-sulfophenyl)azo]-2-naphthalenesulfonic acid), CI17200 (5-amino-4-hydroxy-3-(phenylazo)- Disodium salt of 2,7-naphthalenedisulfonic acid), CI20470 (disodium salt of 1-amino-2-(4'-nitrophenylazo)-7-phenylazo-8-hydroxy-3,6-naphthalenedisulfonic acid), CI42090 (disodium salt of N-ethyl-N-[4-[[4-[ethyl(3-sulfophenyl)methyl]amino]phenyl](2-sulfophenyl)methylene]-2,5-cyclohexadiene-1-ylidene]-3-sulfobenzamide hydroxide, inner salt), CI61570 (disodium salt of 2,2'-[(9,10-dihydro-9,10-dioxo-1,4-anthratridiyl)diimino]-bis-[5-methyl]benzenesulfonic acid).

[0381] Compounds corresponding to the meso or tautomer forms of structures (III) to (X) can also be used.

[0382] Natural dyes

[0383] Direct dyes (b) can be selected from natural direct dyes.

[0384] Among the natural direct dyes that can be used according to the present invention are lawsone, juglone, alizarin, purpurin, carminic acid, kernelesic acid, purpurogallin, protocatechaldehyde, indigo, indigo, curcumin, spinulosin, apigenidin, orcein, brassinolide, oxybrassinolide, heme, and hematoxylin. Extracts or decoctions containing these natural dyes, and especially poultices or extracts based on henna, may also be used.

[0385] According to a preferred embodiment, the direct dye b) is selected from triarylmethane direct dyes of the following formulas (IIa1) and (IIa2) and mixtures thereof:

[0386]

[0387] in:

[0388] ■ R1, R2, R3, and R4 may be the same or different, representing a hydrogen atom or one of the following groups: optionally preferably a (C1-C6) alkyl group substituted with a hydroxyl group; aryl such as phenyl, aryl (C1-C4) alkyl such as benzyl, heteroaryl, heteroaryl (C1-C4) alkyl, or additionally, two groups R1 and R2, and / or R3 and R4 on the same nitrogen atom together with the nitrogen atom containing them to form an optionally substituted heterocyclic alkyl group, such as morpholino, piperazine, or piperidinyl, preferably R1, R2, R3, and R4 may be the same or different, representing a hydrogen atom or a (C1-C4) alkyl group;

[0389] ■R5, R6, R7, R8, R9, R 10 R 11 R 12 R 13 R 14 R 15 and R 16 The groups can be the same or different, representing hydrogen or halogen atoms, or selected from 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) amide (-NR-C(O)R'), wherein the R group is a hydrogen atom, optionally a C1-C4 alkyl group with at least one hydroxyl group, and the R' group is a C1-C2 alkyl group; viii) carbamoyl ((R)2N-C(O)-), wherein the R group can be the same or different, representing hydrogen atom or optionally a C1-C4 alkyl group with at least one hydroxyl group; ix) carboxylic acid or ester (-OC(O)R') or (-C( O)OR'), wherein the R' group is a hydrogen atom or a C1-C4 alkyl group optionally having at least one hydroxyl group, and the R' group is a C1-C2 alkyl group; x) optionally, particularly, an alkyl group substituted with a hydroxyl group; xi) alkylsulfonylamino (R'SO2-NR-), wherein the R group represents a hydrogen atom or a C1-C4 alkyl group optionally having at least one hydroxyl group, and the R' group represents a C1-C4 alkyl group, phenyl group; xii) aminosulfonyl ((R)2N-SO2-), wherein the R groups may be the same or different, representing a hydrogen atom or a C1-C4 alkyl group optionally having at least one hydroxyl group; xiii) (C1-C4) alkoxy group; and xiv) (C1-C4) alkylthio group;

[0390] ■Or, alternatively, two adjacent carbon atoms bearing 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 16 Together with the carbon atoms containing them, they form aryl or heteroaryl groups, preferably benzo[a], 6-membered fused rings, which may also be optionally substituted, preferably unsubstituted benzo[a] rings;

[0391] ■Q - This refers to anionic counterions used to achieve electroneutrality, which are preferably selected from halide ions such as chloride or bromide ions, and phosphate ions.

[0392] Direct dyes (b) may preferably be selected from Basic Violet 1, Basic Violet 2, Basic Violet 3, Basic Violet 4, Basic Blue 1, Basic Blue 7, Basic Green 1 and HC Blue 15, and mixtures thereof.

