PROCESS FOR DYEING KERATIN MATERIALS USING A DIRECT DYE AND AN UNSATURATED HETEROCYCLIC SALT, AND COMPOSITION COMPRISING SAME

Abstract

The present invention relates to a cosmetic process for treating keratin materials, in particular keratin fibers, preferably human keratin fibers such as the hair, using a) one or more direct dyes and b) one or more particular heterocyclic salts, to a composition comprising ingredients a) and b) and to a kit comprising a) and b).

Claims

1. A process for dyeing keratin materials, in particular keratin fibers, preferably human keratin fibers such as the hair, using: a) at least one direct dye; and b) at least one heterocyclic salt of formula (A) and also the optical, geometrical or tautomeric isomers thereof, and the solvates such as hydrates: ##STR00036## in which formula (A): Het represents a 5- to 10-membered (preferentially 5- or 6-membered) cationic unsaturated aromatic heterocyclic group comprising, besides the ammonium, from 1 to 3 heteroatoms, preferentially 1 or 2 nitrogen or oxygen atoms, preferably 1 nitrogen atom, said heterocyclic group being optionally substituted with one or more groups R′.sub.1 or R.sub.2; R.sub.1 and R′.sub.1, which may be identical or different, represent a linear or branched, saturated or unsaturated (C.sub.1-C.sub.12) hydrocarbon-based group optionally substituted notably with one or more groups chosen from hydroxyl, amino, (C.sub.1-C.sub.6)dialkylamino, (C.sub.1-C.sub.6)alkylamino, carboxyl, carboxylate, carbamide, (C.sub.1-C.sub.4)alkoxy, —SO.sub.3H, sulfonate and phenyl; R.sub.2 represents a hydroxyl radical, an amino radical, a linear or branched, saturated or unsaturated (C.sub.1-C.sub.12) hydrocarbon-based group optionally substituted notably with one or more groups chosen from hydroxyl, amino, (C.sub.1-C.sub.6)dialkylamino, (C.sub.1-C.sub.6)alkylamino, carboxyl, carboxylate, carbamide, (C.sub.1-C.sub.4)alkoxy, —SO.sub.3H, sulfonate and phenyl; and Y.sup.− represents an anionic counterion; it being understood that: when one of the hydrocarbon-based groups of R.sub.1, R′.sub.1 or R.sub.2 is substituted with a carboxylate or sulfonate group, then Y.sup.− is absent to ensure the electrical neutrality of the salt of formula (A), and ingredients a) and b) are applied to said materials, together or separately, i.e. sequentially; preferably, ingredients a) and b) are applied together to said fibers.

2. The process as claimed in the preceding claim, in which the direct dyes a) are neutral, cationic or anionic direct dyes chosen from: acridines; acridones; anthranthrones; anthrapyrimidines; anthraquinones; azines; (poly)azos or azos, hydrazono or hydrazones, in particular arylhydrazones; azomethines; benzanthrones; benzimidazoles; benzimidazolones; benzindoles; benzoxazoles; benzopyrans; benzothiazoles; benzoquinones; bis-isoindolines; carboxanilides; coumarins; cyanines, such as (di)azacarbocyanines, (di)azahemicyanines, hemicyanines or tetraazacarbocyanines; (di)azines; bis-azines; (di)oxazines; (di)thiazines; (di)phenylamines; (di)phenylmethanes; (di)ketopyrrolopyrroles; flavonoids, such as flavanthrones and flavones; fluorindines; formazans; indamines; indanthrones; indigoids, thioindigoids and pseudoindigoids; indophenols; indoanilines; isoindolines; isoindolinones; isoviolanthrones; lactones; (poly)methines, such as dimethines of stilbene or styryl types; naphthalimides; naphthanilides; naphtholactams; naphthoquinones; nitro, notably nitro(hetero)aromatics; oxadiazoles; oxazines; perilones; perinones; perylenes; phenazines; phenoxazines; phenothiazines; phthalocyanines; polyenes/carotenoids; porphyrins; pyranthrones; pyrazolanthrones; pyrazolones; pyrimidinoanthrones; pyronines; quinacridones; quinolines; quinophthalones; squaranes; tetrazolines; thiazines; thiopyronines; triarylmethanes or xanthenes and natural direct dyes; more preferentially chosen from anthraquinones, (poly)azos, azomethines and stilbenes.

