阅读说明：本技术 使用直接染料和不饱和杂环盐染色角蛋白材料的方法及包含所述直接染料和不饱和杂环盐的组合物 (Process for dyeing keratin materials using a direct dye and an unsaturated heterocyclic salt, and composition comprising said direct dye and an unsaturated heterocyclic salt ) 是由 S·萨贝勒 O·盖拉尔 于 2019-12-17 设计创作，主要内容包括：本发明涉及：一种用于处理角蛋白材料、特别是角蛋白纤维、优选人类角蛋白纤维如头发的美容方法,该美容方法使用a)一种或多种直接染料和b)一种或多种特定杂环盐；一种包含成分a)和b)的组合物以及一种包含a)和b)的试剂盒。(The present invention relates to: a cosmetic process for treating keratin materials, in particular keratin fibres, preferably human keratin fibres such as the hair, using a) one or more direct dyes and b) one or more specific heterocyclic salts; a composition comprising components a) and b) and a kit comprising a) and b).)

1. A process for dyeing keratin materials, in particular keratin fibres, preferably human keratin fibres such as the hair, using:

a) at least one direct dye; and

b) at least one heterocyclic salt of formula (a) and also optical isomers, geometric isomers or tautomers thereof, and solvates such as hydrates:

in the formula (A):

het represents a 5-to 10-membered (preferably 5-or 6-membered) cationic unsaturated aromatic heterocyclic group comprising, in addition to ammonium, 1 to 3 heteroatoms, preferably 1 or 2 nitrogen or oxygen atoms, preferably 1 nitrogen atom, said heterocyclic group being optionally substituted by oneOr more radicals R'₁Or R₂Substitution;

·R₁and R'₁May be the same or different and represents a linear or branched, saturated or unsaturated radical based on (C)₁-C₁₂) A hydrocarbon-based group optionally substituted with one or more groups selected from among: hydroxy, amino, (C)₁-C₆) Dialkylamino group, (C)₁-C₆) Alkylamino, carboxyl, carboxylate, urea, (C)₁-C₄) Alkoxy, -SO₃H. Sulfonate and phenyl;

·R₂represents a hydroxyl group, an amino group, a linear or branched, saturated or unsaturated radical based on (C)₁-C₁₂) A hydrocarbon-based group optionally substituted with one or more groups selected from among: hydroxy, amino, (C)₁-C₆) Dialkylamino group, (C)₁-C₆) Alkylamino, carboxyl, carboxylate, urea, (C)₁-C₄) Alkoxy, -SO₃H. Sulfonate and phenyl; and is

·Y^-Represents an anionic counterion;

it should be understood that:

when R is₁、R’₁Or R₂Is substituted by a carboxylate or sulfonate group, then Y^-Is absent to ensure electroneutrality of the salt of formula (a); and is

-applying the components a) and b) to the material together or separately, i.e. sequentially; preferably, the components a) and b) are applied together to the fiber.

2. Process according to the preceding claim, in which the direct dye a) is a neutral, cationic or anionic direct dye selected from: acridines; acridones; anthra associated anthrones; anthrapyrimidines; anthraquinones; azines; (poly) azo or azo, hydrazono or hydrazone, in particular arylhydrazone; azomethines; benzanthracene ketones; benzimidazoles; benzimidazolones; benzazoles; benzoxazoles; benzopyrans; benzothiazoles; benzoquinones; bis-isoindolines; carboxanilides; coumarins; (ii) cyanine groups such as (di) azacarbonylcyanine groups, (di) azahemicyanine groups, hemicyanine groups or tetraazacarbonylcyanine groups; (di) azines; bis-azines; (di) oxazines; (di) thiazines; (di) phenylamines; (di) phenylmethanes; (di) ketopyrrolopyrroles; flavonoids such as flavanthrones and flavones; fluoropyridines; formazans; indamines; indanthrones; indigoids, thioindigoids, and pseudoindigoids; indophenols; indoaniline compounds; isoindolines; isoindolinones; isoviolanthrones; lactones; (poly) methines, such as methines of the stilbene or styryl type; naphthalimides; naphthanilides; naphthalimides; naphthoquinones; nitro, especially nitro (hetero) aromatic compounds; an oxadiazole; oxazines; perilla ketones; a cyanocyclic ketone; perylene; phenothiazines; phenoxazines; phenothiazines; phthalocyanines; polyenes/carotenoids; porphyrins; pyranthrones; pyrazole anthrones; pyrazolones; pyrimidoanthracene ketones; pyronine compounds; quinacridones; quinolines; quinophthalones; squalane species; tetrazolines; thiazines; thiopyronines; triarylmethanes or xanthenes and natural direct dyes; more preferably neutral, cationic or anionic direct dyes selected from the group consisting of anthraquinones, (poly) azos, methylenes and stilbenes.