[0393] More preferably, the direct dye b) is HC Blue 15.

[0394] The direct dye b) may be present in the composition in a total amount ranging from 0.001% to 10% by weight, preferably from 0.05% to 5% by weight, and more preferably from 0.1% to 3% by weight relative to the total weight of the composition.

[0395] Heterocyclic salts of formula (A):

[0396] The compositions according to the invention comprise c) one or more heterocyclic salts of formula (A):

[0397]

[0398] in:

[0399] ■Het represents cationic, aromatic, unsaturated heterocyclic groups, which include:

[0400] -5 to 10 ring members, preferably 5 or 6 ring members; and

[0401] - One or two atoms other than ammonium with R1, selected from nitrogen or oxygen atoms, preferably nitrogen atoms;

[0402] The heterocyclic group is optionally substituted with one or more R'1 or R2 groups;

[0403] ■ R1 and R'1 can be the same or different, representing straight or branched chains, saturated or unsaturated chains based on C1-C. 12The hydrocarbon group, wherein the hydrocarbon-based group is optionally, in particular, substituted with one or more groups selected from the following: hydroxyl, amino, (C1-C6)dialkylamino, (C1-C6)alkylamino, carboxyl, carboxylate, urea, (C1-C4)alkoxy, -SO3H, sulfonate and phenyl.

[0404] ■R2 indicates a hydroxyl, amino, straight-chain or branched saturated or unsaturated C1-C group. 12 The hydrocarbon group, wherein the hydrocarbon-based group is optionally, in particular, substituted with one or more groups selected from: hydroxyl, amino, (C1-C6)dialkylamino, (C1-C6)alkylamino, carboxyl, carboxyl, urea, (C1-C4)alkoxy, -SO3H, sulfonate, and phenyl; and

[0405] ■Y - Indicates anion counterion;

[0406] It should be understood that:

[0407] - When one of the hydrocarbon-based groups of R1, R'1, or R2 is replaced by a carboxylate group or a sulfonate group, then Y - There is no salt that can ensure the electroneutrality of the salt of formula (A).

[0408] Preferably, the salt of formula (A) is selected from those of formula (I):

[0409]

[0410] Equation (I), where:

[0411] ■R1 indicates whether the chain is straight or branched, saturated or unsaturated, based on C1-C. 12 The hydrocarbon group, wherein the hydrocarbon-based group is optionally substituted by one or more groups selected from the following: hydroxyl, amino, (C1-C6)dialkylamino, (C1-C6)alkylamino, carboxyl, carboxylate, urea, (C1-C4)alkoxy, -SO3H, sulfonate and phenyl.

[0412] ■R'1 indicates that the hydrogen atom, straight chain, or branched chain is saturated or unsaturated based on C1-C. 12 The hydrocarbon group, wherein the hydrocarbon-based group is optionally substituted by one or more groups selected from: hydroxyl, amino, (C1-C6)dialkylamino, (C1-C6)alkylamino, carboxyl, carboxyl, urea, (C1-C4)alkoxy, -SO3H, sulfonate, and phenyl; and

[0413] ■R2 indicates hydroxyl groups, straight-chain or branched saturated or unsaturated C1-C. 12The hydrocarbon-based group, wherein the hydrocarbon-based group is optionally substituted by one or more groups selected from the group consisting of: hydroxyl, (C1-C4)alkoxy, -SO3H, sulfonate and phenyl;

[0414] ■n is 0, 1, 2 or 3, preferably n is 0 or 1;

[0415] ■Y - Indicates anion counterion;

[0416] It should be understood that:

[0417] - When one of the hydrocarbon-based groups of R1, R'1, or R2 is replaced by a carboxylate group or a sulfonate group, then Y - There is no salt that can ensure the electroneutrality of the salt of formula (A), and

[0418] When n is 2 or 3, the substituents are either the same or different.

[0419] According to one specific embodiment, the salt of formula (I) is a C1-C8 hydrocarbon-based group, such that R'1 represents a hydrogen atom or a straight-chain or branched, saturated or unsaturated group, optionally selected from hydroxyl, (C1-C2)alkoxy, -SO3H, -SO3 - The phenyl group may be substituted with one or more groups; preferably, R'1 represents a hydrogen atom or a saturated, straight-chain or branched, more preferably straight-chain group based on a C1-C6 hydrocarbon; even more preferably, R'1 represents a methyl group.

