Process for treating keratin fibers using an anhydrous composition comprising a compound of azomethine type comprising two pyrazolopyridine units and an aqueous composition

Abstract

The subject of the present invention is a process for treating keratin fibers using an anhydrous dye composition comprising at least one compound of azomethine type comprising two pyrazolopyridine units of formula (I) or (II) and an aqueous composition. The invention also relates to a kit comprising an anhydrous dyeing composition and an aqueous composition. ##STR00001##

Claims

1. A process for dyeing keratin fibers which comprises mixing together at least compositions (1) and (2) and applying the mixture to the keratin fibers, wherein: composition (1) is anhydrous and comprises one or more dyes chosen from compounds of formulae (I) and/or (II) below: ##STR00026## wherein in formulae (I) and (II): Z.sub.1 represents an oxygen atom or a group N(R.sub.6); Z.sub.1 represents an oxygen atom or a group N(R.sub.6); with the proviso that when Z.sub.1 represents N(R.sub.6) and/or Z.sub.1 represents N(R.sub.6), then R.sub.1 and R.sub.6 and/or R.sub.1 and R.sub.6, respectively, may form, together with the nitrogen atom to which they are attached, an optionally substituted, 5- to 8-membered, optionally cationic, saturated, unsaturated, or aromatic heterocycle; R.sub.1, R.sub.1, R.sub.6, and R.sub.6 each independently represent: a hydrogen atom, a C.sub.1-C.sub.10 alkyl radical optionally interrupted with one or more non-adjacent heteroatoms, and/or optionally substituted; R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.2, R.sub.3, R.sub.4, and R.sub.5 each independently represent: a hydrogen atom, an optionally substituted C.sub.1-C.sub.4 alkyl radical, or a group chosen from NH.sub.2, N(H)R.sub.10, N(R.sub.11)R.sub.12, OH, or OR.sub.9, with R.sub.9 and R.sub.10 representing an optionally substituted, linear or branched C.sub.1-C.sub.6 alkyl, R.sub.11 and R.sub.12, which may be identical or different, representing an optionally substituted, linear or branched C.sub.1-C.sub.6 alkyl, wherein R.sub.11 and R.sub.12 optionally form, together with the nitrogen atom to which they are attached, a saturated, unsaturated or aromatic 5- to 8-membered heterocycle optionally containing one or more other heteroatoms or groups chosen from N, O, S, S(O).sub.2, or C(O), the heterocycle being optionally substituted, and/or R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.2, R.sub.3, R.sub.4, and R.sub.5 form, in pairs with adjacent radicals, an optionally substituted, saturated or unsaturated (hetero)cycle; wherein when the compound of formula (I) and/or (II) is positively charged, then it comprises as many anionic counterions as cationic charges to achieve the electrical neutrality of the molecule; and composition (2) is aqueous, and comprises one or more ingredients chosen from: i) hydrotropic solvents; ii) anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric or zwitterionic surfactants, or mixtures of two or more thereof; iii) anionic polymers, cationic polymers, nonionic polymers, amphoteric or zwitterionic polymers, any of which may be optionally associative, or optionally substantive, or mixtures of two or more thereof; wherein composition (2) does not comprise any dye (I) or (II).

2. The process according to claim 1, wherein R.sub.1 and R.sub.1 are chosen from the following groups: i) C.sub.1-C.sub.6 alkyl; ii) C.sub.1-C.sub.10 alkyl substituted with one or more hydroxyl groups; iii) C.sub.1-C.sub.6 alkyl substituted with one or more amino or (di)(C.sub.1-C.sub.4) alkylamino groups; iv) C.sub.1-C.sub.6 alkyl substituted with a nitrogenous heterocycle; or v) [(CH.sub.2).sub.mO].sub.p-L-Y, with: p=1, 2, or 3, m=1, 2, or 3, L chosen from linear or branched, saturated C.sub.1-C.sub.6 divalent hydrocarbon-based groups, and Y chosen from hydroxyl groups or a hydrogen atom.

3. The process according to claim 1, wherein R.sub.2, R.sub.2, R.sub.3, R.sub.3, R.sub.4, R.sub.4, R.sub.5, and R.sub.5 independently represent a hydrogen atom or a C.sub.1-C.sub.4 alkyl radical.