3. The process as claimed in claim 1 or 2, in which the direct dye(s) a) are neutral direct dyes; preferably chosen from the hydrazono dyes of formulae (IIIa) and (III′a), the azo and styryl dyes (IVa), the diazo and distyryl dyes (IV′a) and (IV″a), the anthraquinone dyes (Va) and the azomethine dyes (VIa) and (VI′a) below: ##STR00037## in which formulae (IIIa), (III′a), (IVa), (IV′a), (IV″a), (Va), (VIa) and (VI′a): Ar represents an aryl radical, such as phenyl or naphthyl, substituted with at least one electron-donating group such as i) optionally substituted (C.sub.1-C.sub.8)alkyl, ii) optionally substituted (C.sub.1-C.sub.8)alkoxy, iii) (di)(C.sub.1-C.sub.8)(alkyl)amino optionally substituted on the alkyl group(s) with a hydroxyl group, iv) aryl(C.sub.1-C.sub.8)alkylamino, v) optionally substituted N—(C.sub.1-C.sub.8)alkyl-N-aryl(C.sub.1-C.sub.8)alkylamino or, as a variant, Ar represents a julolidine group; Ar′ represents an optionally substituted divalent (hetero)arylene group such as phenylene, particularly para-phenylene, or naphthalene, which is optionally substituted, preferably with one or more (C.sub.1-C.sub.8)alkyl, hydroxyl or (C.sub.1-C.sub.8)alkoxy groups; Ar″ represents a (hetero)aryl radical, which is optionally substituted, preferably with at least i) an electron-withdrawing group such as nitro, nitroso, —C(X)—X′—R′ or ii) a (di)(C.sub.1-C.sub.6)(alkyl)amino group, iii) hydroxyl, iv) (C.sub.1-C.sub.6)alkoxy; (hetero)aryl is particularly chosen from imidazolyl, triazolyl, indolyl or pyridyl or phenyl optionally substituted with at least one group chosen from nitro, nitroso and amino, preferably substituted in the position para to the phenyl group; X, X′ and X″, which may be identical or different, represent an oxygen or sulfur atom, or a group NR″, preferably an oxygen atom; R.sub.1, R.sup.2, R.sup.3 and R.sup.4, which may be identical or different, represent a hydrogen or halogen atom, or a group chosen from hydroxyl, thiol, (C.sub.1-C.sub.4)alkyl, (C.sub.1-C.sub.4)alkoxy, (di)(C.sub.1-C.sub.4)(alkyl)amino, nitro and nitroso; R′ and R″ represent a (C.sub.1-C.sub.4)alkyl group; R.sub.a and R.sub.b, which may be identical or different, represent a hydrogen atom or a (C.sub.1-C.sub.8)alkyl group, which is optionally substituted, preferably with a hydroxyl group; or, as a variant, the substituent R.sub.a with a substituent of Ar″ and/or R.sub.b with a substituent of Ar and/or R.sub.a with R.sub.b form, together with the atoms that bear them, a (hetero)cycloalkyl; particularly, R.sub.a and R.sub.b represent a hydrogen atom or a (C.sub.1-C.sub.4)alkyl group, which is optionally substituted with a hydroxyl group; T and T′, which may be identical or different, represent a group C(R.sub.a) or N, preferably N; and L represents a divalent group -ALK-, —C(X)-ALK-, -ALK—C(X)— or —C(X)-ALK—C(X)— with ALK representing a linear or branched (C.sub.1-C.sub.6)alkylene group, such as methylene, R.sub.22, R.sub.23, R.sub.24, R.sub.25, R.sub.26 and R.sub.27, which may be identical or different, represent a hydrogen or halogen atom, or a group chosen from: (C.sub.1-C.sub.6)alkyl; hydroxyl, mercapto; (C.sub.1-C.sub.6)alkoxy, (C.sub.1-C.sub.6)alkylthio; aryloxy or arylthio; aryl(C.sub.1-C.sub.6)(alkyl)amino; (di)(C.sub.1-C.sub.6)(alkyl)amino; (di)(hydroxy(C.sub.1-C.sub.6)alkyl)amino; Z′ represents a hydrogen atom or a group NR.sub.28R.sub.29 with R.sub.28 and R.sub.29, which may be identical or different, representing a hydrogen atom or a group chosen from: (C.sub.1-C.sub.6)alkyl; polyhydroxy(C.sub.1-C.sub.6)alkyl such as hydroxyethyl; aryl optionally substituted with one or more groups, particularly i) (C.sub.1-C.sub.6)alkyl; iii) R.sup.o—C(X)—X′—, R.sup.o—X′—C(X)—, R.sup.o—X′—C(X)—X″— with R.sup.o representing a (C.sub.1-C.sub.6)alkyl group, iv) a sulfonate; cycloalkyl; notably cyclohexyl; Z represents a group chosen from hydroxyl and NR′.sub.28R′.sub.29 with R′.sub.28 and R′.sub.29, which may be identical or different, representing the same atoms or groups as R.sub.28 and R.sub.29 as defined previously; in particular, the direct dyes of formula (IV″a) are of formula (IV′″a), and also the optical, geometrical or tautomeric isomers thereof, the organic or mineral acid or base salts thereof, and solvates thereof such as hydrates: ##STR00038## in which formula (IV″′a): R.sub.1 and R.sub.3, which may be identical or different, preferably identical, represent a hydrogen atom, a (C.sub.1-C.sub.4)alkyl group such as methyl or a sugar such as glucosyl, preferably a hydrogen atom; R.sub.2 and R.sub.4, which may be identical or different, preferably identical, represent a hydrogen atom, a (C.sub.1-C.sub.4)alkyl or (C.sub.1-C.sub.4)alkoxy group or an —O-sugar group such as —O-glucosyl, preferably (C.sub.1-C.sub.4)alkoxy; such as methoxy; X, which may be identical or different, preferably identical, represents an oxygen or sulfur atom or N—R with R representing a hydrogen atom, preferably an oxygen atom; ALK represents a (C.sub.1-C.sub.4) alkylene group such as methylene or ethylene, preferably methylene.

4. The process as claimed in the preceding claim, in which the direct dyes a) are neutral direct dyes chosen from: ##STR00039## ##STR00040## and also the organic or mineral acid or base salts thereof, the optical or geometrical isomers thereof, and the solvates thereof such as hydrates.