[0420] According to one specific embodiment, the salt of formula (I) is such that R2 represents a straight-chain or branched, saturated C1-C6 hydrocarbon-based group such as methyl, and preferably n is 1 and R2 is at position 2.

[0421] According to a preferred embodiment of the present invention, the salt of formula (A) is selected from compounds 1 to 27 and mixtures thereof:

[0422]

[0423]

[0424]

[0425]

[0426] Where Y - Indicates anion counterion;

[0427] Preferably selected from compounds 2, 3, 4, 5 and 25 and mixtures thereof, more preferably selected from compounds 2, 4, 5 and 25 and mixtures thereof, and even more preferably selected from compound 4 and mixtures thereof.

[0428] According to a preferred embodiment of the present invention, the salt of formula (A) is such that Y - The following are selected as counterions of anions: i) halide ions such as chloride or bromide ions; ii) hydrosulfide ions; iii) dihalogenated (C1-C2) ... 12 (iv) Alkyl)sulfonyl imides such as bis(trifluoromethylsulfonyl)imide and bis(fluorosulfonyl)imide; 12 ) alkyl sulfate; v)(poly)halophosphate such as hexafluorophosphate; vi)(C1-C 12 (alkyl) phosphate, such as phosphate; vii (poly) haloborate, such as tetrafluoroborate; viiii) carbonate; ix) bicarbonate; x) (C1-C 12 ) alkyl carbonate; xi) dicyandiamide; xii) nitrate; xiii) thiocyanate; xiv) formate; xv)(C1-C 12 )alkylcarboxylate group, wherein (C1-C 12 Alkyl groups may be substituted with one or more halogen atoms or groups selected from the following: hydroxyl, (C1-C6) (di) (alkyl)amino, phenyl, imidazole, (C1-C4) alkyl carbonyl, (C1-C4) alkyl carbonyloxy, (C1-C4) alkyl carbonylamino, guanidine, thiol, -SO3H, (C1-C8) alkoxy such as trifluoroacetate; xvi) (C1-C 20 ) olefin carboxylate group, wherein (C1-C 20 ) An olefinic group may have one or more double bonds and may be substituted by one or more hydroxyl groups; xvii)(C6-C 12 ) aryl carboxylate group, wherein the aryl group may be substituted by one or more halogen atoms or groups selected from: hydroxyl, (C1-C6) (bis(alkyl)amino, phenyl, imidazole, (C1-C4) alkyl carbonyl, (C1-C4) alkyl carbonyloxy, (C1-C4) alkyl carbonylamino, guanidine, thiol, -SO3H, (C1-C8) alkoxy; xviii)(C1-C 12 )alkyl sulfonate, wherein (C1-C 12 Alkyl groups may be substituted with one or more halogen atoms or groups selected from the following: hydroxyl, (C1-C6)(bis(alkyl)amino, phenyl, imidazole, (C1-C4)alkylcarbonyl, (C1-C4)alkylcarbonyloxy, (C1-C4)alkylcarbonylamino, guanidine, thiol, -SO3H, (C1-C8)alkoxy, such as trifluoromethanesulfonate, especially (C1-C6)alkylsulfonate, such as methanesulfonate or methanesulfonate; and xix)(C6-C 12) aryl sulfonate, wherein the aryl group may be substituted by 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 carbonylamino, guanidine, thiol, -SO3H, (C1-C8) alkoxy, such as benzenesulfonate and toluenesulfonate (toluenesulfonate or tosylate); preferably, Y - The following are selected anion counterions:

[0429]

[0430] More preferably, Y - The following are selected anion counterions:

[0431]

[0432] Even more preferably, Y - The following are selected anion counterions:

[0433]

[0434] According to a particularly preferred embodiment, the salt of formula (A) is selected from compounds 4a, 4b, 4c and 4d, and mixtures thereof:

[0435]

[0436] 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 preferably from 5% to 80% by weight, even more preferably from 5% to 60% by weight, most preferably from 5% to 50% by weight, and even more preferably from 5% to 40% by weight, relative to the total weight of the composition.

[0437] peroxide d)

[0438] The composition according to the invention preferably contains d) one or more peroxides. The peroxide is preferably selected from persulfates, perborates or percarbonates of alkali metals or alkaline earth metals or ammonium, and mixtures thereof, more preferably from sodium persulfate, potassium persulfate or ammonium persulfate and mixtures thereof.