3. The method according to claim 1 or 2, wherein the direct dye a) is a neutral direct dye; it is preferably selected from hydrazono dyes, azo and styryl dyes (IVa), diazo and distyryl dyes (IV ' a) and (IV "a), anthraquinone dyes (Va) and azomethine dyes (VIa) and (VI ' a) of the following formulae (IIIa) and (III ' a):

in said formulae (IIIa), (III ' a), (IVa), (IV ' a), (IV "a), (Va), (VIa) and (VI ' a):

ar represents an aryl group, such as phenyl or naphthyl, substituted with at least one electron donating group, such as i) optionally substituted (C)₁-C₈) Alkyl, ii) optionally substituted (C)₁-C₈) Alkoxy, iii) di (C) optionally substituted on the alkyl by hydroxy₁-C₈) (alkyl) amino group, iv) aryl group (C)₁-C₈) Alkylamino, v) optionally substituted N- (C)₁-C₈) alkyl-N-aryl (C)₁-C₈) Alkylamino, or, as a variant, Ar represents a julolidine group;

ar' represents an optionally substituted divalent (hetero) arylene group, such as phenylene, in particular p-phenylene, or naphthylene, optionally, preferably substituted by one or more (C)₁-C₈) Alkyl, hydroxy or (C)₁-C₈) Alkoxy substitution;

ar ″ represents a (hetero) aryl group, optionally, preferably substituted by at least: i) electron withdrawing groups such as nitro, nitroso, -C (X) -X '-R' or ii) (di) (C)₁-C₆) (alkyl) amino, iii) hydroxy, iv) (C)₁-C₆) An alkoxy group; (hetero) aryl is in particular chosen from imidazolyl, triazolyl, indolyl or pyridyl or phenyl, said phenyl being optionally substituted by at least one group chosen from nitro, nitroso and amino, preferably in the position para to said phenyl;

x, X' and X ", which may be identical or different, represent an oxygen or sulfur atom, or a group NR", preferably an oxygen atom;

R₁、R²、R³and R⁴Which may be identical or different, represent a hydrogen or halogen atom, or a group chosen from: hydroxy, thiol, (C)₁-C₄) Alkyl, (C)₁-C₄) Alkoxy, (di) (C)₁-C₄) (alkyl) amino, nitro and nitroso groups;

r ' and R ' ' represent (C)₁-C₄) An alkyl group;

R^aand R^bMay be the same or different and represents a hydrogen atom or (C)₁-C₈) Alkyl, said alkyl being optionally, preferablySubstituted by hydroxy;

or, as a variant, the substituent R^aWith substituents of Ar' and/or R^bWith substituents of Ar and/or R^aAnd R^bTogether with the atoms carrying them form a (hetero) cycloalkyl group;

in particular, R^aAnd R^bRepresents a hydrogen atom or (C)₁-C₄) An alkyl group optionally substituted with a hydroxyl group;

t and T', which may be identical or different, represent a group C (R)^a) Or N, preferably N; and is

L represents a divalent group-ALK-, -C (X) -ALK-, -ALK-C (X) -or-C (X) -ALK-C (X) -wherein ALK represents a linear or branched (C)₁-C₆) An alkylene group, such as methylene,

R₂₂、R₂₃、R₂₄、R₂₅、R₂₆and R₂₇Which may be identical or different, represent a hydrogen or halogen atom, or a group chosen from:

-(C₁-C₆) An alkyl group;

-hydroxy, mercapto;

-(C₁-C₆) Alkoxy group, (C)₁-C₆) An alkylthio group;

-aryloxy or arylthio;

aryl (C)₁-C₆) (alkyl) amino;

- (two) (C)₁-C₆) (alkyl) amino;

- (di) (hydroxy (C)₁-C₆) Alkyl) amino;

z' represents a hydrogen atom or a group NR₂₈R₂₉Wherein R is₂₈And R₂₉Which may be identical or different, represent a hydrogen atom or a group chosen from:

-(C₁-C₆) An alkyl group;

-polyhydroxy (C)₁-C₆) Alkyl groups such as hydroxyethyl;

-aryl, optionally substituted with one or more groups, in particular: i) (C)₁-C₆) An alkyl group; iii) R^o-C(X)-X'-、R^o-X'-C(X)-、R^o-X' -C (X) -X "-, wherein R^oIs represented by (C)₁-C₆) Alkyl, iv) sulfonate;