4. The process according to claim 1, wherein the compound(s) of formula (I) and/or (II) are chosen from those of formulae (I) or (II): ##STR00027## wherein in formulae (I) and (II): Z.sub.1 is chosen from an oxygen atom or a group N(R.sub.6); with the proviso that when Z.sub.1 represents N(R.sub.6), then R.sub.1 and R.sub.6 may form, together with the nitrogen atom to which they are attached, an optionally substituted, 5- or 6-membered, saturated, unsaturated or aromatic heterocycle; R.sub.1 represents a C.sub.1-C.sub.6 alkyl radical, optionally interrupted with one or more non-adjacent oxygen atoms, and/or optionally substituted with: a hydroxyl radical, a di(C.sub.1-C.sub.4)alkylamino radical, or a heterocycle optionally substituted with one or more C.sub.1-C.sub.4 alkyl and/or hydroxyl radicals and chosen selected from pyrrolidine, piperidine, morpholine, piperazine, or imidazole; R.sub.6 represents: a hydrogen atom, or a C.sub.1-C.sub.10 alkyl radical optionally substituted with a hydroxyl radical; and R.sub.2, R.sub.3, R.sub.4, and R.sub.5 each independently represent: a hydrogen atom, or a C.sub.1-C.sub.4 alkyl radical.

5. The process according to claim 4, wherein Z.sub.1 represents NH, and R1 denotes a C.sub.1-C.sub.6 hydroxyalkyl radical, a di(C.sub.1-C.sub.4 alkyl)amino(C.sub.1-C.sub.6 alkyl) radical, or an alkyl radical substituted with a heterocycle chosen from pyrrolidinyl, piperidyl, morpholinyl, piperazinyl, or imidazolyl, said heterocycle being optionally substituted with one or more C.sub.1-C.sub.4 alkyl radicals.

6. The process according to claim 4, wherein Z.sub.1 represents N(R.sub.6), and: R.sub.1 and R.sub.6 each independently denote a C.sub.1-C.sub.6 alkyl radical or a C.sub.1-C.sub.6 hydroxyalkyl radical; or R.sub.1 forms with R.sub.6 a ring, this ring being chosen from pyrrolidinyl, piperidyl, morpholinyl, or piperazinyl rings optionally substituted with one or more C.sub.1-C.sub.4 alkyl and/or hydroxyl radicals.

