Anionic dye or brightener bearing an ammonium or phosphonium counterion, dye composition comprising them and process for dyeing keratin fibres using these dyes

Abstract

The invention relates to the dyeing of human keratin fibres, especially the hair, using anionic direct dyes bearing a particular ammonium or phosphonium counterion of formula (Ia) and/or optical brighteners of formula (Ib) Col.sup.(−).sub.m[X.sup.+].sub.n (Ia) Azu.sup.(−).sub.m[X.sup.+].sub.n (Ib) in which formulae (Ia) and (Ib): Azu/Col.sup.(−)m, R.sub.1, R.sub.2, R.sub.3, R.sub.4, m and n are as defined in the description. The invention relates to a dye composition comprising an anionic compound of formula (Ia) and/or (Ib), and to a process for dyeing keratin fibres such as the hair, using the said composition. Similarly, the invention relates to novel anionic compounds of formula (Ia) or (Ib) and to the uses thereof for dyeing keratin fibres. This composition makes it possible to obtain chromatic, powerful and particularly fast coloration on keratin fibres and particularly lightening coloration via an optical effect on dark hair.

Claims

1. A method for treating keratin fibres comprising applying a cosmetic composition to said fibers, said composition comprising: at least one compound chosen from anionic compounds of formula (Ia) and formula (Ib):
Col.sup.(−).sub.m[X.sup.+].sub.n  (Ia)
Azu.sup.(−).sub.m[X.sup.+].sub.n  (Ib) optical isomers, geometrical isomers, and solvates thereof; wherein: Col.sup.(−) represents the anionic part of an anionic direct dye comprising m anionic charges chosen from acidic nitro direct dyes, acidic azo dyes, acidic azine dyes, acidic triarylmethane dyes, acidic indoamine dyes, acidic anthraquinone dyes, anionic styryl dyes, indigoids, or acidic natural dyes; Azu.sup.(−) represents the anionic part of an anionic optical brightener comprising m anionic charges chosen from stilbene derivatives, coumarin derivatives, (benz)oxazole derivatives, (benz)imidazole derivatives, (benz)oxazole derivatives, (benzo)furan derivatives, pyrazoline derivatives, or naphthalimide derivatives; m and n are independently chosen from an integer ranging from 1 to 10, inclusive; X.sup.+ represents a monocationic or polycationic counterion or mixture of counterions chosen from: a) the ammoniums and phosphoniums of formulae (1) and (2) below: ##STR00055## b) optionally substituted heteroaromatic groups bearing exocyclic or endocyclic, cationic charges, including (benz)imidazolium, indolinium, (benzo)triazolium, (benzo)pyrylium and (benzo)pyridinium groups, of formulae (3) and (4) below: ##STR00056## c) symmetrical or dissymmetrical dimers of formulae (1), (2), (3) and (4) chosen from those of formulae (1′) to (8′): ##STR00057## d) metallic cations of copper, iron, lithium, magnesium, manganese, gold and zinc, chosen from: Cu.sup.+, Cu.sup.2+, Fe.sup.2+, Fe.sup.3+, Li.sup.+, Mg.sup.2+, Mn.sup.4+, Au.sup.3+ and Zn.sup.2+; and e) cationic oligomers or polymers; wherein, in formulae (1) to (4) and (1′) to (8′): R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are independently chosen from i) linear or branched (C.sub.1-C.sub.20)alkyl; ii) (C.sub.2-C.sub.20)alkenyl; iii) (hetero)aryl(C.sub.1-C.sub.20)alkyl; (hetero)cycloalkyl(C.sub.1-C.sub.20)alkyl, or iv) (hetero)aryl;  the alkyl or alkenyl group of the groups of i), ii), iii) or iv) optionally interrupted with one or more identical or different heteroatoms chosen from an oxygen or sulfur atom, the amino —N(R)—, ammonium —N.sup.+(R.sub.a)(R.sub.b)—, —C(O)—, —C(S)— group or a combination thereof, wherein R, R.sub.a and R.sub.b are independently chosen from hydrogen atoms or alkyl groups; or alternatively the radicals R.sub.1 and R.sub.2 form, together with the quaternized nitrogen or phosphorus atom, a saturated 5- or 6-membered heterocycle, the said heterocycle optionally partially unsaturated, optionally interrupted with a heteroatom chosen from an oxygen atom, the group —N(R)—, or ammonium —N.sup.+(R.sub.a)(R.sub.b)— wherein R, R.sub.a and R.sub.b are independently chosen from hydrogen atoms or alkyl groups, and/or the said heterocycle optionally substituted with one or more alkyl groups; R′.sub.1, R″.sub.1 and R″.sub.2 are independently chosen from i) linear or branched (C.sub.1-C.sub.20)alkyl; ii) (C.sub.2-C.sub.20)alkenyl;  the alkyl or alkenyl group of the groups of i) and ii) optionally interrupted with one or more identical or different heteroatoms chosen from an oxygen or sulfur atom or ammonium —N.sup.