-a cycloalkyl group; especially cyclohexyl;

z represents a group selected from hydroxyl and NR'₂₈R’₂₉Wherein R'₂₈And R'₂₉May be the same or different and represents R as previously defined₂₈And R₂₉The same atom or group;

in particular, said direct dye of formula (IV "a) is a direct dye of formula (IV'" a), and also optical isomers, geometrical isomers or tautomers thereof, organic or inorganic acid or base salts thereof, and solvates thereof such as hydrates:

in the formula (IV' "a):

R¹and R³May be the same or different, preferably the same, and represents a hydrogen atom or (C)₁-C₄) Alkyl groups such as methyl groups or sugars such as glucosyl groups, preferably hydrogen atoms;

R²and R⁴May be the same or different, preferably the same, and represents a hydrogen atom or (C)₁-C₄) Alkyl or (C)₁-C₄) Alkoxy or-O-sugar radicals such as-O-glucosyl, preferably (C)₁-C₄) An alkoxy group; such as methoxy;

x, which may be identical or different, preferably identical, represent an oxygen or sulphur atom or N-R, wherein R represents a hydrogen atom, preferably an oxygen atom;

ALK denotes (C)₁-C₄) Alkylene groups such as methylene or ethylene, preferably methylene.

4. The process according to the preceding claim, wherein the direct dye a) is a neutral direct dye selected from:

and also organic or inorganic acid or base salts thereof, optical or geometric isomers thereof, and solvates thereof such as hydrates.

5. The process according to any one of the preceding claims, wherein the direct dye a) is selected from anionic direct dyes of the following formulae (III), (III '), (IV'), (V '), (VI'), (VII), (VIII), (IX) and (X):

a) a diaryl anionic azo dye of formula (III) or (III'):

in the formulae (III) and (III'):

R₇、R₈、R₉、R₁₀、R'₇、R'₈、R'₉and R'₁₀Which may be identical or different, represent a hydrogen atom or a group chosen from:

-(C₁-C₆) An alkyl group;

-(C₁-C₆) Alkoxy group, (C)₁-C₆) An alkylthio group;

-hydroxy, mercapto;

-nitro, nitroso;

-R^o-C(X)-X’-、R^o-X’-C(X)-、R^o-X' -C (X) -X "-, wherein R^oRepresents a hydrogen atom or (C)₁-C₆) Alkyl or aryl groups such as phenyl; x, X 'and X' which may be the same or different, represent an oxygen or sulfur atom, or NR wherein R represents a hydrogen atom or (C)₁-C₆) An alkyl group;

-(O)₂S(O^-)-,M⁺wherein M is⁺Represents a hydrogen atom or a cationic counterion;

-(O)CO^--,M⁺wherein M is⁺As described previouslyDefining;

-R”-S(O)₂-, wherein R' represents a hydrogen atom, an alkyl group, or an aryl group, or (di) (C)₁-C₆) (alkyl) amino or aryl (C)₁-C₆) (alkyl) amino; preferably phenylamino or phenyl;

-R”’-S(O)₂-X '-, wherein R' "represents optionally substituted (C)₁-C₆) Alkyl or aryl, X' is as previously defined;

- (two) (C)₁-C₆) (alkyl) amino;

aryl (C)₁-C₆) (alkyl) amino optionally substituted with one or more groups selected from: i) a nitro group; ii) a nitroso group; iii) (O)₂S(O^-)-,M⁺And iv) alkoxy, where M⁺As previously defined;

-optionally substituted heteroaryl; preferably a benzothiazolyl group;

-a cycloalkyl group; especially cyclohexyl;

-Ar-N ═ N-, wherein Ar represents an optionally substituted aryl group; preferably optionally substituted by one or more alkyl groups, (O)₂S(O^-)-,M⁺Or phenyl substituted with phenylamino;

-or alternatively, two contiguous radicals R₇And R₈Or R₈And R₉Or R₉And R₁₀Together form a fused benzo group a'; and R'₇And R'₈Or R'₈And R'₉Or R'₉And R'₁₀Together form a fused benzo group B'; wherein a 'and B' are optionally substituted with one or more groups selected from: i) a nitro group; ii) a nitroso group; iii) (O)₂S(O^-)-,M⁺(ii) a iv) a hydroxyl group; v) a mercapto group; vi) (di) (alkyl) amino; 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 (C)₁-C₆) (alkyl) amino; wherein M is⁺、R^oX, X ', X' and Ar are as previously defined;

w represents WestA sigma bond sigma, an oxygen or sulfur atom, or a divalent group i) -NR-, wherein R is as previously defined, or ii) methylene-C (R)_a)(R_b) -, wherein R_aAnd R_bMay be the same or different and represents a hydrogen atom or an aryl group, or alternatively, R_aAnd R_bForm a spirocycloalkyl group with the carbon atom bearing them; preferably, W represents a sulfur atom or R_aAnd R_bTogether form a cyclohexyl group;

it is understood that formulae (III) and (III ') contain at least one sulfonate group (O) at one of rings A, A ', B, B ' or C₂S(O^-)-,M⁺Or a carboxylate group (O) CO^--,M⁺(ii) a Sodium sulfonate is preferred;

b) pyrazolone anionic azo dyes of the formulae (IV) and (IV'):

in said formulae (IV) and (IV'):