7. The process according to claim 4, wherein the compound(s) of formula (I), (II), (I), or (II) are chosen from: 2,2-[(5-amino-3-iminopyridine-2,6(1H,3H)-diylidene)bis(nitrilopyrazolo[1,5-a]pyridine-3,2-diylimino)]diethanol; 3,3-[(5-amino-3-iminopyridine-2,6(1H,3H)-diylidene)bis(nitrilopyrazolo[1,5-a]pyridine-3,2-diylimino)]dipropan-1-ol; N3,N3-(5-amino-3-iminopyridine-2,6(1H,3H)-diylidene)bis{N2-[2-(dimethylamino)ethyl]pyrazolo[1,5-a]pyridine-2,3-diamine}; N3,N3-(5-amino-3-iminopyridine-2,6(1H,3H)-diylidene)bis{N2-[3-(dimethylamino)propyl]pyrazolo-[1,5-a]pyridine-2,3-diamine}; N3,N3-(5-amino-3-iminopyridine-2,6(1H,3H)-diylidene)-bis{N2-[2-(pyrrolidin-1-yl)ethyl]pyrazolo[1,5-a]pyridine-2,3-diamine}; N3,N3-(5-amino-3-iminopyridine-2,6(1H,3H)-diylidene)bis{N2-[3-(pyrrolidin-1-yl)propyl]pyrazolo[1,5-a]pyridine-2,3-diamine}; N3,N3-(5-amino-3-iminopyridine-2,6(1H,3H)-diylidene)bis{N2-[2-(piperidin-1-yl)ethyl]pyrazolo[1,5-a]pyridine-2,3-diamine}; N3,N3-(5-amino-3-iminopyridine-2,6(1H,3H)-diylidene)bis{N2-[3-(piperidin-1-yl)propyl]pyrazolo[1,5-a]pyridine-2,3-diamine}; N3,N3-(5-amino-3-iminopyridine-2,6(1H,3H)-diylidene)bis{N2-[2-(morpholin-4-yl)ethyl]pyrazolo[1,5-a]pyridine-2,3-diamine}; N3,N3-(5-amino-3-iminopyridine-2,6(1H,3H)-diylidene)bis{N2-[3-(morpholin-4-yl)propyl]pyrazolo[1,5-a]pyridine-2,3-diamine}; N3,N3-(5-amino-3-iminopyridine-2,6(1H,3H)-diylidene)bis{N2-[2-(4-methylpiperazin-1-yl)ethyl]pyrazolo[1,5-a]pyridine-2,3-diamine}; N3,N3-(5-amino-3-iminopyridine-2,6(1H,3H)-diylidene)bis{N2-[3-(4-methylpiperazin-1-yl)propyl]pyrazolo-[1,5-a]pyridine-2,3-diamine}; N3,N3-(5-amino-3-iminopyridine-2,6(1H,3H)-diylidene)bis{N2-[2-(1H-imidazol-1-yl)ethyl]pyrazolo[1,5-a]pyridine-2,3-diamine; N3,N3-(5-amino-3-iminopyridine-2,6(1H,3H)-diylidene)bis{N2-[3-(1H-imidazol-1-yl)propyl]pyrazolo[1,5-a]pyridine-2,3-diamine}; 2,2-[(5-amino-3-iminopyridine-2,6(1H,3H)-diylidene)bis(nitrilopyrazolo[1,5-a]pyridine-3,2-diyloxy)]diethanol; 3,3-[(5-amino-3-iminopyridine-2,6(1H,3H)diylidene)bis(nitrilopyrazolo[1,5-a]pyridine-3,2-diyloxy)]dipropan-1-ol; N,N-(5-amino-3-iminopyridine-2,6(1H,3H)-diylidene)bis{2-[2-(dimethylamino)ethoxy]pyrazolo[1,5-a]pyridin-3-amine}; N,N-(5-amino-3-iminopyridine-2,6(1H,3H)-diylidene)bis{2-[3-(dimethylamino)propoxy]pyrazolo[1,5-a]pyridin-3-amine}; N,N-(5-amino-3-iminopyridine-2,6(1H,3H)-diylidene)bis{2-[2-(pyrrolidin-1-yl)ethoxy]pyrazolo[1,5-a]pyridin-3-amine}; N,N-(5-amino-3-iminopyridine-2,6(1H,3H)-diylidene)bis{2-[3-(pyrrolidin-1-yl)propoxy]pyrazolo[1,5-a]pyridin-3-amine}; N,N-(5-amino-3-iminopyridine-2,6(1H,3H)-diylidene)bis{2-[2-(piperidin-1-yl)ethoxy]pyrazolo[1,5-a]pyridin-3-amine}; N,N-(5-amino-3-iminopyridine-2,6(1H,3H)-diylidene)bis{2-[3-(piperidin-1-yl)propoxy]pyrazolo[1,5-a]pyridin-3-amine}; N,N-(5-amino-3-iminopyridine-2,6(1H,3H)-diylidene)bis{2-[2-(morpholin-4-yl)ethoxy]pyrazolo[1,5-a]pyridin-3-amine}; N,N-(5-amino-3-iminopyridine-2,6(1H,3H)-diylidene)bis{2-[3-(morpholin-4-yl)propoxy]pyrazolo[1,5-a]pyridin-3-amine}; N,N-(5-amino-3-iminopyridine-2,6(1H,3H)-diylidene)bis{2-[2-(4-methylpiperazin-1-yl)ethoxy]pyrazolo[1,5-a]pyridin-3-amine}; N,N-(5-amino-3-iminopyridine-2,6(1H,3H)-diylidene)bis{2-[3-(4-methylpiperazin-1-yl)propoxy]pyrazolo[1,5-a]pyridin-3-amine}; N,N-(5-amino-3-iminopyridine-2,6(1H,3H)-diylidene)bis{2-[2-(1H-imidazol-1-yl)ethoxy]pyrazolo[1,5-a]pyridin-3-amine}; N,N-(5-amino-3-iminopyridine-2,6(1H,3H)-diylidene)bis{2-[3-(1H-imidazol-1-yl)propoxy]pyrazolo[1,5-a]pyridin-3-amine}; N,N-(5-amino-3-iminopyridine-2,6(1H,3H)-diylidene)bis(2-methoxypyrazolo[1,5-a]pyridin-3-amine); N,N-(5-amino-3-iminopyridine-2,6(1H,3H)-diylidene)bis(2-ethoxypyrazolo[1,5-a]pyridin-3-amine); N,N-(5-amino-3-iminopyridine-2,6(1H,3H)-diylidene)bis(2-propoxypyrazolo[1,5-a]pyridin-3-amine); N,N-(5-amino-3-iminopyridine-2,6(1H,3H)-diylidene)bis[2-(propan-2-yloxy)pyrazolo[1,5-a]pyridin-3-amine]; N,N-(5-amino-3-iminopyridine-2,6(1H,3H)-diylidene)bis{2-[2-(2-ethoxyethoxy)ethoxy]-6,7-dimethylpyrazolo[1,5-a]pyridin-3-amine}; 2-{2-[(3-([3-amino-6-({2-[2-(2-hydroxyethoxy)ethoxy]pyrazolo[1,5-a]pyridin-3-yl}amino)-5-imino-5,6-dihydropyridin-2(1H)-ylidene]amino}pyrazolo[1,5-a]pyridin-2-yl)oxy]ethoxy}ethanol; N,N-(5-amino-3-iminopyridine-2,6(1H,3H)-diylidene)bis{2-[2-(propan-2-yloxy)ethoxy]pyrazolo[1,5-a]pyridin-3-amine}; N,N-(5-amino-3-iminopyridine-2,6(1H,3H)-diylidene)bis(2-tert-butoxypyrazolo[1,5-a]pyridin-3-amine); N3,N3-(5-amino-3-iminopyridine-2,6(1H,3H)diylidene)bis{N2,N2-dimethylpyrazolo[-1,5-a]pyridine-2,3-diamine}; N3,N3-(5-amino-3-iminopyridine-2,6(1H,3H)diylidene)bis{N2,N2-diethylpyrazolo[1,5-a]pyridine-2,3-diamine}; 2,2,2,2-[(5-amino-3-iminopyridine-2,6(1H,3H)-diylidene)bis(nitrilopyrazolo[1,5-a]pyridine-3,2-diylnitrilo)]tetraethanol; N,N-(5-amino-3-iminopyridine-2,6(1H,3H)diylidene)bis[2-(pyrrolidin-1-yl)pyrazolo[1,5-a]pyridin-3-amine]; N,N-(5-amino-3-iminopyridine-2,6(1H,3H)diylidene)bis[2-(piperidin-1-yl)pyrazolo[1,5-a]pyridin-3-amine]; N,N-(5-amino-3-iminopyridine-2,6(1H,3H)diylidene)bis[2-(morpholin-4-yl)pyrazolo[1,5-a]pyridin-3-amine]; N,N-(5-amino-3-iminopyridine-2,6(1H,3H)diylidene)bis[2-(4-methylpiperazin-1-yl)pyrazolo[1,5-a]pyridin-3-amine]; 1,1-[(5-amino-3-iminopyridine-2,6(1H,3H)diylidene)bis(nitrilopyrazolo[1,5-a]pyridine-3,2-diyl)]dipyrrolidin-3-ol; 1,1-[(5-amino-3-iminopyridine-2,6(1H,3H)diylidene)bis(nitrilopyrazolo[1,5-a]pyridine-3,2-diyl)]dipyrrolidine-3,4-diol; 2,2-{(5-amino-3-iminopyridine-2,6(1H,3H)diylidene)bis[nitrilo(6,7-dimethylpyrazolo[1,5-a]pyridine-3,2-diyl)imino]}diethanol; 