+(R.sub.a)(R.sub.b)—, —C(O)—, —C(S)— or a combination thereof, wherein R, R.sub.a and R.sub.b are independently chosen from hydrogen atoms or alkyl groups; wherein R′.sub.1, R″.sub.1 and R″.sub.2, may optionally be substituted with at least one hydroxyl, hydroxycarbonyl or carboxyl, (C.sub.1-C.sub.6)alkoxycarbonyl, alkyl(C.sub.1-C.sub.6)carbonyloxy, carbamoyloxy, (di)(C.sub.1-C.sub.6)(alkyl)silyl or tri(C.sub.1-C.sub.5)alkylsilyl group; R′ and R″ are independently chosen from i) (C.sub.1-C.sub.5)alkyl optionally substituted with one or more radicals chosen from hydroxyl radicals, ii) (C.sub.1-C.sub.5)alkoxycarbonyl, iii) hydroxyl, iv) halogen, v) (C.sub.1-C.sub.5)alkoxy, vi) (poly)hydroxy(C.sub.1-C.sub.5)alkoxy, vii) (di)(C.sub.1-C.sub.5)(alkyl)amino, viii) nitro, ix) acylamino (—N(R)—C(O)R′) with R chosen from a hydrogen atom or a (hydroxy)(C.sub.1-C.sub.5)alkyl radical, x) carbamoyl ((R).sub.2N—C(O)—) with R as defined for ix), xi) carboxylic acid or ester, (—O—C(O)R′) or (—C(O)OR′) with R′ as defined for ix) the carboxylic radical optionally in acid or salified form, xii) alkylsulfonylamino (R′S(O).sub.2—N(R)—) or am inosulfonyl ((R).sub.2N—S(O).sub.2—) with R as defined for ix), xiii) (poly)haloalkyl; or alternatively when p is greater than or equal to 2, two groups R′ or R″ borne by two contiguous carbon atoms together form a (hetero)cycle or a (hetero)aryl; R′″.sub.1, R′″.sub.2, R′″.sub.3 and R′″.sub.4 independently chosen from i) linear or branched (C.sub.1-C.sub.20)alkyl; ii) (C.sub.2-C.sub.20)alkenyl;  the alkyl or alkenyl group of the groups of i) and ii) optionally substituted and/or interrupted with one or more identical or different heteroatoms chosen from an oxygen or sulfur atom, the amino —N(R)—, ammonium —N.sup.+(R.sub.a)(R.sub.b)—, —C(O)—, —C(S)— group or a combination thereof, with R, R.sub.a and R.sub.b independently chosen from hydrogen atoms or alkyl groups; p is equal to 0, 1, 2, 3 or 4; L represents a linear or branched, saturated or unsaturated divalent C.sub.1-C.sub.30 hydrocarbon-based chain, optionally interrupted and/or optionally terminated at one or both of its ends with one or more divalent groups or combinations thereof chosen from: —N(R.sub.a)—; —N.sup.+(R.sub.a)(R.sub.b)—, Q.sup.−; —O—; —S—; —S(O)—, —S(O).sub.2—, —C(O)— and —C(S)— with R.sub.a and R.sub.b independently chosen from hydrogen atoms and a C.sub.1-C.sub.4 alkyl, hydroxy(C.sub.1-C.sub.8)alkyl or amino(C.sub.1-C.sub.8)alkyl radicals and Q.sup.− represents an organic or mineral anionic counterion; an aromatic or non-aromatic, saturated or unsaturated, fused or non-fused, cationic or non-cationic (hetero)cyclic radical optionally comprising one or more identical or different, optionally substituted heteroatoms; wherein: when the dyes of formula (Ia) are such that R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are independently chosen from i) linear or branched (C.sub.1-C.sub.20)alkyl; ii) (C.sub.2-C.sub.20)alkenyl; the alkyl or alkenyl group of the groups of i) and ii) optionally interrupted with one or more identical or different heteroatoms chosen from an oxygen or sulfur atom or the amino —N(R)— group, then at least one of the said radicals R.sub.1, R.sub.2, R.sub.3 and R.sub.4 is substituted with at least one hydroxyl, hydroxycarbonyl or carboxyl, (C.sub.1-C.sub.6)alkoxycarbonyl, (C.sub.1-C.sub.6)alkylcarbonyloxy, carbamoyloxy, (di)(C.sub.1-C.sub.6)(alkyl)silyl or tri(C.sub.1-C.sub.5)alkylsilyl group; when p is equal to 2, 3 or 4, then the groups R′ are identical or different and R″ are identical or different; when the anionic part of the anionic direct dye or of the anionic optical brightener contains a sulfonate group or a carboxylate group, then m=n=1; and when the anionic part of the anionic direct dye or of the anionic optical brightener contains anionic groups other than the sulfonate or carboxylate group, it is combined with one or more organic or mineral cationic counterions or X.sup.+ for affording the electrical neutrality of formula (Ia) or (Ib).