5. The process as claimed in any one of the preceding claims, in which the direct dyes a) are chosen from the anionic direct dyes of formulae (III), (III′), (IV), (IV′), (V), (V′), (VI), (VI′), (VII), (VIII), (IX) and (X) below: a) the diaryl anionic azo dyes of formula (III) or (III′): ##STR00041## in which formulae (III) and (III′): R.sub.7, R.sub.8, R.sub.9, R.sub.10, R′.sub.7, R′.sub.8, R′.sub.9 and R′.sub.10, which may be identical or different, represent a hydrogen atom or a group chosen from: (C.sub.1-C.sub.6)alkyl; (C.sub.1-C.sub.6)alkoxy, (C.sub.1-C.sub.6)alkylthio; hydroxyl, mercapto; nitro, nitroso; R.sup.o—C(X)—X′—, R.sup.o—X′—C(X)—, R.sup.o—X′—C(X)—X″— with R.sup.o representing a hydrogen atom or a (C.sub.1-C.sub.6)alkyl or aryl group such as phenyl; X, X′ and X″, which may be identical or different, representing an oxygen or sulfur atom, or NR with R representing a hydrogen atom or a (C.sub.1-C.sub.6)alkyl group; (O).sub.2S(O.sup.−)—, M.sup.+ with M.sup.+ representing a hydrogen atom or a cationic counterion; (O)CO.sup.−—, M.sup.+ with M.sup.+ as defined previously; R″—S(O).sub.2—, with R″ representing a hydrogen atom, an alkyl group, or an aryl, (di)(C.sub.1-C.sub.6)(alkyl)amino or aryl(C.sub.1-C.sub.6)(alkyl)amino group; preferentially a phenylamino or phenyl group; R″′—S(O).sub.2—X′— with R″′ representing a (C.sub.1-C.sub.6)alkyl group or an aryl group which is optionally substituted, X′ as defined previously; (di)(C.sub.1-C.sub.6)(alkyl)amino; aryl(C.sub.1-C.sub.6)(alkyl)amino optionally substituted with one or more groups chosen from i) nitro; ii) nitroso; iii) (O).sub.2S(O.sup.−)—, M.sup.+ and iv) alkoxy with M.sup.+ as defined previously; optionally substituted heteroaryl; preferentially a benzothiazolyl group; cycloalkyl; notably cyclohexyl; Ar-N═N— with Ar representing an optionally substituted aryl group; preferentially a phenyl optionally substituted with one or more alkyl, (O).sub.2S(O.sup.−)—, M.sup.+ or phenylamino groups; or alternatively two contiguous groups R.sub.7 with R.sub.8 or R.sub.8 with R.sub.9 or R.sub.9 with R.sub.10 together form a fused benzo group A′; and R′.sub.7 with R′.sub.8 or R′.sub.8 with R′.sub.9 or R′.sub.9 with R′.sub.10 together form a fused benzo group B′; with A′ and B′ optionally substituted with one or more groups chosen from i) nitro; ii) nitroso; iii) (O).sub.2S(O.sup.−)—, M.sup.+; iv) hydroxyl; v) mercapto; vi) (di)(alkyl)amino; vii) R.sup.o—C(X)—X′—; viii) R.sup.o—X′—C(X)—; ix) R.sup.o—X′—C(X)—X″—; x) Ar-N═N— and xi) optionally substituted aryl(C.sub.1-C.sub.6)(alkyl)amino; with M.sup.+, R.sup.o, X, X′, X″ and Ar as defined previously; W represents a sigma bond σ, an oxygen or sulfur atom, or a divalent radical i) —NR— with R as defined previously, or ii) methylene —C(R.sub.a)(R.sub.b)— with R.sub.a and R.sub.b, which may be identical or different, representing a hydrogen atom or an aryl group, or alternatively R.sub.a and R.sub.b form, with the carbon atom that bears them, a spiro cycloalkyl; preferentially, W represents a sulfur atom or R.sub.a and R.sub.b together form a cyclohexyl; it being understood that formulae (III) and (III′) comprise at least one sulfonate radical (O).sub.2S(O.sup.−)—, M.sup.+ or one carboxylate radical (O)CO.sup.−—, M.sup.+ on one of the rings A, A′, B, B′ or C; preferentially sodium sulfonate; b) the pyrazolone anionic azo dyes of formulae (IV) and (IV′): ##STR00042## in which formulae (IV) and (IV′): R.sub.11, R.sub.12 and R.sub.13, which may be identical or different, represent a hydrogen or halogen atom, a (C.sub.1-C.sub.6)alkyl group or —(O).sub.2S(O.sup.−)—, M.sup.+ with M.sup.+ as defined previously; R.sub.14 represents a hydrogen atom, a (C.sub.1-C.sub.6)alkyl group or a —C(O)O.sup.−, M.sup.+ group with M.sup.+ as defined previously; R.sub.15 represents a hydrogen atom; R.sub.16 represents an oxo group, in which case R′.sub.16 is absent, or alternatively R.sub.15 with R.sub.16 together form a double bond; R.sub.17 and R.sub.18, which may be identical or different, represent a hydrogen atom or a group chosen from: (O).sub.2S(O.sup.−)—, M.sup.+ with M.sup.+ as defined previously; Ar-O—S(O).sub.2— with Ar representing an optionally substituted aryl group, preferentially a phenyl optionally substituted with one or more alkyl groups; R.sub.19 and R.sub.20 together form either a double bond, or a benzo group D′, which is optionally substituted; R′.sub.16, R′.sub.19 and R′.sub.20, which may be identical or different, represent a hydrogen atom or a (C.sub.1-C.sub.6)alkyl or hydroxyl group; R.sub.21 represents a hydrogen atom or a (C.sub.1-C.sub.6)alkyl or (C.sub.1-C.sub.6)alkoxy group; R.sub.a and R.sub.b, which may be identical or different, are as defined previously; preferentially, R.sub.a represents a hydrogen atom and R.sub.b represents an aryl group such as phenyl; Y represents either 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 being understood that formulae (IV) and (IV′) comprise at least one sulfonate radical (O).sub.2S(O.sup.−)—, M.sup.+ or one carboxylate radical C(O)O.sup.−—, M.sup.+ on one of the rings D or E; preferentially sodium sulfonate; c) the anthraquinone dyes of formulae (V) and (V′): ##STR00043## in which formulae (V) and (V′): R.sub.22, R.sub.23, R.sub.24, R.sub.25, R.sub.26 and R.sub.27, which may be identical or different, represent a hydrogen or halogen atom, or a group chosen from: (C.sub.1-C.sub.6)alkyl; hydroxyl, mercapto; (C.sub.1-C.sub.6)alkoxy, (C.sub.1-C.sub.6)alkylthio; optionally substituted aryloxy or arylthio, preferentially substituted with one or more groups chosen from alkyl and (O).sub.2S(O.sup.−)—, M.sup.+ with M.sup.+ as defined previously; aryl(C.sub.1-C.sub.6)(alkyl)amino optionally substituted with one or more groups chosen from alkyl and (O).sub.2S(O.sup.−)—, M.sup.+ with M.sup.+ as defined previously; (di)(C.sub.1-C.sub.6)(alkyl)amino; (di)(hydroxy(C.sub.1-C.sub.6)alkyl)amino; (O).sub.2S(O.sup.−)—, M.sup.+ with M.sup.+ as defined previously; Z′ represents a hydrogen atom or a group NR.sub.28R.sub.29 with R.sub.28 and R.sub.29, which may be identical or different, representing a hydrogen atom or a group chosen from: (C.sub.1-C.sub.6)alkyl; polyhydroxy(C.sub.1-C.sub.6)alkyl such as hydroxyethyl; aryl optionally substituted with one or more groups, particularly i) (C.sub.1-C.sub.6)alkyl such as methyl, n-dodecyl, n-butyl; ii) (O).sub.2S(O.sup.−)—, M.sup.+ with M.sup.+ as defined previously; iii) R.sup.o—C(X)—X′—, R.sup.o—X′—C(X)—, R.sup.o—X′—C(X)—X″— with R.sup.o, X, X′ and X″ as defined previously, preferentially R.sup.o represents a (C.sub.1-C.sub.6)alkyl group; cycloalkyl; notably cyclohexyl; Z represents a group chosen from hydroxyl and NR′.sub.28R′.sub.29 with R′.sub.28 and R′.sub.29, which may be identical or different, representing the same atoms or groups as R.sub.28 and R.sub.29 as defined previously; it being understood that formulae (V) and (V′) comprise at least one sulfonate radical (O).sub.2S(O.sup.−)—, M.sup.+ or one carboxylate radical —C(O)O.sup.−, M.sup.+; preferentially sodium sulfonate; d) the nitro dyes of formulae (VI), (VI′) and (VI″): ##STR00044## in which formulae (VI) and (VI′): R.sub.30, R.sub.31 and R.sub.32, which may be identical or different, represent a hydrogen or halogen atom, or a group chosen from: (C.sub.1-C.sub.6)alkyl; (C.sub.1-C.sub.6)alkoxy optionally substituted with one or more hydroxyl groups, (C.sub.1-C.sub.6)alkylthio optionally substituted with one or more hydroxyl groups; hydroxyl, mercapto; nitro, nitroso; polyhalo(C.sub.1-C.sub.6)alkyl; R.sup.o—C(X)—X′—, R.sup.o—X′—C(X)—, R.sup.o—X′—C(X)—X″— with R.sup.o, X, X′ and X″ as defined previously; (O).sub.2S(O.sup.