[0439] The peroxide (d) is preferably present in the composition in a total content ranging from 0.1% to 50% by weight, and more preferably from 1% to 25% by weight, relative to the total weight of the composition.

[0440] Alkali e)

[0441] The composition according to the invention preferably comprises e) one or more alkaline agents. The alkaline agent is preferably selected from 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 agent is selected from ammonia, monoethanolamine, and silicates such as sodium silicate, and mixtures thereof.

[0442] The alkali agent e) is preferably present in the composition in a total content ranging from 0.01% to 40% by weight, and preferably from 0.1% to 30% by weight, relative to the total weight of the composition.

[0443] The compositions according to the present invention are cosmetic compositions, i.e., they are in a cosmetic medium.

[0444] The term "cosmetic medium" is intended to refer to a medium applied to dyed keratin fibers, also known as a dye support, which is a cosmetic medium typically formed of water or a mixture of water and one or more organic solvents or a mixture of organic solvents.

[0445] The composition preferably contains water in an amount ranging from 5% to 99% by weight, more preferably from 5% to 95% by weight, relative to the total weight of the composition.

[0446] The term "organic solvent" is intended to refer to organic substances that can dissolve another substance without chemically modifying it.

[0447] As organic solvents, examples 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; and aromatic alcohols such as benzyl alcohol or phenoxyethanol, and mixtures thereof.

[0448] The organic solvent is present in a proportion preferably ranging from 0.1% to 40% by weight, more preferably from 1% to 30% by weight, and even more preferably from 1% to 25% by weight relative to the total weight of the composition.

[0449] According to a preferred embodiment, the composition according to the invention comprises:

[0450] a) One or more chemical oxidants selected from hydrogen peroxide, hydrogen peroxide generating agents other than peroxide salts, and mixtures thereof;

[0451] b) One or more direct dyes;

[0452] c) One or more heterocyclic salts of formula (A) as previously defined;

[0453] d) One or more peroxide salts;

[0454] e) One or more alkaline agents.

[0455] According to another preferred embodiment, the composition according to the invention comprises:

[0456] a) One or more chemical oxidants selected from hydrogen peroxide, hydrogen peroxide generating agents other than peroxide salts, and mixtures thereof;

[0457] b) One or more direct dyes;

[0458] c) One or more heterocyclic salts of formula (A) as previously defined;

[0459] d) One or more peroxide salts;

[0460] e) One or more alkaline agents;

[0461] f) Water or a mixture of water and one or more organic solvents selected from lower C2-C4 alkanols, preferably ethanol.

[0462] pH

[0463] The pH of the composition according to the invention is preferably 3 to 12, more preferably 5 to 11, and even more preferably 8 to 10.5.

[0464] The pH of this composition can be adjusted using acidifiers or alkalis commonly used in cosmetics.

[0465] Examples of acidifiers that can be mentioned include organic or inorganic acids.

[0466] The term "inorganic acid" is intended to refer to any acid derived from inorganic compounds. Among inorganic acids, hydrochloric acid, phosphoric acid, sulfuric acid, sulfonic acid, and nitric acid may be mentioned.

[0467] The term "organic acid" is intended to refer to any acid derived from organic compounds. Among organic acids, acetic acid, tartaric acid, citric acid, lactic acid, and sulfonic acid may be mentioned.

[0468] In particular, inorganic or organic acids can be used, such as hydrochloric acid, phosphoric acid, sulfuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid, lactic acid, and sulfonic acid.

[0469] Examples of alkaline agents that may be mentioned include ammonia, alkali metal carbonates, alkanolamines (such as monoethanolamine, diethanolamine, and triethanolamine) and their derivatives, sodium hydroxide, potassium hydroxide, and compounds of the following formula (B):

[0470]

[0471] Formula (B), wherein W is an (C1-C6) alkylene group optionally substituted with one or more hydroxyl groups; R a R b R c and R d These can be the same or different, representing hydrogen atoms or (C1-C4) alkyl groups optionally substituted with one or more hydroxyl groups. Preferably, the pH adjuster can be selected from alkaline agents such as ammonia, monoethanolamine, diethanolamine, triethanolamine, 1,3-propanediamine, or alkaline hydroxides such as 2-amino-2-methyl-1-propanol, or acidifying agents such as phosphoric acid or hydrochloric acid.