2. The method of claim 1, wherein the composition comprises at least one anionic compound of formula (Ib) wherein the anionic counterion(s) X.sup.+ are of ammonium type R.sub.1R.sub.2R.sub.3R.sub.4N.sup.+ and wherein R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are independently chosen from i) (C.sub.1-C.sub.20)alkyl; ii) (C.sub.2-C.sub.20)alkenyl; the alkyl or alkenyl group of the groups i) and ii) optionally interrupted with one or more identical or different heteroatoms chosen from oxygen, sulfur or N(Rα) with Rα representing a hydrogen atom or an alkyl group.

3. The method of claim 2, wherein the composition comprises at least one anionic compound of formula (Ib) wherein the anionic counterion(s) X.sup.+ are ammonium R.sub.1R.sub.2R.sub.3R.sub.4N.sup.+ with R.sub.1, R.sub.2, R.sub.3, and R.sub.4 independently chosen from linear (C.sub.1-C.sub.20)alkyl groups.

4. The method of claim 1, wherein the composition comprises at least one anionic compound of at least one of formula (Ia) and (Ib), wherein the counterions X.sup.+ are chosen from 1 to 172: TABLE-US-00005 N,N,N-trimethyl-1-hexanaminium N,N-dimethylpyrrolidinium 1 2 1-ethyl-1- N-ethyl-N-methyl-N-(1- methylpyrrolidinium methylethyl)-2-propanaminium 3 4 N,N,N-tributyl-1-heptanaminium N,N,N-tributyl-1-hexanaminium 5 6 N,N,N-triethyl-1-octanaminium 1-methyl-1-pentylpyrrolidinium 7 8 1-hexyl-1-methylpyrrolidinium N,N,N-trimethyl-1-octanaminium 9 10 cocoalkylpentaethoxymethyl- N-hexyl-N,N,N- ammonium triethylammonium 11 12 Cetyltrimethylammonium N,N,N-triethyl-1-heptanaminium 13 14 N,N,N-tributyl-1- N-ethyl-N,N-bis(1-methylethyl)-1- hexanaminium heptanaminium 15 16 N,N,N-tributyl-1-octanaminium 17 17a 17b 17c in which formulae 17a, b and c R.sub.a1 represents a hydrogen atom or a (C.sub.1-C.sub.10)alkyl or (C.sub.1-C.sub.10)alkylcarbonyl radical; and R.sub.a2 represents a hydrogen atom or a (C.sub.1-C.sub.10)alkyl radical TABLE-US-00006 (CH.sub.3).sub.3N.sup.+—(CH.sub.2).sub.5—N.sup.+(CH.sub.3).sub.3 (CH.sub.3).sub.3N.sup.+—(CH.sub.2).sub.6—N.sup.+(CH.sub.3).sub.3 18 19 (CH.sub.3).sub.3N.sup.+—(CH.sub.2).sub.7—N.sup.+(CH.sub.3).sub.3 (CH.sub.3).sub.3N.sup.+—(CH.sub.2).sub.8—N.sup.+(CH.sub.3).sub.3 20 21 (CH.sub.3).sub.3N.sup.+—(CH.sub.2).sub.9—N.sup.+(CH.sub.3).sub.3 (CH.sub.3).sub.3N.sup.+—(CH.sub.2).sub.10—N.sup.+(CH.sub.3).sub.3 22 23 (n-Bu).sub.3N.sup.+—(CH.sub.2).sub.6—N.sup.+(n-Bu).sub.3 [CH.sub.3—(CH.sub.2).sub.7—N.sup.+(CH.sub.3).sub.2—(CH.sub.2).sub.2—].sub.2 24 25 n-oct-N.sup.+(CH.sub.3).sub.2—(CH.sub.2).sub.3—N.sup.+(CH.sub.3).sub.2-n-oct [CH.sub.3—(CH.sub.2).sub.7—N.sup.+(CH.sub.3).sub.2—(CH.sub.2).sub.2—].sub.2 26 27 n-oct-N.sup.+(CH.sub.3).sub.2—(CH.sub.2).sub.5—N.sup.+(CH.sub.3).sub.2-n-oct [CH.sub.3—(CH.sub.2).sub.7—N.sup.+(CH.sub.3).sub.2—(CH.sub.2).sub.3—].sub.2 28 29 n-oct-N.sup.+(CH.sub.3).sub.2—(CH.sub.2).sub.7—N.sup.+(CH.sub.3).sub.2-n-oct n-hex-N.sup.+(CH.sub.3).sub.2—(CH.sub.2).sub.4—N.sup.+(CH.sub.3).sub.2-n-hex 30 31 n-hex-N.sup.+(CH.sub.3).sub.2—(CH.sub.2).sub.8—N.sup.+(CH.sub.3).sub.2-n-hex CH.sub.3—N.sup.