R₁₁、R₁₂and R₁₃May be the same or different and represents a hydrogen or halogen atom, (C)₁-C₆) Alkyl or- (O)₂S(O^-),M⁺Wherein M is⁺As previously defined;

R₁₄represents a hydrogen atom or (C)₁-C₆) Alkyl or-C (O) O^-,M⁺Group, wherein M⁺As previously defined;

R₁₅represents a hydrogen atom;

R₁₆represents an oxo group, in which case R'₁₆Is absent, or alternatively, R₁₅And R₁₆Together form a double bond;

R₁₇and R₁₈Which may be identical or different, represent a hydrogen atom or a group chosen from:

-(O)₂S(O^-)-,M⁺wherein M is⁺As previously defined;

-Ar-O-S(O)₂-, wherein Ar representsAn optionally substituted aryl group, preferably a phenyl group optionally substituted with one or more alkyl groups;

R₁₉and R₂₀Together form a double bond, or an optionally substituted benzo group D';

R'₁₆、R'₁₉and R'₂₀May be the same or different and represents a hydrogen atom or (C)₁-C₆) Alkyl or hydroxy;

R₂₁represents a hydrogen atom or (C)₁-C₆) Alkyl or (C)₁-C₆) An alkoxy group;

R_aand R_bMay be the same or different, are as previously defined; preferably, R_aRepresents a hydrogen atom and R_bRepresents an aryl group such as phenyl;

y represents a hydroxyl group or an oxo group;

represents a single bond when Y is an oxo group; and represents a double bond when Y represents a hydroxyl group;

it is understood that formulae (IV) and (IV') contain at least one sulfonate group (O) on one of rings D or E₂S(O^-)-,M⁺Or a carboxylate group C (O) O^--,M⁺(ii) a Sodium sulfonate is preferred;

c) anthraquinone dyes of the formulae (V) and (V'):

in the formulae (V) and (V'):

R₂₂、R₂₃、R₂₄、R₂₅、R₂₆and R₂₇Which may be identical or different, represent a hydrogen or halogen atom, or a group chosen from:

-(C₁-C₆) An alkyl group;

-hydroxy, mercapto;

-(C₁-C₆) Alkoxy radical、(C₁-C₆) An alkylthio group;

-optionally substituted aryloxy or arylthio, preferably substituted by a group selected from alkyl and (O)₂S(O^-)-,M⁺Wherein M is substituted by one or more groups of⁺As previously defined;

aryl (C)₁-C₆) (alkyl) amino optionally selected from alkyl and (O)₂S(O^-)-,M⁺Wherein M is substituted by one or more groups of⁺As previously defined;

- (two) (C)₁-C₆) (alkyl) amino;

- (di) (hydroxy (C)₁-C₆) Alkyl) amino;

-(O)₂S(O^-)-,M⁺wherein M is⁺As previously defined;

z' represents a hydrogen atom or a group NR₂₈R₂₉Wherein R is₂₈And R₂₉Which may be identical or different, represent a hydrogen atom or a group chosen from:

-(C₁-C₆) An alkyl group;

-polyhydroxy (C)₁-C₆) Alkyl groups such as hydroxyethyl;

-aryl, optionally substituted with one or more groups, in particular: i) (C)₁-C₆) Alkyl groups such as methyl, n-dodecyl, n-butyl; ii) (O)₂S(O^-)-,M⁺Wherein M is⁺As previously defined; iii) R^o-C(X)-X’-、R^o-X’-C(X)-、R^o-X' -C (X) -X "-, wherein R^oX, X 'and X' are as previously defined, preferably R^oIs represented by (C)₁-C₆) An alkyl group;

-a cycloalkyl group; especially cyclohexyl;

z represents a group selected from hydroxyl and NR'₂₈R’₂₉Wherein R'₂₈And R'₂₉May be the same or different and represents R as previously defined₂₈And R₂₉The same atom or group;

it is understood that the formulae (V) and (V)(V') comprises at least one sulfonate group (O)₂S(O^-)-,M⁺Or a carboxylate group-C (O) O^-,M⁺(ii) a Sodium sulfonate is preferred;

d) nitro dyes of the formulae (VI), (VI ') and (VI'):

in said formulae (VI) and (VI'):

R₃₀、R₃₁and R₃₂Which may be identical or different, represent a hydrogen or halogen atom, or a group chosen from:

-(C₁-C₆) An alkyl group;

-optionally substituted by one or more hydroxyl groups (C)₁-C₆) Alkoxy, optionally substituted by one or more hydroxy (C)₁-C₆) An alkylthio group;

-hydroxy, mercapto;

-nitro, nitroso;

poly (C) halide₁-C₆) An alkyl group;

-R^o-C(X)-X’-、R^o-X’-C(X)-、R^o-X' -C (X) -X "-, wherein R^oX, X 'and X' are as previously defined;

-(O)₂S(O^-)-,M⁺wherein M is⁺As previously defined;

-(O)CO^--,M⁺wherein M is⁺As previously defined;

- (two) (C)₁-C₆) (alkyl) amino;

- (di) (hydroxy (C)₁-C₆) Alkyl) amino;

-heterocycloalkyl, such as piperidino, piperazino or morpholino;

in particular, R₃₀、R₃₁And R₃₂Represents a hydrogen atom;

-R_cand R_dMay be the same or different and represents a hydrogen atom or (C)₁-C₆) An alkyl group;

w is as previously defined; w represents in particular a-N (H) -group;

ALK represents a linear or branched divalent C₁-C₆An alkylene group; in particular, ALK represents-CH₂-CH₂-a group;

n is 1 or 2;

p represents an integer between 1 and 5 inclusive;

q represents an integer between 1 and 4 inclusive;

u is 0 or 1;

when n is 1, J represents a nitro group or a nitroso group; in particular nitro;

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-SO₂-a group;

m' represents a hydrogen atom or a cationic counterion;

may be present or absent and represents optionally substituted by one or more radicals R as previously defined₃₀A substituted benzo group;

it is understood that formulae (VI) and (VI') comprise at least one sulfonate group (O)₂S(O^-)-,M⁺Or a carboxylate group-C (O) O^-,M⁺(ii) a Sodium sulfonate is preferred;

d) a triarylmethane dye of formula (VII):

in the formula (VII):

R₃₃、R₃₄、R₃₅and R₃₆Which may be identical or different, represent a hydrogen atom or a group chosen from: (C)₁-C₆) Alkyl, optionally substituted aryl and optionally substituted aryl (C)₁-C₆) An alkyl group; in particular (C)₁-C₆) Alkyl and optionally (O)_mS(O^-)-,M⁺A benzyl group substituted by radicals in which M⁺And m is as previously defined;

R₃₇、R₃₈、R₃₉、R₄₀、R₄₁、R₄₂、R₄₃and R₄₄Which may be identical or different, represent a hydrogen atom or a group chosen from:

-(C₁-C₆) An alkyl group;

-(C₁-C₆) Alkoxy group, (C)₁-C₆) An alkylthio group;

- (two) (C)₁-C₆) (alkyl) amino;

-hydroxy, mercapto;

-nitro, nitroso;

-R^o-C(X)-X’-、R^o-X’-C(X)-、R^o-X' -C (X) -X "-, wherein R^oRepresents a hydrogen atom or an alkyl or aryl group; x, X 'and X' which may be the same or different, represent an oxygen or sulfur atom, or NR wherein R represents a hydrogen atom or (C)₁-C₆) An alkyl group;

-(O)₂S(O^-)-,M⁺wherein M is⁺Represents a hydrogen atom or a cationic counterion;

-(O)CO^--,M⁺wherein M is⁺As previously defined;

-or alternatively, two contiguous radicals R₄₁And R₄₂Or R₄₂And R₄₃Or R₄₃And R₄₄Together form a fused benzo group, said benzo group being optionally substituted with one or more groups selected from: i) a nitro group; ii) a nitroso group; iii) (O)₂S(O^-)-,M⁺(ii) a iv) a hydroxyl group; v) a mercapto group; vi) (II) (C)₁-C₆) (alkyl) amino; vii) R^o-C(X)-X'-；viii)R^o-X'-C(X)-；ix)R^o-X' -c (X) -X "-; wherein M is⁺、R^oX, X ' and X ' ' are as previously defined;

in particular, R₃₇To R₄₀Represents a hydrogen atom, and R₄₁To R₄₄May be the same or different and represents a hydroxyl group or (O)₂S(O^-)-,M⁺(ii) a And when R is₄₃And R₄₄When taken together to form a benzo group, it is preferably substituted with (O)₂S(O^-) -a group substitution;

it is understood that at least one of rings G, H, I or I' includes at least one sulfonate group (O)₂S(O^-) Or carboxylate groups-C (O) O^-(ii) a Preferably a sulfonate group;

e) a xanthene-based dye of formula (VIII):

in said formula (VIII):

R₄₅、R₄₆、R₄₇and R₄₈May be the same or different and represents a hydrogen or halogen atom;