−)—, M.sup.+ with M.sup.+ as defined previously; (O)CO.sup.−—, M.sup.+ with M.sup.+ as defined previously; (di)(C.sub.1-C.sub.6)(alkyl)amino; (di)(hydroxy(C.sub.1-C.sub.6)alkyl)amino; heterocycloalkyl such as piperidino, piperazino or morpholino; in particular, R.sub.30, R.sub.31 and R.sub.32 represent a hydrogen atom; R.sub.c and R.sub.d, which may be identical or different, represent a hydrogen atom or a (C.sub.1-C.sub.6)alkyl group; W is as defined previously; W particularly represents an —N(H)— group; ALK represents a linear or branched divalent C.sub.1-C.sub.6 alkylene group; in particular, ALK represents a —CH.sub.2—CH.sub.2— 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 or nitroso group; particularly nitro; when n is 2, J represents an oxygen or sulfur atom, or a divalent radical —S(O).sub.m— with m representing an integer 1 or 2; preferentially, J represents an —SO.sub.2— radical; M′ represents a hydrogen atom or a cationic counterion; ##STR00045## which may be present or absent, represents a benzo group optionally substituted with one or more groups R.sub.30 as defined previously; it being understood that formulae (VI) and (VI′) comprise at least one sulfonate radical (O).sub.2S(O.sup.−)—, M.sup.+ or one carboxylate radical —C(O)O.sup.−, M.sup.+; preferentially sodium sulfonate; d) the triarylmethane dyes of formula (VII): ##STR00046## in which formula (VII): R.sub.33, R.sub.34, R.sub.35 and R.sub.36, which may be identical or different, represent a hydrogen atom or a group chosen from (C.sub.1-C.sub.6)alkyl, optionally substituted aryl and optionally substituted aryl(C.sub.1-C.sub.6)alkyl; particularly a (C.sub.1-C.sub.6)alkyl group and benzyl optionally substituted with an (O).sub.mS(O.sup.−)—, M.sup.+ group with M.sup.+ and m as defined previously; R.sub.37, R.sub.38, R.sub.39, R.sub.40, R.sub.41, R.sub.42, R.sub.43 and R.sub.44, which may be identical or different, represent a hydrogen atom or a group chosen from: (C.sub.1-C.sub.6)alkyl; (C.sub.1-C.sub.6)alkoxy, (C.sub.1-C.sub.6)alkylthio; (di)(C.sub.1-C.sub.6)(alkyl)amino; hydroxyl, mercapto; nitro, nitroso; R.sup.o—C(X)—X′—, R.sup.o—X′—C(X)—, R.sup.o—X′—C(X)—X″— with R.sup.o representing a hydrogen atom or an alkyl or aryl group; X, X′ and X″, which may be identical or different, representing an oxygen or sulfur atom, or NR with R representing a hydrogen atom or a (C.sub.1-C.sub.6)alkyl group; (O).sub.2S(O.sup.−)—, M.sup.+ with M.sup.+ representing a hydrogen atom or a cationic counterion; (O)CO.sup.−—, M.sup.+ with M.sup.+ as defined previously; or alternatively two contiguous groups R.sub.41 with R.sub.42 or R.sub.42 with R.sub.43 or R.sub.43 with R.sub.44 together form a fused benzo group optionally substituted with one or more groups chosen from i) nitro; ii) nitroso; iii) (O).sub.2S(O.sup.−)—, M.sup.+; iv) hydroxyl; v) mercapto; vi) (di)(C.sub.1-C.sub.6)(alkyl)amino; vii) R.sup.o—C(X)—X′—; viii) R.sup.o—X′—C(X)—; ix) R.sup.o—X′—C(X)—X″—; with M.sup.+, R.sup.o, X, X′ and X″ as defined previously; particularly, R.sub.37 to R.sub.40 represent a hydrogen atom, and R.sub.43 to R.sub.44, which may be identical or different, represent a hydroxyl group or (O).sub.2S(O.sup.−)—, M.sup.+; and when R.sub.43 with R.sub.44 together form a benzo group, it is preferentially substituted with an (O).sub.2S(O.sup.−)— group; it being understood that at least one of the rings G, H, I or I′ comprises at least one sulfonate radical (O).sub.2S(O.sup.−)— or a carboxylate radical —C(O)O.sup.−; preferentially sulfonate; e) the xanthene-based dyes of formula (VIII): ##STR00047## in which formula (VIII): R.sub.45, R.sub.46, R.sub.47 and R.sub.48, which may be identical or different, represent a hydrogen or halogen atom; R.sub.49, R.sub.50, R.sub.51 and R.sub.52, which may be identical or different, represent a hydrogen or halogen atom, or a group chosen from: (C.sub.1-C.sub.6)alkyl; (C.sub.1-C.sub.6)alkoxy, (C.sub.1-C.sub.6)alkylthio; hydroxyl, mercapto; nitro, nitroso; (O).sub.2S(O.sup.−)—, M.sup.+ with M.sup.+ representing a hydrogen atom or a cationic counterion; (O)CO.sup.−—, M.sup.+ with M.sup.+ as defined previously; G represents an oxygen or sulfur atom or a group NR.sub.e with R.sub.e as defined previously; particularly, G represents an oxygen atom; L represents an alkoxide O.sup.−, M.sup.+; a thioalkoxide S.sup.−, M.sup.+ or a group NR.sub.f, with R.sub.f representing a hydrogen atom or a (C.sub.1-C.sub.6)alkyl group, and M.sup.+ as defined previously; M.sup.+ is particularly sodium or potassium; L′ represents an oxygen or sulfur atom or an ammonium group: N.sup.+R.sub.fR.sub.g, with R.sub.f and R.sub.g, which may be identical or different, representing a hydrogen atom, a (C.sub.1-C.sub.6)alkyl group or an optionally substituted aryl group; L′ represents particularly an oxygen atom or a phenylamino group optionally substituted with one or more alkyl or (O).sub.mS(O.sup.−)—, M.sup.+ groups with m and M.sup.+ as defined previously; Q and Q′, which may be identical or different, represent an oxygen or sulfur atom; particularly Q and Q′ represent an oxygen atom; M.sup.+ is as defined previously; f) the indole-based dyes of formula (IX): ##STR00048## in which formula (IX): R.sub.53, R.sub.54, R.sub.55, R.sub.56, R.sub.57, R.sub.58, R.sub.59 and R.sub.60, which may be identical or different, represent a hydrogen atom or a group chosen from: (C.sub.1-C.sub.6)alkyl; (C.sub.1-C.sub.6)alkoxy, (C.sub.1-C.sub.6)alkylthio; hydroxyl, mercapto; nitro, nitroso; R.sup.o—C(X)—X′—, R.sup.o—X′—C(X)—, R.sup.o—X′—C(X)—X″— with R.sup.o representing a hydrogen atom or an alkyl or aryl group; X, X′ and X″, which may be identical or different, representing an oxygen or sulfur atom, or NR with R representing a hydrogen atom or a (C.sub.1-C.sub.6)alkyl group; (O).sub.2S(O.sup.−)—, M.sup.+ with M.sup.+ representing a hydrogen atom or a cationic counterion; (O)CO.sup.−—, M.sup.+ with M.sup.+ as defined previously; G represents an oxygen or sulfur atom or a group NR.sub.e with R.sub.e as defined previously; particularly, G represents an oxygen atom; R.sub.i and R.sub.h, which may be identical or different, represent a hydrogen atom or a (C.sub.1-C.sub.6)alkyl group; it being understood that formula (IX) comprises at least one sulfonate radical (O).sub.2S(O.sup.−)—, M.sup.+ or one carboxylate radical —C(O)O.sup.−, M.sup.+; preferentially sodium sulfonate; g) the quinoline-based dyes of formula (X): ##STR00049## in which formula (X): R.sub.61 represents a hydrogen or halogen atom or a (C.sub.1-C.sub.6)alkyl group; R.sub.62, R.sub.63 and R.sub.64, which may be identical or different, represent a hydrogen atom or a group (O).sub.2S(O−)—, M+ with M+ representing a hydrogen atom or a cationic counterion; or alternatively R.sub.61 with R.sub.62, or R.sub.61 with R.sub.64, together form a benzo group optionally substituted with one or more groups (O).sub.2S(O.sup.−)—, M.sup.+ with M.sup.+ representing a hydrogen atom or a cationic counterion; it being understood that formula (X) comprises at least one sulfonate radical (O).sub.2S(O.sup.−)—, M.sup.+ preferentially sodium sulfonate; more particularly, the anionic dye(s) are chosen from the dyes of formula (V) such as Acid Violet 43.