3,3-{(5-amino-3-iminopyridine-2,6(1H,3H)diylidene)bis[nitrilo(6,7-dimethylpyrazolo-[1,5-a]pyridine-3,2-diyl)imino]}dipropan-1-ol; N3,N3-(5-amino-3-iminopyridine-2,6(1H,3H)diylidene)bis{N2-[2-(dimethylamino)ethyl]-6,7-dimethylpyrazolo[1,5-a]pyridine-2,3-diamine}; N3,N3-(5-amino-3-iminopyridine-2,6(1H,3H)diylidene)bis{N2-[3-(dimethylamino)propyl]-6,7-dimethylpyrazolo[1,5-a]pyridine-2,3-diamine}; N3,N3-(5-amino-3-iminopyridine-2,6(1H,3H)-diylidene)bis{6,7-dimethyl-N2-[2-(pyrrolidin-1-yl)ethyl]pyrazolo[1,5-a]pyridine-2,3-diamine}; N3,N3-(5-amino-3-iminopyridine-2,6(1H,3H)-diylidene)bis{6,7-dimethyl-N2-[3-(pyrrolidin-1-yl)propyl]pyrazolo[1,5-a]pyridine-2,3-diamine}; N3,N3-(5-amino-3-iminopyridine-2,6(1H,3H)diylidene)bis{6,7-dimethyl-N2-[2-(piperidin-1-yl)ethyl]pyrazolo-[1,5-a]pyridine-2,3-diamine}; N3,N3-(5-amino-3-iminopyridine-2,6(1H,3H)diylidene)bis{6,7-dimethyl-N2-[3-(piperidin-1-yl)propyl]pyrazolo[1,5-a]pyridine-2,3-diamine}; N3,N3-(5-amino-3-iminopyridine-2,6(1H,3H)diylidene)bis{6,7-dimethyl-N2-[2-(morpholin-4-yl)ethyl]pyrazolo[1,5-a]pyridine-2,3-diamine}; N3,N3-(5-amino-3-iminopyridine-2,6(1H,3H)diylidene)bis{6,7-dimethyl-N2-[3-(morpholin-4-yl)propyl]pyrazolo[1,5-a]pyridine-2,3-diamine}; N3,N3-(5-amino-3-iminopyridine-2,6(1H,3H)diylidene)bis{6,7-dimethyl-N2-[2-(4-methylpiperazin-1-yl)ethyl]pyrazolo[1,5-a]pyridine-2,3-diamine}; N3,N3-(5-amino-3-iminopyridine-2,6(1H,3H)diylidene)bis{6,7-dimethyl-N2-[3-(4-methylpiperazin-1-yl)propyl]pyrazolo[1,5-a]pyridine-2,3-diamine}; N3,N3-(5-amino-3-iminopyridine-2,6(1H,3H)-diylidene)bis{N2-[2-(1H-imidazol-1-yl)ethyl]-6,7-dimethylpyrazolo[1,5-a]pyridine-2,3-diamine}; N3,N3-(5-amino-3-iminopyridine-2,6(1H,3H)-diylidene)bis{N2-[3-(1H-imidazol-1-yl)propyl]-6,7-dimethylpyrazolo[1,5-a]pyridine-2,3-diamine}; 2,2-{(5-amino-3-iminopyridine-2,6(1H,3H)-diylidene)bis[nitrilo-(6,7-dimethylpyrazolo-[1,5-a]pyridine-3,2-diyl)oxy]}diethanol; 3,3-{(5-amino-3-iminopyridine-2,6(1H,3H)-diylidene)bis[nitrilo(6,7-dimethylpyrazolo-[1,5-a]pyridine-3,2-diyl)oxy]}dipropan-1-ol; N,N-(5-amino-3-iminopyridine-2,6(1H,3H)-diylidene)bis{2-[2-(dimethylamino)ethoxy]-6,7-dimethylpyrazolo[1,5-a]pyridin-3-amine; N3,N3-(5-amino-3-iminopyridine-2,6(1H,3H)-diylidene)bis{N2-[3-(dimethylamino)propyl]-6,7-dimethyl-pyrazolo[1,5-a]pyridine-2,3-diamine}; N3,N3-(5-amino-3-iminopyridine-2,6(1H,3H)-diylidene)bis{6,7-dimethyl-N2-[2-(pyrrolidin-1-yl)ethyl]pyrazolo[1,5-a]pyridine-2,3-diamine}; N,N-(5-amino-3-iminopyridine-2,6(1H,3H)-diylidene)bis{6,7-dimethyl-2-[3-(pyrrolidin-1-yl)propoxy]pyrazolo[1,5-a]pyridin-3-amine}; N,N-(5-amino-3-iminopyridine-2,6(1H,3H)-diylidene)bis{6,7-dimethyl-2-[2-(piperidin-1-yl)ethoxy]pyrazolo-[1,5-a]pyridin-3-amine}; N,N-(5-amino-3-iminopyridine-2,6(1H,3H)-diylidene)bis{6,7-dimethyl-2-[3-(piperidin-1-yl)propoxy]pyrazolo[1,5-a]pyridin-3-amine}; N,N-(5-amino-3-iminopyridine-2,6(1H,3H)-diylidene)bis{6,7-dimethyl-2-[2-(morpholin-4-yl)ethoxy]pyrazolo[1,5-a]pyridin-3-amine}; N,N-(5-amino-3-iminopyridine-2,6(1H,3H)-diylidene)bis{6,7-dimethyl-2-[3-(morpholin-4-yl)propoxy]pyrazolo[1,5-a]pyridin-3-amine}; N,N-(5-amino-3-iminopyridine-2,6(1H,3H)-diylidene)bis{6,7-dimethyl-2-[2-(4-methyl-piperazin-1-yl)ethoxy]pyrazolo[1,5-a]pyridin-3-amine}; N,N-(5-amino-3-iminopyridine-2,6(1H,3H)-diylidene)bis{6,7-dimethyl-2-[3-(4-methylpiperazin-1-yl)propoxy]pyrazolo[1,5-a]pyridin-3-amine}; N,N-(5-amino-3-iminopyridine-2,6(1H,3H)-diylidene)bis{2-[2-(1H-imidazol-1-yl)ethoxy]-6,7-dimethylpyrazolo[1,5-a]pyridin-3-amine}; N,N-(5-amino-3-iminopyridine-2,6(1H,3H)-diylidene)bis{2-[3-(1H-imidazol-1-yl)propoxy]-6,7-dimethyl-pyrazolo[1,5-a]pyridin-3-amine}; N,N-(5-amino-3-iminopyridine-2,6(1H,3H)-diylidene)bis{2-methoxy-6,7-dimethylpyrazolo[1,5-a]pyridin-3-amine}; N2-(2-ethoxy-6,7-dimethylpyrazolo[1,5-a]pyridin-3-yl)-6-[(2-ethoxy-6,7-dimethylpyrazolo[1,5-a]pyridin-3-yl)imino]-3-imino-3,6-dihydropyridine-2,5-diamine; N,N-(5-amino-3-iminopyridine-2,6(1H,3H)-diylidene)bis{6,7-dimethyl-2-propoxypyrazolo[1,5-a]pyridin-3-amine}; N,N-(5-amino-3-iminopyridine-2,6(1H,3H)-diylidene)bis[6,7-dimethyl-2-(propan-2-yloxy)-pyrazolo[1,5-a]pyridin-3-amine]; N,N-(5-amino-3-iminopyridine-2,6(1H,3H)-diylidene)bis{2-tert-butoxy-6,7-dimethylpyrazolo[1,5-a]pyridin-3-amine}; N3,N3-(5-amino-3-iminopyridine-2,6(1H,3H)-diylidene)bis{N2,N2,6,7-tetramethylpyrazolo[1,5-a]pyridine-2,3-diamine}; N3,N3-(5-amino-3-iminopyridine-2,6(1H,3H)-diylidene)bis{N2,N2-diethyl-6,7-dimethylpyrazolo[1,5-a]pyridine-2,3-diamine}; 2,2,2,2-{(5-amino-3-iminopyridine-2,6(1H,3H)-diylidene)bis[nitrilo(6,7-dimethyl-pyrazolo[1,5-a]pyridine-3,2-diyl)nitrilo]}tetraethanol; N,N-(5-amino-3-iminopyridine-2,6(1H,3H)-diylidene)bis[6,7-dimethyl-2-(pyrrolidin-1-yl)pyrazolo[1,5-a]pyridin-3-amine]; N,N-(5-amino-3-iminopyridine-2,6(1H,3H)-diylidene)bis[6,7-dimethyl-2-(piperidin-1-yl)pyrazolo[1,5-a]pyridin-3-amine]; N,N-(5-amino-3-iminopyridine-2,6(1H,3H)-diylidene)bis[6,7-dimethyl-2-(morpholin-4-yl)pyrazolo[1,5-a]pyridin-3-amine]; N,N-(5-amino-3-iminopyridine-2,6(1H,3H)-diylidene)bis[6,7-dimethyl-2-(4-methylpiperazin-1-yl)pyrazolo[1,5-a]pyridin-3-amine]; 1,1-{(5-amino-3-iminopyridine-2,6(1H,3H)-diylidene)bis[nitrilo(6,7-dimethylpyrazolo[1,5-a]pyridine-3,2-diyl)]}dipyrrolidin-3-ol; 1,1-{(5-amino-3-iminopyridine-2,6(1H,3H)-diylidene)bis[nitrilo(6,7-dimethylpyrazolo[1,5-a]pyridine-3,2-diyl)]}dipyrrolidine-3,4-diol or leuco forms thereof, optical isomers, geometrical isomers, tautomers, solvates or addition salts thereof.