R₄₉、R₅₀、R₅₁and R₅₂Which may be identical or different, represent a hydrogen or halogen atom, or a group chosen from:

-(C₁-C₆) An alkyl group;

-(C₁-C₆) Alkoxy group, (C)₁-C₆) An alkylthio group;

-hydroxy, mercapto;

-nitro, nitroso;

-(O)₂S(O^-)-,M⁺wherein M is⁺Represents a hydrogen atom or a cationic counterion;

-(O)CO^--,M⁺wherein M is⁺As previously defined;

g represents an oxygen or sulfur atom or a group NR_eWherein R is_eAs previously defined; in particular, G represents an oxygen atom;

l represents an alkoxide O^-,M⁺(ii) a Mercaptides S^-,M⁺Or a group NR_fWherein R is_fRepresents a hydrogen atom or (C)₁-C₆) Alkyl radical, and M⁺As previously defined; m⁺In particular sodium or potassium;

l' represents an oxygen or sulfur atom or an ammonium group: n is a radical of⁺R_fR_gWherein R is_fAnd R_gMay be the same or different and represents a hydrogen atom or a group (C)₁-C₆) Alkyl or optionally substituted aryl; l' represents in particular an oxygen atom or optionally substituted by one or more alkyl groups or (O)_mS(O^-)-,M⁺Phenylamino substituted by radicals in which M and M⁺As previously defined;

q and Q', which may be the same or different, represent an oxygen or sulfur atom; in particular, Q and Q' represent oxygen atoms;

M⁺is as previously defined;

f) an indole-based dye of formula (IX):

in said formula (IX):

R₅₃、R₅₄、R₅₅、R₅₆、R₅₇、R₅₈、R₅₉and R₆₀Which may be identical or different, represent a hydrogen atom or a group chosen from:

-(C₁-C₆) An alkyl group;

-(C₁-C₆) Alkoxy group, (C)₁-C₆) An alkylthio group;

-hydroxy, mercapto;

-nitro, nitroso;

-R^o-C(X)-X’-、R^o-X’-C(X)-、R^o-X' -C (X) -X "-, wherein R^oRepresents a hydrogen atom or an alkyl or aryl group; x, X 'and X' which may be the same or different, represent an oxygen or sulfur atom, or NR wherein R represents a hydrogen atom or (C)₁-C₆) An alkyl group;

-(O)₂S(O^-)-,M⁺wherein M is⁺Represents a hydrogen atom or a cationic groupBalancing ions;

-(O)CO^--,M⁺wherein M is⁺As previously defined;

g represents an oxygen or sulfur atom or a group NR_eWherein R is_eAs previously defined; in particular, G represents an oxygen atom;

R_iand R_hMay be the same or different and represents a hydrogen atom or (C)₁-C₆) An alkyl group;

it is understood that formula (IX) comprises at least one sulfonate group (O)₂S(O^-)-,M⁺Or a carboxylate group-C (O) O^-,M⁺(ii) a Sodium sulfonate is preferred;

g) a quinoline-based dye of formula (X):

in the formula (X):

R₆₁represents a hydrogen or halogen atom or (C)₁-C₆) An alkyl group;

R₆₂、R₆₃and R₆₄May be the same or different and represents a hydrogen atom or a group (O)2S (O-) -, M +, wherein M + represents a hydrogen atom or a cationic counterion;

or alternatively, R₆₁And R₆₂Or R₆₁And R₆₄Together form a benzo group optionally substituted with one or more groups (O)₂S(O^-)-,M⁺Is substituted, wherein M⁺Represents a hydrogen atom or a cationic counterion;

it is understood that formula (X) contains at least one sulfonate group (O)₂S(O^-)-,M⁺Preferably sodium sulfonate;

more preferably, the anionic dye is selected from dyes of formula (V), such as acid violet 43.

6. The process of any one of the preceding claims, wherein the salt of formula (A) is such that R₁Represents a straight chain orBranched, preferably linear, saturated or unsaturated, based on (C)₁-C₁₀) A hydrocarbon radical, optionally selected from hydroxyl, (C)₁-C₄) Alkoxy, -SO₃H、-SO₃ ^-And phenyl substituted with one or more groups; preferably, R₁Represents linear or branched, more preferably linear (C)₁-C₈) Alkyl optionally substituted by one or more hydroxy, phenyl, -SO₃H and-SO₃ ^-Is substituted by a group, or alternatively, R₁Represents a linear or branched (C)₂-C₆) Alkenyl, preferably vinyl or allyl.