6. The process as claimed in any one of the preceding claims, in which the salt(s) of formula (A) are such that R.sub.1 represents a linear or branched, preferably linear, saturated or unsaturated (C.sub.1-C.sub.10) hydrocarbon-based group, optionally substituted with one or more groups chosen from hydroxyl, (C.sub.1-C.sub.4)alkoxy, —SO.sub.3H, —SO.sub.3.sup.− and phenyl; preferentially, R.sub.1 represents a linear or branched, more preferentially linear, (C.sub.1-C.sub.8)alkyl group, optionally substituted with one or more hydroxyl, phenyl, —SO.sub.3H and —SO.sub.3.sup.− groups, or alternatively R.sub.1 represents a linear or branched (C.sub.2-C.sub.6)alkenyl group, preferably vinyl or allyl.

7. The process as claimed in any one of the preceding claims, in which the salt(s) of formula (A) are such that Y′ represents an anionic counterion chosen from i) halides such as chloride, bromide, ii) hydrogen sulfates, iii) (bis)(poly)halo(C.sub.1-C.sub.12)(alkyl)sulfonylimides such as bis(trifluoromethylsulfonyl)imide and bis(fluorosulfonyl)imide, iv) (C.sub.1-C.sub.12)alkyl sulfates, v) (poly)halophosphates such as hexafluorophosphate, vi) (C.sub.1-C.sub.12)(alkyl)phosphates such as phosphate, vii) (poly)haloborates such as tetrafluoroborate, viii) carbonate, ix) bicarbonate, x) (C.sub.1-C.sub.12)alkylcarbonates, xi) dicyanamide, xii) nitrate, xiii) thiocyanate, xiv) formate, xv) (C.sub.1-C.sub.12)alkylcarboxylates in which the (C.sub.1-C.sub.12)alkyl group may be substituted with one or more halogen atoms or groups chosen from hydroxyl, (C.sub.1-C.sub.6)(di)(alkyl)amino, phenyl, imidazole, (C.sub.1-C.sub.4)alkylcarbonyl, (C.sub.1-C.sub.4)alkylcarbonyloxy, (C.sub.1-C.sub.4)alkylcarbonylamino, guanidine, thiol, —SO.sub.3H, (C.sub.1-C.sub.8)alkoxy such as trifluoroacetate; xvi) (C.sub.6-C.sub.12)arylcarboxylates in which the aryl group may be substituted with one or more halogen atoms or groups chosen from hydroxyl, (C.sub.1-C.sub.6)(di)(alkyl)amino, phenyl, imidazole, (C.sub.1-C.sub.4)alkylcarbonyl, (C.sub.1-C.sub.4)alkylcarbonyloxy, (C.sub.1-C.sub.4)alkylcarbonylamino, guanidine, thiol, —SO.sub.3H, (C.sub.1-C.sub.8)alkoxy; xvii) (C.sub.1-C.sub.12)alkylsulfonates in which the (C.sub.1-C.sub.12)alkyl group may be substituted with one or more halogen atoms or groups chosen from hydroxyl, (C.sub.1-C.sub.6)(di)(alkyl)amino, phenyl, imidazole, (C.sub.1-C.sub.4)alkylcarbonyl, (C.sub.1-C.sub.4)alkylcarbonyloxy, (C.sub.1-C.sub.4)alkylcarbonylamino, guanidine, thiol, —SO.sub.3H, (C.sub.1-C.sub.8)alkoxy such as triflate, in particular (C.sub.1-C.sub.6)alkylsulfonates such as methylsulfonate or mesylate; and xviii) (C.sub.6-C.sub.12)arylsulfonates in which the aryl group may be substituted with one or more halogen atoms or groups chosen from hydroxyl, (C.sub.1-C.sub.6)(di)(alkyl)amino, phenyl, imidazole, (C.sub.1-C.sub.4)alkylcarbonyl, (C.sub.1-C.sub.4)alkylcarbonyloxy, (C.sub.1-C.sub.4)alkylcarbonylamino, guanidine, thiol, —SO.sub.3H, (C.sub.1-C.sub.8)alkoxy such as benzenesulfonate and toluenesulfonate ortosylate; preferentially, Y.sup.− represents ##STR00050## more preferentially, Y.sup.− is chosen from i), xvii) and xviii); more preferentially, Y.sup.− is chosen from chloride, bromide, methyl sulfate and tosylate.