8. The process according to claim 4, wherein the total amount of compound(s) of formulae (I), (I), (II), and (II) ranges from 0.01% to 15% by weight.

9. The process according to claim 4, wherein the total amount of compound(s) of formulae (I), (I), (II), and (II) ranges from 0.05% to 10% by weight.

10. The process according to claim 1, wherein the composition (1) comprises one or more hydrotropic solvent(s) chosen from alcohol ethers, aliphatic esters, aliphatic ethers, aromatic ethers, alkanols bearing aryl substituents, lactones, or mixtures of two or more thereof.

11. The process according to claim 1, wherein the composition (1) comprises one or more hydrotropic solvent(s) chosen from: C.sub.1-C.sub.4 ethers of C.sub.5-C.sub.30 alcohols; aliphatic esters of C.sub.1-C.sub.4 carboxylic acids and of C.sub.3-C.sub.10 monoalcohols or polyhydroxylated alcohols, interrupted with one or more non-adjacent ether functions; aromatic ethers of a C.sub.6-C.sub.10 alkyl, optionally bearing a hydroxyl group; (C.sub.6-C.sub.10)aryl(C.sub.1-C.sub.6)alkyl ethers, of a C.sub.1-C.sub.6 alkyl optionally bearing a hydroxyl group; alkanols bearing an aryl substituent; or lactones of formula (iii): ##STR00028## wherein in formula (iii), R represents a hydrogen, a linear or branched C.sub.1-C.sub.8 alkyl, or a linear or branched C.sub.1-C.sub.4 hydroxyalkyl, and n has the value 1, 2, or 3.

12. The process according to claim 1, wherein the composition (1) comprises one or more solvent(s) other than hydrotropic solvent(s), chosen from i) C.sub.1-C.sub.4 lower alkanols; ii) polyols; iii) polyol ethers; or mixtures of two or more thereof.

13. The process according to claim 1, wherein the composition (1) comprises one or more solvent(s) chosen from C.sub.1-C.sub.4 lower alkanols, present in an amount ranging from about 5% to 80% by weight, relative to the total weight of the composition (1).

14. The process according to claim 1, wherein composition (1) comprises one or more solvents other than hydrotropic solvents and composition (2) comprises one or more hydrotropic solvents chosen from alkanols bearing aryl substituents.

15. The process according to claim 1, wherein the composition (2) comprises one or more optionally associative, optionally substantive anionic, cationic, nonionic, amphoteric or zwitterionic polymers, or mixtures of two or more thereof.

16. The process according to claim 15, wherein the composition (2) comprises one or more polymer(s) chosen from (poly)hydroxy(C.sub.1-C.sub.4)alkylcellulose nonionic cellulose ethers.

17. The process according to claim 1, wherein i) the mixture of the compositions (1) and (2) is applied to the keratin fibers and left on the keratin fibers for a leave-on time ranging from 3 to 60 minutes at a temperature ranging from 25-55 C., and ii) the keratin fibers are optionally subsequently rinsed, shampooed, and/or dried.

18. The process according to claim 1, wherein i) the mixture is applied to the keratin fibers and left on the keratin fibers for a leave-on time ranging from 10 to 30 minutes at a temperature ranging from 25-55 C., and ii) the keratin fibers are optionally subsequently rinsed, shampooed, and/or dried.

19. The process according to claim 17, wherein the dyeing process is repeated from 1 to 6 times.

20. A device or kit comprising at least two compartments separate from one another comprising, composition (1) in a first compartment and composition (2) in a second compartment, wherein: composition (1) is anhydrous and comprises one or more dyes chosen from compounds of formulae (I) and/or (II) below: ##STR00029## wherein in formulae (I) and (II): Z.sub.1 represents an oxygen atom or a group N(R.sub.6); Z.sub.1 represents an oxygen atom or a group N(R.sub.6); with the proviso that when Z.sub.1 represents N(R.sub.6) and/or Z.sub.1 represents N(R.sub.6), then R.sub.1 and R.sub.6 and/or R.sub.1 and R.sub.6, respectively, may form, together with the nitrogen atom to which they are attached, an optionally substituted, 5- to 8-membered, optionally cationic, saturated, unsaturated, or aromatic heterocycle; R.sub.1, R.sub.1, R.sub.6, and R.sub.6 each independently represent: a hydrogen atom, or a C.sub.1-C.sub.10 alkyl radical optionally interrupted with one or more non-adjacent heteroatoms, and/or optionally substituted; R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.2, R.sub.3, R.sub.4, and R.sub.5 each independently represent: a hydrogen atom, an optionally substituted C.sub.1-C.sub.4 alkyl radical, or a group chosen from NH.sub.2, N(H)R.sub.10, N(R.sub.11)R.sub.12, OH, or OR.sub.9, with R.sub.9 and R.sub.10 representing an optionally substituted, linear or branched C.sub.1-C.sub.6 alkyl, R.sub.11 and R.sub.12, which may be identical or different, representing an optionally substituted, linear or branched C.sub.1-C.sub.6 alkyl, wherein R.sub.11 and R.sub.12 optionally form, together with the nitrogen atom to which they are attached, a saturated, unsaturated or aromatic 5- to 8-membered heterocycle optionally containing one or more other heteroatoms or groups chosen selected from N, O, S, S(O).sub.2, and C(O), the heterocycle being optionally substituted, and/or R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.2, R.sub.3, R.sub.4, and R.sub.5 form, in pairs with adjacent radicals, an optionally substituted, saturated or unsaturated (hetero)cycle; wherein when the compound of formula (I) and/or (II) is positively charged, then it comprises as many anionic counterions as cationic charges to achieve the electrical neutrality of the molecule; and composition (2) is aqueous, and comprises one or more ingredients chosen from: i) hydrotropic solvents; ii) anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric or zwitterionic surfactants, or mixtures of two or more thereof; iii) anionic polymers, cationic polymers, nonionic polymers, amphoteric or zwitterionic polymers, any of which may be optionally associative, or optionally substantive, or mixtures of two or more thereof; wherein composition (2) does not comprise any dye (I) or (II).