7. The process of any one of the preceding claims, wherein the salt of formula (a) is such that Y^-Represents an anionic counterion selected from: i) halide ions such as chloride ion, bromide ion; ii) hydrogen sulfate; iii) (bis) (poly) halo (C)₁-C₁₂) (alkyl) sulfonyl imides such as bis (trifluoromethylsulfonyl) imide and bis (fluorosulfonyl) imide; iv) (C)₁-C₁₂) An alkyl sulfate radical; v) (poly) halophosphate, such as hexafluorophosphate; vi) (C)₁-C₁₂) (alkyl) phosphates, such as phosphate; vii) (poly) haloborates, such as tetrafluoroborate; viii) carbonate; ix) bicarbonate; x) (C)₁-C₁₂) An alkyl carbonate radical; xi) dicyandiamide; xii) nitrate radical; xiii) thiocyanate; xiv) formate; xv) (C)₁-C₁₂) Alkyl carboxylate radical, in which (C)₁-C₁₂) Alkyl groups may be substituted with one or more halogen atoms or groups selected from: hydroxy, (C)₁-C₆) (di) (alkyl) amino, phenyl, imidazole, (C)₁-C₄) Alkylcarbonyl group, (C)₁-C₄) Alkylcarbonyloxy, (C)₁-C₄) Alkylcarbonylamino, guanidine, thiol, -SO₃H、(C₁-C₈) Alkoxy, such as trifluoroacetate; xvi) (C₆-C₁₂) Arylcarboxylates, wherein the aryl group may be substituted by one or more halogen atoms or groups selected from: hydroxy, (C)₁-C₆) (di) (alkyl) amino, phenyl, imidazole, (C)₁-C₄) Alkylcarbonyl group, (C)₁-C₄) Alkylcarbonyloxy, (C)₁-C₄) Alkylcarbonylamino, guanidine, thiol, -SO₃H、(C₁-C₈) An alkoxy group; xvii) (C)₁-C₁₂) Alkyl sulfonate radical, wherein (C)₁-C₁₂) Alkyl groups may be substituted with one or more halogen atoms or groups selected from: hydroxy, (C)₁-C₆) (di) (alkyl) amino, phenyl, imidazole, (C)₁-C₄) Alkylcarbonyl group, (C)₁-C₄) Alkylcarbonyloxy, (C)₁-C₄) Alkylcarbonylamino, guanidine, thiol, -SO₃H、(C₁-C₈) Alkoxy, e.g. trifluoromethanesulfonate, especially (C)₁-C₆) Alkyl sulfonates such as methylsulfonate or methanesulfonate; and xviii) (C₆-C₁₂) Arylsulfonate in which the aryl radical can be substituted by one or more halogen atoms or groups chosen from: hydroxy, (C)₁-C₆) (di) (alkyl) amino, phenyl, imidazole, (C)₁-C₄) Alkylcarbonyl group, (C)₁-C₄) Alkylcarbonyloxy, (C)₁-C₄) Alkylcarbonylamino, guanidine, thiol, -SO₃H、(C₁-C₈) Alkoxy groups such as benzenesulfonate and tosylate or tosylate; preferably, Y^-To represent

More preferably, Y^-Selected from i), xvii), and xviii); more preferably, Y "is selected from chloride, bromide, methylsulfate and tosylate.

8. The process according to any one of the preceding claims, wherein the salt of formula (a) is selected from those of formulae (I) and (II) below, and also tautomeric forms thereof:

in the formulae (I) and (II):

R₁represents a linear or branched, saturated or unsaturated radical based on (C)₁-C₁₂) A hydrocarbon-based group optionally substituted with one or more groups selected from: hydroxy, amino, (C)₁-C₆) Dialkylamino group, (C)₁-C₆) Alkylamino, carboxyl, carboxylate, urea, (C)₁-C₄) Alkoxy, -SO₃H. Sulfonate and phenyl;

R’₁represents a hydrogen atom, a linear or branched, saturated or unsaturated radical based on (C)₁-C₁₂) A hydrocarbon-based group optionally substituted with one or more groups selected from: hydroxy, amino, (C)₁-C₆) Dialkylamino group, (C)₁-C₆) Alkylamino, carboxyl, carboxylate, urea, (C)₁-C₄) Alkoxy, -SO₃H. Sulfonate and phenyl; and is

R₂Represents a hydroxyl group, a linear or branched, saturated or unsaturated radical based on (C)₁-C₁₂) A hydrocarbon-based group optionally substituted with one or more groups selected from: hydroxy, (C)₁-C₄) Alkoxy, -SO₃H. Sulfonate and phenyl;

n is 0, 1,2 or 3; preferably, n is 0 or 1;

Y^-represents an anionic counterion;

it should be understood that:

when R is₁、R’₁Or R₂Is substituted by a carboxylate or sulfonate group, then Y^-Is absent to ensure electroneutrality of the salt of formula (a); and is

When n is equal to 2 or 3, the substituents are identical or different.