8. The process as claimed in any one of the preceding claims, in which the salt(s) of formula (A) are chosen from those of formulae (I) and (II) below, and also the tautomeric forms thereof: ##STR00051## in which formulae (I) and (II): R.sub.1 represents a linear or branched, saturated or unsaturated (C.sub.1-C.sub.12) hydrocarbon-based group optionally substituted with one or more groups chosen from hydroxyl, amino, (C.sub.1-C.sub.6)dialkylamino, (C.sub.1-C.sub.6)alkylamino, carboxyl, carboxylate, carbamide, (C.sub.1-C.sub.4)alkoxy, —SO.sub.3H, sulfonate and phenyl; R′.sub.1 represents a hydrogen atom, a linear or branched, saturated or unsaturated (C.sub.1-C.sub.12) hydrocarbon-based group optionally substituted with one or more groups chosen from hydroxyl, amino, (C.sub.1-C.sub.6)dialkylamino, (C.sub.1-C.sub.6)alkylamino, carboxyl, carboxylate, carbamide, (C.sub.1-C.sub.4)alkoxy, —SO.sub.3H, sulfonate and phenyl; and R.sub.2 represents a hydroxyl group, a linear or branched, saturated or unsaturated (C.sub.1-C.sub.12) hydrocarbon-based group optionally substituted with one or more groups chosen from hydroxyl, (C.sub.1-C.sub.4)alkoxy, —SO.sub.3H, sulfonate and benzene; n is 0, 1, 2 or 3; preferably, n is 0 or 1; Y.sup.− represents an anionic counterion; it being understood that: when one of the hydrocarbon-based groups of R.sub.1, R′.sub.1 or R.sub.2 is substituted with a carboxylate or sulfonate group, then Y.sup.− is absent to ensure the electrical neutrality of the salt of formula (A), and when n is equal to 2 or 3, then the substituents are identical or different.