+(CH.sub.3CH.sub.2).sub.2—(CH.sub.2).sub.3—N.sup.+(CH.sub.3).sub.2-n-Bu 32 33 (CH.sub.3).sub.3N.sup.+—CH.sub.2—CH(OH)—CH.sub.2—N.sup.+(CH.sub.3).sub.3 HO—CH.sub.2—CH.sub.2—N.sup.+(CH.sub.3).sub.2—CH.sub.2—CH(OH)—CH.sub.2—N.sup.+(CH.sub.3).sub.2—CH.sub.2—CH.sub.2—OH 34 35 (CH.sub.3).sub.3N.sup.+—(CH.sub.2).sub.2—O—C(O)—CH.sub.2—].sub.2 (CH.sub.3).sub.3N.sup.+—(CH.sub.2).sub.2—O—C(O)—(CH.sub.2).sub.3—].sub.2 36 37 (CH.sub.3).sub.3N.sup.+—(CH.sub.2).sub.2—O—C(O)—(CH.sub.2).sub.2—N.sup.+(CH.sub.3).sub.3 [CH.sub.3CH.sub.2O—C(O)—CH.sub.2—N.sup.+(CH.sub.3).sub.2—(CH.sub.2).sub.3—].sub.2 38 39 CH.sub.3O—C(O)—CH.sub.2—N.sup.+(CH.sub.3).sub.2—(CH.sub.2).sub.3—N.sup.+(CH.sub.3).sub.2—CH.sub.2—C(O)—OCH.sub.3 40 [H.sub.2N—C(O)—CH.sub.2—N.sup.+(CH.sub.3).sub.2—CH.sub.2—].sub.2 [HO—CH.sub.2—NH—C(O)—CH.sub.2—N.sup.+(CH.sub.3).sub.2—CH.sub.2—].sub.2 41 42 [CH.sub.3—(CH.sub.2).sub.6—N.sup.+(CH.sub.3).sub.2—(CH.sub.2).sub.2—S].sub.2 (CH.sub.3).sub.3N.sup.+—(CH.sub.2).sub.2—S—S—(CH.sub.2).sub.2—N.sup.+(CH.sub.3).sub.3 43 44 [CH.sub.3—(CH.sub.2).sub.15—N.sup.+(CH.sub.3).sub.2—CH.sub.2—C(O)—NH—(CH.sub.2).sub.2—S—].sub.2 45 [HO—CH.sub.2—NH—C(O)—CH.sub.2—N.sup.+(CH.sub.3).sub.2—(CH.sub.2).sub.2—S—].sub.2 46 (CH.sub.3—CH.sub.2).sub.3N.sup.+—CH.sub.2—CH.sub.2—O—CH.sub.2—CH.sub.2—N.sup.+(CH.sub.2—CH.sub.3).sub.3 47 48 49 50 51 52 53 54 55 56 57 58 N-ethylpyridinium 1-ethyl-3-methylpyridinium 59 60 N-butylpyridinium 4-(dimethylamino)-1-ethylpyridinium 61 62 1-ethylnicotinic acid ethyl ester 1-hexyl-3-methylpyridinium 63 64 1-butyl-3-methylpyridinium 1-hexyl-3,5-dimethylpyridinium 65 66 4-(dimethylamino)-1-hexylpyridinium 1-butylnicotinic acid butyl ester 67 68 1-methyl-3-octylpyridinium; 1- 1-hexyl-3-methyl-4-(dimethylamino)pyridinium 69 70 1-hexyl-4-(4-methylpiperidino)pyridinium 1-hexyl-4-(4-methylpiperidino)pyridinium 71 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86 87 88 89 90 91 92 93 94 95 96 97 98 99 100 101 102 103 104 105 106 107 108 109 110 1,3-dimethylimidazolium 1-ethyl-3-methylimidazolium 111 112 2,4,5-trimethylimidazolium 1-(2-hydroxyethyl)-3-methylimidazolium 113 114 1,3-diethylimidazolium 1-propyl-3-methylimidazolium 115 116 1-ethyl-2,3-dimethylimidazolium 1-methyl-3-(1-methylethyl)imidazolium 117 118 1-butyl-3-methylimidazolium 1-methyl-3-(2-methylprop-1-enyl)imidazolium 119 120 1,2-dimethyl-3-propylimidazolium 1,2,3,4,5-pentamethylimidazolium 121 122 1-butyl-2,3-dimethylimidazolium 1-pentyl-3-methylimidazolium 123 124 1-butyl-3-ethylimidazolium 1-hexyl-3-methylimidazolium 125 126 1-hexyl-2,3-dimethylimidazolium 1-heptyl-3-methylimidazolium 127 128 1-octyl-3-methylimidazolium 1-methyl-3-nonylimidazolium 129 130 1-decyl-3-methylimidazolium 1-dodecyl-3-methylimidazolium 131 132 1-dodecyl-3-methylimidazolium 133 134 135 136 137 138 139 140 141 142 143 144 145 146 147 148 149 150 151 152 153 154 155 156 157 158 159 160 161 162 163 164 165 166 167 triisobutylmethylphosphonium trihexyl(tetradecyl)phosphonium 168 169 tetrabutylphosphonium tri-i-butyl(methyl)phosphonium 170 171 tributyl(tetradecyl)phosphonium 172 tetrabutylammonium. 173