[0472] The compositions according to the invention can be in liquid form, slurry form, thickened form (particularly in gel, cream, wax or paste form), or foam form.

[0473] The compositions according to the invention may also contain one or more additional compounds selected from the following: nonionic, anionic, cationic or amphoteric surfactants; cationic, anionic, nonionic or amphoteric, associated or non-associated thickening polymers of natural or synthetic origin; silicone or non-silicone plant extracts in the form of oils, gums or resins; mineral oils or synthetic oils; UV-masking agents; fillers (such as mother-of-pearl) and metal oxides (such as titanium dioxide); clay; fragrances; adhesives; vitamins and preservatives.

[0474] Method for simultaneously bleaching and dyeing keratin fibers

[0475] According to a second aspect, the subject of the present invention is a method for simultaneously bleaching and dyeing keratin fibers, the method comprising applying a composition as previously defined to the keratin fibers.

[0476] This composition can be applied to wet or dry keratin fibers.

[0477] Preferably, the application of the composition according to the invention to keratin fibers is carried out at an ambient temperature, i.e., at a temperature of 25°C to 30°C.

[0478] The method may include the step of leaving the composition on keratin fibers for a duration ranging from 5 to 60 minutes.

[0479] According to an advantageous variant of the invention, after the application of the composition or after a dwell time (if present), for example at a temperature greater than or equal to 30°C, the keratin fibers are rinsed, optionally shampooed, and then left to dry or air-dried.

[0480] According to one embodiment, the temperature is greater than 40°C. According to another embodiment, the temperature is greater than 45°C and less than 220°C.

[0481] Preferably, if drying keratin fibers, they are dried using an airflow in addition to heating.

[0482] During the drying process, mechanical actions can be applied to the fibers, such as combing, brushing, or running fingers through them. This process can be repeated once the keratin fibers have dried naturally or otherwise.

[0483] The drying process can be carried out using drying devices such as hoods, hair dryers, or Climazon.

[0484] The drying process can be carried out using a hood or a hair dryer, with a drying temperature range of 40°C to 110°C, preferably 50°C to 90°C.

[0485] Once dry, you may choose to rinse or shampoo your hair.

[0486] The composition is preferably applied to moist or dry keratin fibers at a weight ratio of 0.1 to 10, and more particularly 0.2 to 7.5, of the amount of the composition applied relative to the amount of hair.

[0487] Reagent test kit

[0488] According to a third aspect, the subject of the present invention is a multi-compartment device or reagent kit comprising:

[0489] ■ A first compartment containing a composition comprising a) one or more chemical oxidants selected from hydrogen peroxide, hydrogen peroxide generating agents other than peroxide salts, and mixtures thereof; and

[0490] ■ Contains a second compartment comprising the following composition:

[0491] b) one or more direct dyes; and

[0492] c) One or more salts as previously defined in formula (A);

[0493] or

[0494] ■ A first compartment containing a composition comprising a) one or more chemical oxidants selected from hydrogen peroxide, hydrogen peroxide generating agents other than peroxide salts, and mixtures thereof; and

[0495] ■ A second compartment containing a composition comprising b) one or more direct dyes; and

[0496] ■ A third compartment containing a composition comprising c) one or more salts of formula (A) as previously defined.

[0497] In embodiments where the composition according to the invention comprises d) one or more peroxide salts and / or e) one or more alkali agents, they may be present in the composition contained in the second or third compartment.

[0498] The technical features of the various components of the compositions according to the invention previously defined also apply to the components of the kit.

[0499] Example

[0500] The following examples will make the invention clearer, but are not limiting in nature.

[0501] Example 1

[0502] Prepare the following composition and then administer it according to the administration regimen described below:

[0503] [Table 1]

[0504]

[0505] Application plan

[0506] In a bath at 33°C, apply 10g of composition 1, 2, or 3 to 1g of Caucasian hair strand with a tint depth of 4 (TD4) for 50 minutes. Then rinse the hair strand, shampoo, and dry.

[0507] Colorimetric measurement

[0508] Color accumulation (ΔE*) was evaluated using a Minolta CM3610A spectrophotometer (light source D65) according to the CIE L*a*b* system. In this L*a*b* system, L* represents the intensity of the color, a* indicates the hue of the color on the green / red axis, and b* indicates the hue of the color on the blue / yellow axis. The lower the value of L*, the deeper or more intense the color. The higher the value of a*, the redder the hue, and the higher the value of b*, the bluer the hue.