9. The process as claimed in claim 8, in which the salt(s) of formula (I) are such that R′.sub.1 represents a hydrogen atom or a linear or branched, saturated or unsaturated (C.sub.1-C.sub.8) hydrocarbon-based group optionally substituted with one or more groups chosen from hydroxyl, (C.sub.1-C.sub.2)alkoxy, —SO.sub.3H, —SO.sub.3.sup.− and phenyl; preferentially, R′.sub.1 represents a hydrogen atom or a saturated, linear or branched, more preferentially linear, (C.sub.1-C.sub.6) hydrocarbon-based group, particularly methyl.

10. The process as claimed in claim 8 or 9, in which the salt(s) of formula (I) are such that R.sub.2 represents a linear or branched, saturated (C.sub.1-C.sub.6) hydrocarbon-based group such as methyl; preferably, n is 1 and R.sub.2 is in position 2.

11. The process as claimed in claim 8, in which the salt(s) of formula (II) are such that R.sub.1 represents a linear or branched, saturated or unsaturated (C.sub.1-C.sub.12) hydrocarbon-based group; in particular, R.sub.1 represents a linear or branched (C.sub.1-C.sub.8)alkyl group, preferably R.sub.1 represents a (C.sub.1-C.sub.4)alkyl group such as methyl.

12. The process as claimed in claim 8 or 11, in which the salt(s) of formula (II) are such that R.sub.2 represents a hydroxyl group, a linear or branched, saturated or unsaturated (C.sub.1-C.sub.12) hydrocarbon-based group, optionally substituted with one or more hydroxyl, (C.sub.1-C.sub.4)alkoxy, —SO.sub.3H, —SO.sub.3.sup.− and phenyl groups; preferentially, R.sub.2 represents a hydroxyl group or a (C.sub.1-C.sub.4)alkyl group such as methyl; R.sub.2 is preferably positioned in position 2′, 3′ or 4′.

13. The process as claimed in any one of claims 1 to 7, in which the salt(s) of formula (A) are chosen from compounds 1 to 40: ##STR00052## ##STR00053## ##STR00054## ##STR00055## ##STR00056## ##STR00057## ##STR00058## preferably 2, 3, 4, 5, 34 and 36, more preferentially 2, 4, 5 and 36.

14. The process as claimed in any one of the preceding claims, which comprises the step of applying to said fibers 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 process as claimed in any one of claims 1 to 13, which comprises: either i) a first step of applying to said materials 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 materials 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 materials 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 materials a composition, preferably an aqueous composition, comprising a) one or more direct dyes as defined in any one of claims 1 to 5.

16. The process as claimed in either of claims 14 and 15, in which a) the direct dye(s) as defined in any one of claims 1 to 5 represent from 0.001% to 10% by weight, preferentially from 0.05% to 5% by weight relative to the total weight of the composition comprising them, more preferentially from 0.3% to 3% by weight relative to the total weight of the composition comprising them.

17. The process as claimed in any one of the preceding claims, in which a) the direct dye(s) have a solubility in water at a temperature of 22° C. and at atmospheric pressure (760 mmHg, i.e. 1.013×10.sup.5 Pa) of less than 5% by weight, preferably less than 1% by weight and more preferentially less than 0.5% by weight.

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

19. The process as claimed in any one of claims 14 to 18, in which the pH of the composition(s) comprising ingredients a) and b) is between 3 and 13, preferably between 5 and 10 and more preferentially between 6 and 9.5.

20. The 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 a first compartment which contains at least one direct dye as defined in any one of claims 1 to 5, and at least a second compartment which contains at least one heterocyclic salt of formula (A), (I) or (II) as defined in any one of claims 6 to 13.

Description

EXAMPLES

Dyes Evaluated:

[0322] ##STR00032## ##STR00033##

Heterocyclic Salts:

[0323] ##STR00034## ##STR00035##

Preparation of the Compositions:

[0324] The comparative compositions (Comp. 1 to 6) and the compositions of the invention (Inv. 1 to 6) were prepared by adhering to the amounts described in the tables below:

TABLE-US-00002 TABLE 3 Ingredients Comp 1 Inv 1 Comp. 2 Inv. 2.1 Inv. 2.2 Comp. 3 Inv. 3 Dye 1 (g %)  0.5 0.5 — — — — — Dye 2 (g %) — — 0.5 0.5 0.5 — — Dye 3 (g %) — — — — — 0.5 0.5 Ethylmethylimidazolium — 5 5 — chloride (g %) Ethylmethylimidazolium — — — — 5 — — tosylate (g %) Butylpyridinium — — — — — — 50 chloride (g %) Water qs 100 qs 100 qs 100 qs 100 qs 100 qs 100 qs 100

TABLE-US-00003 TABLE 4 Ingredients Comp 4 Inv 4.1 Inv 4.2 Comp 5 Inv 5.1 Inv 5.2 Inv 5.3 Dye 4 (g %) 0.5  0.5  0.5 — — — — Dye 5 (g %) — — — 0.5  0.5  0.5  0.5 Ethylmethylimidazolium — 50 — — 50 — — tosylate (g %) Ethylmethylimidazolium — — 50 — — — — bromide (g %) Ethylmethylimidazolium — — — — — 50 — methyl sulfate (g %) Butylmethylimidazolium — — — — — — 50 methyl sulfate (g %) Water qs 100 qs 100 qs 100 qs 100 qs 100 qs 100 qs 100

TABLE-US-00004 TABLE 5 Ingredients Comp 6 Inv 6.1 Inv 6.2 Inv 6.3 Inv 6.4 Dye 6 (g %) 0.5  0.5  0.5  0.5  0.5 Hexylmethylimidazolium — 10 — — — chloride (g %) 2-Hydroxyethylmethyl- — — 10 — — imidazolium chloride (g %) Butylmethylimidazolium — — — 10 — bromide (g %) 3-Hydroxy-N- — — — — 10 ethylpyridinium bromide (g %) Water qs 100 qs 100 qs 100 qs 100 qs 100