5. The method of claim 1, wherein the composition comprises at least one anionic compound of at least one of formula (Ia) and (Ib), wherein m is equal to n.

6. The method of claim 1, wherein the composition comprises at least one anionic compound of at least one of formula (Ia) and (Ib), wherein m and n are equal to 1, 2 or 3.

7. The method of claim 1, wherein the composition comprises at least one anionic compound of at least one of formula (Ia) and (Ib), wherein at least one of Col.sup.(−)m and Azu.sup.(−)m comprises: at least one sulfonate group and at least one (hetero)aryl group, it being understood that at least one sulfonate group is directly bonded to a (hetero)aryl group; and optionally at least one anionic group G.sup.− with G.sup.− independently chosen from anionic groups chosen from alkoxide O.sup.−, thioalkoxide S.sup.−, carboxylate and thiocarboxylate: C(Q)Q′.sup.− wherein Q and Q′ independently chosen from oxygen or sulfur atoms.

8. The method of claim 1, wherein the composition comprises at least one anionic compound of at least one of formula (Ia) and (Ib), wherein at least one of Col.sup.(−)m and Azu.sup.(−)m comprises at least one carboxylate group and at least one (hetero)aryl group, it being understood that at least one carboxylate group is directly bonded to a (hetero)aryl group.

9. The method of claim 1, wherein the composition comprises at least one anionic compound of at least one of formula (Ia) and formula (Ib); wherein the at least one anionic compound of formula (Ia) is derived from acidic nitro direct dyes, acidic azo dyes, acidic azine dyes, acidic triarylmethane dyes, acidic indoamine dyes, acidic anthraquinone dyes, indigoids and acidic natural dyes; wherein the at least one anionic compound of formula (Ib) is derived from stilbene; wherein the at least one anionic compound of formula (Ia) and formula (Ib) comprises a sulfonate or carboxylate group bearing a cationic counterion X.sup.+, wherein X.sup.+ represents a monocationic or polycationic counterion or mixture of counterions chosen from: f) the ammoniums and phosphoniums of formulae (1) and (2) below: ##STR00144## g) optionally substituted heteroaromatic groups bearing exocyclic or endocyclic, cationic charges, including (benz)imidazolium, indolinium, (benzo)triazolium, (benzo)pyrylium and (benzo)pyridinium groups, of formulae (3) and (4) below: ##STR00145## h) symmetrical or dissymmetrical dimers of formulae (1), (2), (3) and (4) chosen from those of formulae (1′) to (8′): ##STR00146## i) metallic cations of copper, iron, lithium, magnesium, manganese, gold and zinc, chosen from: Cu.sup.+, Cu.sup.2+, Fe.sup.2+, Fe.sup.3+, Li.sup.+, Mg.sup.2+, Mn.sup.4+, Au.sup.3+ and Zn.sup.2+; and j) cationic oligomers or polymers; wherein, in formulae (1) to (4) and (1′) to (8′): R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are independently chosen from v) linear or branched (C.sub.1-C.sub.20)alkyl; vi) (C.sub.2-C.sub.20)alkenyl; vii) (hetero)aryl(C.sub.1-C.sub.20)alkyl; (hetero)cycloalkyl(C.sub.1-C.sub.20)alkyl, or viii) (hetero)aryl;  the alkyl or alkenyl group of the groups of i), ii), iii) or iv) optionally interrupted with one or more identical or different heteroatoms chosen from an oxygen or sulfur atom, the amino —N(R)—, ammonium —N.sup.+(R.sub.a)(R.sub.b)—, —C(O)—, —C(S)— group or a combination thereof, wherein R, R.sub.a and R.sub.b are independently chosen from hydrogen atoms or alkyl groups; or alternatively the radicals R.sub.1 and R.sub.2 form, together with the quaternized nitrogen or phosphorus atom, a saturated 5- or 6-membered heterocycle, the said heterocycle optionally partially unsaturated, optionally interrupted with a heteroatom chosen from an oxygen atom, the group —N(R)—, or ammonium —N.sup.+(R.sub.a)(R.sub.b)— wherein R, R.sub.a and R.sub.b are independently chosen from hydrogen atoms or alkyl groups, and/or the said heterocycle optionally substituted with one or more alkyl groups; R′.sub.1, R″.sub.1 and R″.sub.2 are independently chosen from iii) linear or branched (C.sub.1-C.sub.20)alkyl; iv) (C.sub.2-C.sub.20)alkenyl;  the alkyl or alkenyl group of the groups of i) and ii) optionally interrupted with one or more identical or different heteroatoms chosen from an oxygen or sulfur atom or ammonium —N.sup.+(R.sub.a)(R.sub.b)—, —C(O)—, —C(S)— or a combination thereof, wherein R, R.sub.a and R.sub.b are independently chosen from hydrogen atoms or alkyl groups; wherein R′.sub.1, R″.sub.1 and R″.sub.2, may optionally be substituted with at least one hydroxyl, hydroxycarbonyl or carboxyl, (C.sub.1-C.sub.6)alkoxycarbonyl, alkyl(C.sub.1-C.sub.6)carbonyloxy, carbamoyloxy, (di)(C.sub.1-C.sub.6)(alkyl)silyl or tri(C.sub.1-C.sub.5)alkylsilyl group; R′ and R″ are independently chosen from xiv) (C.sub.1-C.sub.5)alkyl optionally substituted with one or more radicals chosen from hydroxyl radicals, xv) (C.sub.1-C.sub.5)alkoxycarbonyl, xvi) hydroxyl, xvii) halogen, xviii) (C.sub.1-C.sub.5)alkoxy, xix) (poly)hydroxy(C.sub.1-C.sub.5)alkoxy, xx) (di)(C.sub.1-C.sub.5)(alkyl)amino, xxi) nitro, xxii) acylamino (—N(R)—C(O)R′) with R chosen from a hydrogen atom or a (hydroxy)(C.sub.1-C.sub.5)alkyl radical, xxiii) carbamoyl ((R).sub.2N—C(O)—) with R as defined for ix), xxiv) carboxylic acid or ester, (—O—C(O)R′) or (—C(O)OR′) with R′ as defined for ix) the carboxylic radical optionally in acid or salified form, xxv) alkylsulfonylamino (R′S(O).sub.2—N(R)—) or aminosulfonyl ((R).sub.2N—S(O).sub.2—) with R as defined for ix), xxvi) (poly)haloalkyl; or alternatively when p is greater than or equal to 2, two groups R′ or R″ borne by two contiguous carbon atoms together form a (hetero)cycle or a (hetero)aryl; R′″.sub.1, R′″.sub.2, R′″.sub.3 and R′″.sub.4 independently chosen from iii) linear or branched (C.sub.1-C.sub.20)alkyl; iv) (C.sub.2-C.sub.20)alkenyl;  the alkyl or alkenyl group of the groups of i) and ii) optionally substituted and/or interrupted with one or more identical or different heteroatoms chosen from an oxygen or sulfur atom, the amino —N(R)—, ammonium —N.sup.+(R.sub.a)(R.sub.b)—, —C(O)—, —C(S)— group or a combination thereof, with R, R.sub.a and R.sub.b independently chosen from hydrogen atoms or alkyl groups; p is equal to 0, 1, 2, 3 or 4; L represents a linear or branched, saturated or unsaturated divalent C.sub.1-C.sub.30 hydrocarbon-based chain, optionally interrupted and/or optionally terminated at one or both of its ends with one or more divalent groups or combinations thereof chosen from: —N(R.sub.a)—; —N.sup.+(R.sub.a)(R.sub.b)—, Q.sup.−; —O—, —S—; —S(O)—, —S(O).sub.2—, —C(O)— and —C(S)— with R.sub.a and R.sub.b independently chosen from hydrogen atoms and a C.sub.1-C.sub.4 alkyl, hydroxy(C.sub.1-C.sub.8)alkyl or amino(C.sub.1-C.sub.8)alkyl radicals and Q.sup.− represents an organic or mineral anionic counterion; an aromatic or non-aromatic, saturated or unsaturated, fused or non-fused, cationic or non-cationic (hetero)cyclic radical optionally comprising one or more identical or different, optionally substituted heteroatoms.