[0509] In the table below, the value of ΔE* is calculated from the value of L*a*b* according to the following equation:

[0510]

[0511] In the equation, L*, a*, and b* represent the values ​​measured on the pores after treatment with the above scheme, and L0*, a0*, and b0* represent the values ​​measured on the control pores treated with composition 1.

[0512] The higher the ΔE* value, the better the staining accumulation.

[0513] result

[0514] The measurement results are shown in the table below:

[0515] [Table 2]

[0516]

[0517] The results above show that the presence of the salt of formula (A) according to the present invention significantly improves color accumulation.

[0518] Example 2

[0519] Prepare the following composition and then administer it according to the administration regimen described below:

[0520] [Table 3]

[0521]

[0522] Application plan

[0523] In a tub at 33°C, apply 10g of composition 4, 5, or 6 to a 1g TD4 Caucasian hair strand for 50 minutes. Then rinse the hair strand, shampoo, and dry.

[0524] Colorimetric measurement

[0525] Color accumulation (ΔE*) was evaluated using a Minolta CM3610A spectrophotometer (light source D65) according to the CIE L*a*b* system. In this L*a*b* system, L* represents the intensity of the color, a* indicates the hue of the color on the green / red axis, and b* indicates the hue of the color on the blue / yellow axis. The lower the value of L*, the deeper or more intense the color. The higher the value of a*, the redder the hue, and the higher the value of b*, the bluer the hue.

[0526] In the table below, the value of ΔE* is calculated from the value of L*a*b* according to the following equation:

[0527]

[0528] In the equation, L*, a*, and b* represent the values ​​measured on the filaments after treatment with the above scheme, and L0*, a0*, and b0* represent the values ​​measured on the control filaments treated with composition 4.

[0529] The higher the ΔE* value, the better the staining accumulation.

[0530] result

[0531] The measurement results are shown in the table below:

[0532] [Table 4]

[0533]

[0534] The results above show that the presence of the salt of formula (A) according to the present invention significantly improves color accumulation.

[0535] Example 3

[0536] Prepare the following composition and then administer it according to the administration regimen described below:

[0537] [Table 5]

[0538]

[0539]

[0540] Application plan

[0541] In a tub at 33°C, apply 10g of composition 7, 8, or 9 to 1g of 90% white natural Caucasian hair strand for 50 minutes. Then rinse the hair strand, shampoo, and dry.

[0542] Colorimetric measurement

[0543] Color accumulation (ΔE*) was evaluated using a Minolta CM3610A spectrophotometer (light source D65) according to the CIE L*a*b* system. In this L*a*b* system, L* represents the intensity of the color, a* indicates the hue of the color on the green / red axis, and b* indicates the hue of the color on the blue / yellow axis. The lower the value of L*, the deeper or more intense the color. The higher the value of a*, the redder the hue, and the higher the value of b*, the bluer the hue.

[0544] In the table below, the value of ΔE* is calculated from the value of L*a*b* according to the following equation:

[0545]

[0546] In the equation, L*, a*, and b* represent the values ​​measured on the filaments after treatment with the above scheme, and L0*, a0*, and b0* represent the values ​​measured on the control filaments treated with composition 7.

[0547] The higher the ΔE* value, the better the staining accumulation.

[0548] result

[0549] The measurement results are shown in the table below:

[0550] [Table 6]

[0551]

[0552]

[0553] The results above show that the presence of the salt of formula (A) according to the present invention significantly improves color accumulation.

[0554] Example 4

[0555] Prepare the following composition and then administer it according to the administration regimen described below:

[0556] [Table 7]

[0557]

[0558] Application plan

[0559] In a tub at 33°C, apply 10g of composition 10, 11, or 12 to 1g of 90% white natural Caucasian hair strand for 50 minutes. Then rinse the hair strand, shampoo, and dry.

[0560] Colorimetric measurement

[0561] Color accumulation (ΔE*) was evaluated using a Minolta CM3610A spectrophotometer (light source D65) according to the CIE L*a*b* system. In this L*a*b* system, L* represents the intensity of the color, a* indicates the hue of the color on the green / red axis, and b* indicates the hue of the color on the blue / yellow axis. The lower the value of L*, the deeper or more intense the color. The higher the value of a*, the redder the hue, and the higher the value of b*, the bluer the hue.