TABLE-US-00005 TABLE 6 Ingredients Comp 7 Inv 7.1 Inv 7.2 Inv 7.3 Inv 7.4 Inv 7.5 Dye 7 (g %) 0.5  0.5  0.5  0.5  0.5  0.5 Hexylmethylimidazolium chloride — 10 — — — — (g %) 2-Hydroxyethylmethylimidazolium — — 10 — — — chloride (g %) Butylmethylimidazolium bromide — — — 10 — — (g %) Butylmethylimidazolium acetate — — — — 10 — (g %) 3-Hydroxy-N-ethylpyridinium — — — — — 10 bromide (g %) Water qs 100 qs 100 qs 100 qs 100 qs 100 qs 100

TABLE-US-00006 TABLE 7 Ingredients Comp 8 Inv 8.1 Inv 8.2 Inv 8.3 Dye 6 (g %) 0.5 0.5 0.5 0.5 2-Hydroxyethylmethylimidazolium — 10 — — chloride (g %) Butylmethylimidazolium — — 10 — bromide (g %) Butylmethylimidazolium — — — 10 acetate (g %) Water qs 100 qs 100 qs 100 qs 100

Application on Locks:

Protocol 1:

[0325] 5 g of Comparative composition (Comp, x) or of composition according to the invention (Inv. x) are applied to 0.5 g of natural hair containing 90% white hairs, at 33° C. for 30 minutes. The hair is then rinsed, shampooed and dried.

Protocol 2:

[0326] 1 g of Comparative composition (Comp, x) or of composition according to the invention (Inv. x) is applied to 0.5 g of natural hair containing 90% white hairs, at 27° C. for 30 minutes. The hair is then rinsed, shampooed and dried.

Protocol 3:

[0327] The pH of the Comparative composition (Comp, x) or of the composition according to the invention (Inv. x) is adjusted to 3 with lactic acid and 1 g of formula is then applied to 0.5 g of natural hair containing 90% white hairs, at 27° C. for 30 minutes. The hair is then rinsed, shampooed and dried.

Protocol 4:

[0328] The pH of the Comparative composition (Comp, x) or of the composition according to the invention (Inv. x) is adjusted to 7 with aqueous ammonia and 1 g of formula is then applied to 0.5 g of natural hair containing 90% white hairs, at 27° C. for 30 minutes. The hair is then rinsed, shampooed and dried.

Protocol 5:

[0329] 1 g of Comparative composition (Comp, x) or of composition according to the invention (Inv. x) is applied to 0.5 g of natural hair containing 90% white hairs, at 27° C. for 30 minutes, at a pH equal to 9.5. The hair is then rinsed, shampooed and dried.

Protocol 6:

[0330] 1 g of Comparative composition (Comp, x) or of composition according to the invention (Inv. x) is applied to 0.5 g of natural hair containing 90% white hairs, at 33° C. for 30 minutes. The hair is then rinsed, shampooed and dried.

Protocol 7:

[0331] 1 g of Comparative composition (Comp, x) or of composition according to the invention (Inv. x) is applied to 0.5 g of natural hair containing 90% white hairs, at 33° C. for 30 minutes, at a pH equal to 9.5. The hair is then rinsed, shampooed and dried.

Colorimetric Measurements:

[0332] The color build-up (ΔE*) was evaluated in the CIE L* a* b* system using a Minolta Spectrophotometer CM3610A colorimeter, (illuminant D65). In this L*a*b* system, L* represents the intensity of the color, a* indicates the shade of the color on the green/red color axis and b* indicates the shade of the color on the blue/yellow color axis. The lower the value of L*, the darker or more intense the color. The higher the value of a*, the redder the shade, and the higher the value of b*, the bluer the shade.

[0333] In the table below, the value of ΔE* is calculated from the values of L*a*b* according to the following equation:

ΔE*=√{square root over ((L*−L.sub.0*).sup.2+(a*−a.sub.0*).sup.2+(b*−b.sub.0*).sup.2)}

In the equation, L*, a* and b* represent the values measured on the locks after treatment by means of each of the protocols 1 to 4 above, and L.sub.0*, a.sub.0* and b.sub.0* represent the values measured on untreated control locks.

[0334] The higher the ΔE* value, the better the color build-up or variation.

[0335] The results are given in the table below.

Dyeing Results:

[0336] The various build-up results obtained are given in the table below:

TABLE-US-00007 TABLE 6 Protocol ΔE build-up Comparative 1 1 21.1 Invention 1 1 31.5 Protocol L ΔE build-up Comparative 2 2 59.3 8.4 Invention 2.1 2 53.1 13.7 Invention 2.2 2 53.7 14.0 Comparative 3 3 53.0 15.0 Invention 3 3 52.3 17.6 Comparative 4 4 59.7 4.3 Invention 4.1 4 55.3 14.6 Invention 4.2 4 57.4 12.4 Comparative 5 4 55.62 11.42 Invention 5.1 4 45.2 23.5 Invention 5.2 4 46.8 21.5 Invention 5.3 4 51.1 15.62 Comparative 6 6 59.8 5.6 Invention 6.1 6 57.4 16.2 Invention 6.2 6 62 11 Invention 6.3 6 55.8 11.9 Invention 6.4 6 61.8 11.6 Comparative 7 7 50.2 16.3 Invention 7.1 7 32.4 38 Invention 7.2 7 36.8 32 Invention 7.3 7 33.9 36.5 Invention 7.4 7 42.5 23.9 Invention 7.5 7 39 28.1 Comparative 8 7 57.6 6.1 Invention 8.1 7 59.9 23.7 Invention 8.2 7 57.8 15.3 Invention 8.3 7 59 18.1

[0337] It is seen from the above test results that the color build-up is significantly improved by the presence of the saturated heterocyclic salts of formula (A), irrespective of the pH tested. Moreover, the colors obtained are very vivid.