Description

EXAMPLES

Example 1: Synthesis of the Dye Having the Following Formula

(1) ##STR00025##

(2) 500 ml of ethanol are placed in a 1-liter one-necked round-bottomed flask equipped with a calcium chloride guard tube, followed by addition, with stirring, of 50 g (0.2177 mol) of 2-[(3-aminopyrazolo[1,5-a]pyridin-2-yl)oxy]ethanol hydrochloride. 14.2 g (0.986 mol) of 2-chloropyridine-3,5-diamine and 60.3 ml (0.346 mol) of N-ethyl-N-(propan-2-yl)propan-2-amine are added to this solution.

(3) The solution thus obtained is stirred at ambient temperature for 4 days. The black precipitate formed is isolated by filtration, washed with water and dried in a desiccator under vacuum at 30 C. in the presence of a desiccant, to constant weight. A black solid is thus obtained.

(4) The spectrometric analyses show that the compound obtained corresponds to the above structure.

Example 2

(5) The Following Compositions were Produced:

(6) Composition (1)

(7) TABLE-US-00001 ingredients % by weight (g) Dye of example 1 2.44 Benzyl alcohol 24.39 Ethanol qs 100

(8) Composition (2)

(9) TABLE-US-00002 Ingredients % by weight (g) Hydroxyethylcellulose 0.881 Xanthan Gum 0.377 Triethanolamine 0.176 Phenoxyethanol 1.258 Caprylyl glycol 1.258 Water qs 100

(10) At the time of use, 20.5 g of composition (1) are mixed with 79.5 g of composition (2). After mixing the composition (1) with (2), a gel with a pH=7 is obtained.

(11) The mixture is applied to locks of natural hair containing 90% gray hairs.

(12) 1st Application:

(13) After a leave-on time of 30 min at ambient temperature (27 C.), the hair is rinsed, shampooed and then dried. Hair with a uniform light gray shade is obtained.

(14) The 2nd, 3rd, 4th and 5th applications are carried out in an identical manner to the first.

(15) A gradual* coloring is then obtained, which, after several consecutive applications, tends toward a natural dark gray.

(16) *Gradual means that, after each application, a significant darkening and/or uptake of color is obtained after each application.

(17) The colors of the locks thus obtained with dye 1 used in the same pH 7 dye support were evaluated in the CIE L* a* b* system, using a Minolta Spectrophotometer CM2600D colorimeter (specular components included, illuminant D65, angle 10).

(18) In this L* a* b* system, the three parameters denote, respectively, L*: the color intensity, a*: the green/red color axis, and b*: the blue/yellow color axis. For the intensity, the lower the value, the darker and more intense the color.

(19) The variation in coloring or gain in color build-up is the difference in color between the locks of natural gray hair (NG) treated with the composition according to the invention, and the untreated locks, and is measured by (E) according to the following equation:
E={square root over ((L*L.sub.o*).sup.2+(a*a.sub.o*).sup.2+(b*b.sub.o*).sup.2)}

(20) In this equation, L*, a* and b* represent the values measured on NG dyed hair according to the invention, and L0*, a0* and b0* represent the values measured on the untreated locks.

(21) The higher the value of E, the greater the gain in color build-up.

(22) The results are indicated in the table below.

(23) TABLE-US-00003 Dye of example (1) L a b E 1st application 36.6 0.3 4.4 33.50 2nd application 31.6 0.2 2.8 38.73 3rd application 28.5 0.4 2.3 41.79 4th application 26.5 0.2 1.4 43.98

(24) It thus appears that the dyeing process according to the invention makes it possible to obtain very effective coloring in particular in terms of color uptake and of strength, this being as soon as the first application.