[0562] In the table below, the value of ΔE* is calculated from the value of L*a*b* according to the following equation:

[0563]

[0564] In the equation, L*, a*, and b* represent the values ​​measured on the pores after treatment with the above scheme, and L0*, a0*, and b0* represent the values ​​measured on the control pores treated with composition 10.

[0565] The higher the ΔE* value, the better the staining accumulation.

[0566] result

[0567] The measurement results are shown in the table below:

[0568] [Table 8]

[0569]

[0570] The results above show that the presence of the salt of formula (A) according to the present invention significantly improves color accumulation.

Claims

1. A composition comprising: a) One or more chemical oxidants selected from hydrogen peroxide, hydrogen peroxide generating agents other than peroxide salts, and mixtures thereof; b) One or more direct dyes; in, The direct dye b) is HC Blue 15. c) One or more heterocyclic salts: It is selected from compounds 4a, 4b, 4c and 4d and mixtures thereof: Wherein, the chemical oxidant a) exists in the composition in a total content ranging from 0.1% to 40% by weight relative to the total weight of the composition. The one or more heterocyclic salts are present in the composition in a total content ranging from 5% to 40% by weight relative to the total weight of the composition. The direct dye (b) is present in the composition in a total content ranging from 0.05% to 5% by weight relative to the total weight of the composition.

2. The composition of claim 1, wherein, The chemical oxidant is hydrogen peroxide.

3. The composition of claim 1, wherein, The chemical oxidant a) is present in the composition in a total amount ranging from 2% to 15% by weight relative to the total weight of the composition.

4. The composition of claim 1, wherein the composition further comprises: d) one or more peroxide salts.

5. The composition of claim 1, further comprising: d) one or more peroxide salts selected from sodium persulfate, potassium persulfate, or ammonium persulfate and mixtures thereof.

6. The composition of claim 4, wherein, The peroxide (d) is present in the composition in a total amount ranging from 0.1% to 50% by weight relative to the total weight of the composition.

7. The composition of claim 4, wherein, The one or more peroxides (d) are present in the composition in a total amount ranging from 1% to 25% by weight relative to the total weight of the composition.

8. The composition of claim 1, further comprising: e) one or more alkali agents.

9. The composition of claim 8, wherein e) one or more alkaline agents are selected from ammonia, alkanolamine, urea, ammonium salts, silicates, phosphates or carbonates of alkali metals or alkaline earth metals, and mixtures thereof.

10. The composition of claim 8, wherein e) one or more alkaline agents are selected from ammonia, monoethanolamine and silicates, and mixtures thereof.

11. The composition of claim 8, wherein, The alkali agent e) is present in the composition in a total amount ranging from 0.01% to 40% by weight relative to the total weight of the composition.

12. The composition of claim 8, wherein, The alkali agent e) is present in the composition in a total amount ranging from 0.1% to 30% by weight relative to the total weight of the composition.

13. The composition of claim 1, wherein, The direct dye (b) is present in the composition in a total amount ranging from 0.1% to 3% by weight relative to the total weight of the composition.

14. The composition of claim 1, wherein, The pH of the composition is 3 to 12.

15. The composition of claim 1, wherein, The pH of the composition is 8 to 10.

5.

16. A method for simultaneously bleaching and dyeing keratin fibers, the method comprising applying to the keratin fibers a composition as defined in any one of claims 1-15.

17. A multi-compartment device or reagent kit, comprising: ■ A first compartment containing a composition comprising a) one or more chemical oxidants selected from hydrogen peroxide, hydrogen peroxide generating agents other than peroxide salts, and mixtures thereof; as well as ■ Contains a second compartment comprising the following composition: b) one or more direct dyes, wherein the direct dye b) is HC Blue 15; and c) One or more heterocyclic salts as defined in any one of claims 1 to 15; or ■ A first compartment containing a composition comprising a) one or more chemical oxidants selected from hydrogen peroxide, hydrogen peroxide generating agents other than peroxide salts, and mixtures thereof; as well as ■ A second compartment containing a composition comprising one or more direct dyes, wherein the direct dye b) is HC Blue 15; and ■ A third compartment comprising a composition containing one or more heterocyclic salts as defined in any one of claims 1 to 15.

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