9. The process of claim 8, wherein the salt of formula (I) is such that R'₁Represents a hydrogen atom or a linear or branched, saturated or unsaturated radical based on (C)₁-C₈) A hydrocarbon-based radical, optionally selected from hydroxyl, (C)₁-C₂) Alkoxy, -SO₃H、-SO₃ ^-And phenyl substituted with one or more groups; preferably, R'₁Represents a hydrogen atom or a saturated, linear or branched, more preferably linear, radical based on (C)₁-C₆) Hydrocarbon radicals, in particular methyl radicals.

10. The method of claim 8 or 9, wherein the salt of formula (I) is such that R₂Denotes a linear or branched, saturated radical based on (C)₁-C₆) Hydrocarbon groups such as methyl; preferably, n is 1 and R₂In position 2.

11. The method of claim 8, wherein the salt of formula (II) is such that R₁Represents a linear or branched, saturated or unsaturated radical based on (C)₁-C₁₂) A hydrocarbon group; in particular, R₁Represents a linear or branched (C)₁-C₈) Alkyl, preferably R₁Is represented by (C)₁-C₄) Alkyl groups such as methyl.

12. The method of claim 8 or 11, wherein the salt of formula (II) is such that R₂Represents a hydroxyl group, a linear or branched, saturated or unsaturated radical based on (C)₁-C₁₂) A hydrocarbon-based radical optionally substituted with one or more hydroxyl groups, (C)₁-C₄) Alkoxy, -SO₃H、-SO₃ ^-And phenyl substitution; preferably, R₂Represents a hydroxyl group or (C)₁-C₄) Alkyl groups such as methyl; r₂Preferably in positions 2', 3' or 4 '.

13. The method of any one of claims 1 to 7, wherein the salt of formula (A) is selected from compounds 1 to 40:

preferably 2, 3, 4, 5, 34 and 36, more preferably 2,4, 5 and 36.

14. The method according to any one of the preceding claims, comprising the step of applying to the fiber a composition, preferably an aqueous composition, comprising a) one or more direct dyes as defined in any one of claims 1 to 5 and b) one or more unsaturated heterocycles (a), (I) or (II) as defined in any one of claims 6 to 13.

15. The method of any one of claims 1 to 13, comprising:

i) a first step of applying to said material a composition, preferably an aqueous composition, comprising a) one or more direct dyes as defined in any one of claims 1 to 5, and then II) a step of applying to said material a composition, preferably an aqueous composition, comprising b) one or more unsaturated heterocyclic salts of formula (a), (I) or (II) as defined in any one of claims 6 to 13;

or I) a first step of applying to said material a composition, preferably an aqueous composition, comprising b) one or more unsaturated heterocyclic salts of formula (a), (I) or (II) as defined in any one of claims 6 to 13, and then II) a step of applying to said material a composition, preferably an aqueous composition, comprising a) one or more direct dyes as defined in any one of claims 1 to 5.

16. A process according to any one of claims 14 and 15, wherein a) the direct dyes as defined in any one of claims 1 to 5 represent from 0.001% to 10% by weight, preferably from 0.05% to 5% by weight, relative to the total weight of the composition in which they are contained, more preferably from 0.3% to 3% by weight, relative to the total weight of the composition in which they are contained.

17. The process according to any one of the preceding claims, wherein a) the direct dye has a temperature of 22 ℃ and atmospheric pressure (760mmHg, i.e. 1.013 x 10) in water⁵Pa) less than 5 wt. -%, preferably less than 1 wt. -% and more preferably less than 0.5 wt. -%.

18. The process of any one of claims 14 to 17, wherein b) the heterocyclic salt (a), (I) or (II) as defined in any one of claims 6 to 13 is present in an amount ranging from 1 to 99.5% by weight, preferably from 3 to 90% by weight, more preferably from 10 to 90% by weight, better still from 20 to 80% by weight, even more preferably from 30 to 70% by weight and most preferably from 40 to 60% by weight relative to the total weight of the composition comprising them.

19. The method of any one of claims 14 to 18, wherein the pH of the composition comprising components a) and b) is between 3 and 13, preferably between 5 and 10 and more preferably between 6 and 9.5.

20. A composition as defined in any one of claims 14 and 16 to 19, comprising a) one or more direct dyes as defined in any one of claims 1 to 5 and b) one or more unsaturated heterocycles (a), (I) or (II) as defined in any one of claims 6 to 13.

21. A multi-compartment device or kit comprising at least one first compartment containing at least one direct dye as defined in any one of claims 1 to 5 and at least one second compartment containing at least one heterocyclic salt of formula (a), (I) or (II) as defined in any one of claims 6 to 13.