10. The method of claim 1, wherein the composition comprises at least one anionic compound of at least one of formula (Ia) and (Ib) chosen from the following compounds: ##STR00147## ##STR00148## ##STR00149## wherein X.sup.+ represents a monocationic or polycationic counterion or mixture of counterions chosen from: a) the ammoniums and phosphoniums of formulae (1) and (2) below: ##STR00150## b) optionally substituted heteroaromatic groups bearing exocyclic or endocyclic, cationic charges, including (benz)imidazolium, indolinium, (benzo)triazolium, (benzo)pyrylium and (benzo)pyridinium groups, of formulae (3) and (4) below: ##STR00151## c) symmetrical or dissymmetrical dimers of formulae (1), (2), (3) and (4) chosen from those of formulae (1′) to (8′): ##STR00152## d) metallic cations of copper, iron, lithium, magnesium, manganese, gold and zinc, chosen from: Cu.sup.+, Cu.sup.2+, Fe.sup.2+, Fe.sup.3+, Li.sup.+, Mg.sup.2+, Mn.sup.4+, Au.sup.3+ and Zn.sup.2+; and e) cationic oligomers or polymers; wherein, in formulae (1) to (4) and (1′) to (8′): R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are independently chosen from ix) linear or branched (C.sub.1-C.sub.20)alkyl; x) (C.sub.2-C.sub.20)alkenyl; xi) (hetero)aryl(C.sub.1-C.sub.20)alkyl; (hetero)cycloalkyl(C.sub.1-C.sub.20)alkyl, or xii) (hetero)aryl;  the alkyl or alkenyl group of the groups of i), ii), iii) or iv) optionally interrupted with one or more identical or different heteroatoms chosen from an oxygen or sulfur atom, the amino —N(R)—, ammonium —N.sup.+(R.sub.a)(R.sub.b)—, —C(O)—, —C(S)— group or a combination thereof, wherein R, R.sub.a and R.sub.b are independently chosen from hydrogen atoms or alkyl groups; or alternatively the radicals R.sub.1 and R.sub.2 form, together with the quaternized nitrogen or phosphorus atom, a saturated 5- or 6-membered heterocycle, the said heterocycle optionally partially unsaturated, optionally interrupted with a heteroatom chosen from an oxygen atom, the group —N(R)—, or ammonium —N.sup.+(R.sub.a)(R.sub.b)— wherein R, R.sub.a and R.sub.b are independently chosen from hydrogen atoms or alkyl groups, and/or the said heterocycle optionally substituted with one or more alkyl groups; R′.sub.1, R″.sub.1 and R″.sub.2 are independently chosen from v) linear or branched (C.sub.1-C.sub.20)alkyl; vi) (C.sub.2-C.sub.20)alkenyl;  the alkyl or alkenyl group of the groups of i) and ii) optionally interrupted with one or more identical or different heteroatoms chosen from an oxygen or sulfur atom or ammonium —N.sup.+(R.sub.a)(R.sub.b)—, —C(O)—, —C(S)— or a combination thereof, wherein R, R.sub.a and R.sub.b are independently chosen from hydrogen atoms or alkyl groups; wherein R′.sub.1, R″.sub.1 and R″.sub.2, may optionally be substituted with at least one hydroxyl, hydroxycarbonyl or carboxyl, (C.sub.1-C.sub.6)alkoxycarbonyl, alkyl(C.sub.1-C.sub.6)carbonyloxy, carbamoyloxy, (di)(C.sub.1-C.sub.6)(alkyl)silyl or tri(C.sub.1-C.sub.5)alkylsilyl group; R′ and R″ are independently chosen from xxvii) (C.sub.1-C.sub.5)alkyl optionally substituted with one or more radicals chosen from hydroxyl radicals, xxviii) (C.sub.1-C.sub.5)alkoxycarbonyl, xxix) hydroxyl, xxx) halogen, xxxi) (C.sub.1-C.sub.5)alkoxy, xxxii) (poly)hydroxy(C.sub.1-C.sub.5)alkoxy, xxxiii) (di)(C.sub.1-C.sub.5)(alkyl)amino, xxxiv) nitro, xxxv) acylamino (—N(R)—C(O)R′) with R chosen from a hydrogen atom or a (hydroxy)(C.sub.1-C.sub.5)alkyl radical, xxxvi) carbamoyl ((R).sub.2N—C(O)—) with R as defined for ix), xxxvii) carboxylic acid or ester, (—O—C(O)R′) or (—C(O)OR′) with R′ as defined for ix) the carboxylic radical optionally in acid or salified form, xxxviii) alkylsulfonylamino (R′S(O).sub.2—N(R)—) or am inosulfonyl ((R).sub.2N—S(O).sub.2—) with R as defined for ix), xxxix) (poly)haloalkyl; or alternatively when p is greater than or equal to 2, two groups R′ or R″ borne by two contiguous carbon atoms together form a (hetero)cycle or a (hetero)aryl; R″′.sub.1, R″′.sub.2, R″′.sub.3 and R″′.sub.4 independently chosen from v) linear or branched (C.sub.1-C.sub.20)alkyl; vi) (C.sub.2-C.sub.20)alkenyl;  the alkyl or alkenyl group of the groups of i) and ii) optionally substituted and/or interrupted with one or more identical or different heteroatoms chosen from an oxygen or sulfur atom, the amino —N(R)—, ammonium —N.sup.+(R.sub.a)(R.sub.b)13 , —C(O)—, —C(S)— group or a combination thereof, with R, R.sub.a and R.sub.b independently chosen from hydrogen atoms or alkyl groups; p is equal to 0, 1, 2, 3 or 4; L represents a linear or branched, saturated or unsaturated divalent C.sub.1-C.sub.30 hydrocarbon-based chain, optionally interrupted and/or optionally terminated at one or both of its ends with one or more divalent groups or combinations thereof chosen from: —N(R.sub.a)—; —N.sup.+(R.sub.a)(R.sub.b)—, Q.sup.−; —O—; —S—; —S(O)—, —S(O).sub.2—, —C(O)— and —C(S)— with R.sub.a and R.sub.b independently chosen from hydrogen atoms and a C.sub.1-C.sub.4 alkyl, hydroxy(C.sub.1-C.sub.8)alkyl or amino(C.sub.1-C.sub.8)alkyl radicals and Q.sup.− represents an organic or mineral anionic counterion; an aromatic or non-aromatic, saturated or unsaturated, fused or non-fused, cationic or non-cationic (hetero)cyclic radical optionally comprising one or more identical or different, optionally substituted heteroatoms; wherein, when the part Col.sup.− or Azu.sup.− comprises several anionic charges (m=2 or 3) then 2X.sup.+ or 3X.sup.+ may correspond to a dication or a trication.

11. The method of claim 1, wherein the fibers comprise a tone depth of less than or equal to 6, comprising: applying to the said fibers a composition comprising at least one of at least one fluorescent dye of formula (Ia), and at least one optical brightener of formula (Ib).

12. A compound of formula (Ia) or (Ib)
Col.sup.(−).sub.m[X.sup.+].sub.n  (Ia)
Azu.sup.(−).sub.m[X.sup.+].sub.n  (Ib) and optical isomers, geometrical isomers, and solvates thereof; wherein: Col.sup.(−) represents the anionic part of an anionic direct dye comprising m anionic charges chosen from acidic nitro direct dyes, acidic azo dyes, acidic azine dyes, acidic triarylmethane dyes, acidic indoamine dyes, acidic anthraquinone dyes, anionic styryl dyes, indigoids, or acidic natural dyes; Azu.sup.(−) represents the anionic part of an anionic optical brightener comprising m anionic charges chosen from stilbene derivatives, coumarin derivatives, (benz)oxazole derivatives, (benz)imidazole derivatives, (benz)oxazole derivatives, (benzo)furan derivatives, pyrazoline derivatives, or naphthalimide derivatives; m and n are independently chosen from an integer ranging from 1 to 10, inclusive; X.sup.+ represents a monocationic or polycationic counterion or mixture of counterions chosen from: k) the ammoniums and phosphoniums of formulae (1) and (2) below: ##STR00153## l) optionally substituted heteroaromatic groups bearing exocyclic or endocyclic, cationic charges, including (benz)imidazolium, indolinium, (benzo)triazolium, (benzo)pyrylium and (benzo)pyridinium groups, of formulae (3) and (4) below: ##STR00154## m) symmetrical or dissymmetrical dimers of formulae (1), (2), (3) and (4) chosen from those of formulae (1′) to (8′): ##STR00155## n) metallic cations of copper, iron, lithium, magnesium, manganese, gold and zinc, chosen from: Cu.sup.+, Cu.sup.2+, Fe.sup.2+, Fe.sup.3+, Li.sup.+, Mg.sup.2+, Mn.sup.4+, Au.sup.3+ and Zn.sup.2+; and o) cationic oligomers or polymers; wherein, in formulae (1) to (4) and (1′) to (8′): R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are independently chosen from xiii) linear or branched (C.sub.1-C.sub.20)alkyl; xiv) (C.sub.2-C.sub.20)alkenyl; xv) (hetero)aryl(C.sub.1-C.sub.20)alkyl; (hetero)cycloalkyl(C.sub.1-C.sub.20)alkyl, or xvi) (hetero)aryl;  the alkyl or alkenyl group of the groups of i), ii), iii) or iv) optionally interrupted with one or more identical or different heteroatoms chosen from an oxygen or sulfur atom, the amino —N(R)—, ammonium —N.sup.+(R.sub.a)(R.sub.b)—, —C(O)—, —C(S)— group or a combination thereof, wherein R, R.sub.a and R.sub.b are independently chosen from hydrogen atoms or alkyl groups; or alternatively the radicals R.sub.1 and R.sub.2 form, together with the quaternized nitrogen or phosphorus atom, a saturated 5- or 6-membered heterocycle, the said heterocycle optionally partially unsaturated, optionally interrupted with a heteroatom chosen from an oxygen atom, the group —N(R)—, or ammonium —N.sup.+(R.sub.a)(R.sub.b)— wherein R, R.sub.a and R.sub.b are independently chosen from hydrogen atoms or alkyl groups, and/or the said heterocycle optionally substituted with one or more alkyl groups; R′.sub.1, R″.sub.1 and R″.sub.2 are independently chosen from vii) linear or branched (C.sub.1-C.sub.20)alkyl; viii) (C.sub.2-C.sub.20)alkenyl;  the alkyl or alkenyl group of the groups of i) and ii) optionally interrupted with one or more identical or different heteroatoms chosen from an oxygen or sulfur atom or ammonium —N.sup.+(R.sub.a)(R.sub.b)—, —C(O)—, —C(S)— or a combination thereof, wherein R, R.sub.a and R.sub.b are independently chosen from hydrogen atoms or alkyl groups; wherein R′.sub.1, R″.sub.1 and R″.sub.2, may optionally be substituted with at least one hydroxyl, hydroxycarbonyl or carboxyl, (C.sub.1-C.sub.6)alkoxycarbonyl, alkyl(C.sub.1-C.sub.6)carbonyloxy, carbamoyloxy, (di)(C.sub.1-C.sub.6)(alkyl)silyl or tri(C.sub.1-C.sub.5)alkylsilyl group; R′ and R″ are independently chosen from xl) (C.sub.1-C.sub.5)alkyl optionally substituted with one or more radicals chosen from hydroxyl radicals, xli) (C.sub.1-C.sub.5)alkoxycarbonyl, xlii) hydroxyl, xliii) halogen, xliv) (C.sub.1-C.sub.5)alkoxy, xlv) (poly)hydroxy(C.sub.1-C.sub.5)alkoxy, xlvi) (di)(C.sub.1-C.sub.5)(alkyl)amino, xlvii) nitro, xlviii) acylamino (—N(R)—C(O)R′) with R chosen from a hydrogen atom or a (hydroxy)(C.sub.1-C.sub.5)alkyl radical, xlix) carbamoyl ((R).sub.2N—C(O)—) with R as defined for ix), l) carboxylic acid or ester, (—O—C(O)R′) or (—C(O)OR′) with R′ as defined for ix) the carboxylic radical optionally in acid or salified form, li) alkylsulfonylamino (R′S(O).sub.2—N(R)—) or aminosulfonyl ((R).sub.2N—S(O).sub.2—) with R as defined for ix), lii) (poly)haloalkyl; or alternatively when p is greater than or equal to 2, two groups R′ or R″ borne by two contiguous carbon atoms together form a (hetero)cycle or a (hetero)aryl; R′″.sub.1, R′″.sub.2, R′″.sub.3 and R′″.sub.4 independently chosen from vii) linear or branched (C.sub.1-C.sub.20)alkyl; viii) (C.sub.2-C.sub.20)alkenyl;  the alkyl or alkenyl group of the groups of i) and ii) optionally substituted and/or interrupted with one or more identical or different heteroatoms chosen from an oxygen or sulfur atom, the amino —N(R)—, ammonium —N.sup.+(R.sub.a)(R.sub.b)—, —C(O)—, —C(S)— group or a combination thereof, with R, R.sub.a and R.sub.b independently chosen from hydrogen atoms or alkyl groups; p is equal to 0, 1, 2, 3 or 4; L represents a linear or branched, saturated or unsaturated divalent C.sub.1-C.sub.30 hydrocarbon-based chain, optionally interrupted and/or optionally terminated at one or both of its ends with one or more divalent groups or combinations thereof chosen from: —N(R.sub.a)—; —N.sup.+(R.sub.a)(R.sub.b)—, Q.sup.−; —O—, —S—; —S(O)—, —S(O).sub.2—, —C(S)— and —C(S)— with R.sub.a and R.sub.b independently chosen from hydrogen atoms and a C.sub.1-C.sub.4 alkyl, hydroxy(C.sub.1-C.sub.8)alkyl or amino(C.sub.1-C.sub.8)alkyl radicals and Q .sup.− represents an organic or mineral anionic counterion; an aromatic or non-aromatic, saturated or unsaturated, fused or non-fused, cationic or non-cationic (hetero)cyclic radical optionally comprising one or more identical or different, optionally substituted heteroatoms; wherein: when the dyes of formula (Ia) are such that R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are independently chosen from i) linear or branched (C.sub.1-C.sub.20)alkyl; ii) (C.sub.2-C.sub.20)alkenyl; the alkyl or alkenyl group of the groups of i) and ii) optionally interrupted with one or more identical or different heteroatoms chosen from an oxygen or sulfur atom or the amino —N(R)— group, then at least one of the said radicals R.sub.1, R.sub.2, R.sub.3 and R.sub.4 is substituted with at least one hydroxyl, hydroxycarbonyl or carboxyl, (C.sub.1-C.sub.6)alkoxycarbonyl, (C.sub.1-C.sub.6)alkylcarbonyloxy, carbamoyloxy, (di)(C.sub.1-C.sub.6)(alkyl)silyl or tri(C.sub.1-C.sub.5)alkylsilyl group; when p is equal to 2, 3 or 4, then the groups R′ are identical or different and R″ are identical or different; when the anionic part of the anionic direct dye or of the anionic optical brightener contains a sulfonate group or a carboxylate group, then m=n=1; and when the anionic part of the anionic direct dye or of the anionic optical brightener contains anionic groups other than the sulfonate or carboxylate group, it is combined with one or more organic or mineral cationic counterions or X.sup.+ for affording the electrical neutrality of formula (Ia) or (Ib); it being understood that the compound of formula (Ia) cannot represent compound (A), (B) or (C): ##STR00156## and Col.sup.(−).sub.m cannot represent: ##STR00157##

13. A cosmetic composition comprising the compound of claim 12.

Description

Example 1

(1) 409 mg (5×10.sup.−3 mol %) of compound (B) is solubilized in a mixture containing water (1 ml), benzyl alcohol (4 ml), ethanol (1 ml) with sonication in a warm bath (40° C.) for 35 minutes. 2 ml of slightly colored solution is applied on one lock of keratin fibers (1 g, Caucasian White natural hair 90%, Caucasian natural hair of tone height HT4, and Japanese hair of tone height HT=2). After locks are rinced with lukewarm water, and dried for 10 minutes. The compound (A) is applied under the same condition. Colorimetric measurement are realized with the aid of spectrocolorimeter Konica, 24 hours after dyeing treatment.

(2) Color Evaluation on Keratin Fibers

(3) The colour of the hair was determined by using the L*a*b* system, with a Konica spectrophotometer.

(4) According to this system, L* indicates the lightness. The lowest is the value of L*, the most intense is the color of the hair. The chromaticity coordinates are expressed by the parameters a* and b*, a* indicating the axis of red/green shades and b* the axis of yellow/blue shades.

(5) The results are expressed in the following table.

(6) ΔE, which is the color variation between or uptake a colored lock and a colored lock after shampoos, is obtained from the following formula:
ΔE=√{square root over ((L*−L.sub.o*).sup.2+(a*−a.sub.o*).sup.2+(b*−b.sub.o*).sup.2)}
wherein L* indicates lightness and a* and b* are the chromaticity coordinates of the colored locks after hair dyeing step whereas L.sub.0* indicates the lightness and a.sub.0* et b.sub.0* are the initial color of the locks of undyed hair. The highest is the value of ΔE, the most uptake fluorescence or colour on the hair.
On Caucasian 90% White Natural Hair:
brightening effect of anionic dyes with cationic counter-ion according to the invention vs. same anionic dyes with cationic metal (sodium, out of the invention)

(7) ΔE*, is the color variation or uptake between a colored lock and a uncolored lock (reference) with compound of the invention, obtained from the following formula:
ΔE*=√{square root over ((L*−L.sub.o*).sup.2+(a*−a.sub.o*).sup.2+(b*−b.sub.o*).sup.2)}
wherein L* indicates lightness and a* and b* are the chromaticity coordinates of the colored locks after hair dyeing step whereas L.sub.0* indicates the lightness and a.sub.0* et b.sub.0* are the initial color of the locks of undyed hair. The higest is the value of ΔE*, the most visual lightening effect is the color of the hair.

(8) TABLE-US-00003 TABLE 1 L* a* b* ΔE* Before dyeing hair (reference) 53.95 0.72 14.63 1.52 After dyeing hair with dye out 55.13 0.12 14.28 of the invention (sodium) (A)

(9) TABLE-US-00004 TABLE 2 L* a* b* ΔE* Before dyeing hair (reference) 53.95 0.72 14.63 3.36 After dyeing hair with compound (B) 52.99 0.82 11.41 according to the invention

(10) Composition containing compound (B) fold the yellow shade (b* data are significantly lower than the untreated hair (reference)) (ΔE=3.36) more efficiently than comparative compound bearing a sodium counter cation (see b* data and ΔE* which are higher than composition which contains compound (A) (reference)).

(11) Moreover the exchange of the counter anion exarcerbates the fuorescence property on hair i.e. the lightening effect.