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

1-16. (canceled)

17. A process for dyeing keratin fibers, in particular human keratin fibers, which comprises mixing together at least compositions (1) and (2), wherein: composition (1) is anhydrous and comprises one or more dyes selected from dyes of azomethine type comprising two pyrazolopyridine units of formulae (I) and (II) below: ##STR00026## wherein in formulae (I) and (II): Z.sub.1 represents an oxygen atom or a group —N(R.sub.6)—; Z′1 represents an oxygen atom or a group —N(R′.sub.6)—; 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; a group selected 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 selected 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) 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 selected from: i) hydrotropic solvents; ii) anionic, cationic, nonionic, amphoteric or zwitterionic surfactants or mixtures thereof; iii) anionic, cationic, nonionic, amphoteric or zwitterionic, optionally associative, optionally substantive, polymers, or blends thereof; wherein composition (2) does not comprise any dye (I) or (II).

18. The process as claimed in claim 17, characterized in that R.sub.1 and R′.sub.1 are selected 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; v) —[(CH.sub.2).sub.m—O].sub.p-L-Y with p=1, 2 or 3.

19. The process as claimed in claim 17, wherein the compounds of formula (I) or (II) are such that 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.

20. The process as claimed in claim 17, wherein the compound(s) of formula (I) or (II) are selected from those of formulae (I′) and (II′): ##STR00027## wherein formulae (I′) and (II′): Z″.sub.1 is selected from an oxygen atom and a group —N(R″.sub.6)—;  when Z″.sub.1 represents —N(R″.sub.6)—, then R″.sub.1 and R″.sub.r 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, a heterocycle optionally substituted with one or more C.sub.1-C.sub.4 alkyl and/or hydroxyl radicals and selected from pyrrolidine, piperidine, morpholine, piperazine, or imidazole; R″.sub.6 represents: a hydrogen atom, a C.sub.1-C.sub.10 alkyl radical optionally substituted with a hydroxyl radical; R″.sub.2, R″.sub.3, R″.sub.4 and R″.sub.5 each independently represent: a hydrogen atom, a C.sub.1-C.sub.4 alkyl radical; in particular, the compound(s) of formula (I′) or (II′) are such that, when Z″.sub.1 represents an oxygen atom, R″.sub.1 denotes a linear or branched C.sub.1-C.sub.6 alkyl radical; 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; a radical —[(CH.sub.2).sub.m′-O].sub.p-L′-Y′ with p′=1, 2 or 3, L′ denoting a saturated and linear C.sub.1-C.sub.6 divalent hydrocarbon-based radical, and Y′ denoting a hydroxyl radical or a hydrogen atom; an alkyl radical substituted with a heterocycle selected from pyrrolidinyl, piperidinyl, morpholinyl, piperazinyl or imidazolyl, said heterocycle being optionally substituted with one or more C.sub.1-C.sub.4 alkyl radicals.

21. The process as claimed in claim 17, wherein the compounds (I′) or (II′) are such that Z″.sub.1 represents NH, and R″1 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, an alkyl radical substituted with a heterocycle selected from pyrrolidinyl, piperidyl, morpholinyl, piperazinyl, or imidazolyl, said heterocycle being optionally substituted with one or more C.sub.1-C.sub.4 alkyl radicals.

22. The process as claimed in claim 17, wherein the compounds (I′) or (II′) are such that Z″.sub.1 represents —N(R″6)-, 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 selected from pyrrolidinyl, piperidyl, morpholinyl or piperazinyl rings optionally substituted with one or more C.sub.1-C.sub.4 alkyl and/or hydroxyl radicals.

23. The process as claimed in claim 17, wherein the compound(s) of formula (I), (II), (I′) or (II′) are selected from: 1 2,2′-[(5-amino-3-iminopyridine-2,6(1H,3H)-diylidene)bis(nitrilopyrazolo[1,5-a]pyridine-3,2-diylimino)]diethanol; 2 3,3′-[(5-amino-3-iminopyridine-2,6(1H,3H)-diylidene)bis(nitrilopyrazolo[1,5-a]pyridine-3,2-diylimino)]dipropan-1-ol; 3 N3,N3′-(5-amino-3-iminopyridine-2,6(1H,3H)-diylidene)bis{N2-[2-(dimethylamino)ethyl]pyrazolo[1,5-a]pyridine-2,3-diamine}; 4 N3,N3′-(5-amino-3-iminopyridine-2,6(1H,3H)-diylidene)bis{N2-[3-(dimethylamino)propyl]pyrazolo-[1,5-a]pyridine-2,3-diamine}; 5 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}; 6 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}; 7 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}; 8 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}; 9 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}; 10 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}; 11 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}; 12 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}; 13 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; 14 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; 16 3,3′-[(5-amino-3-iminopyridine-2,6(1H,3H)diylidene)bis(nitrilopyrazolo[1,5-a]pyridine-3,2-diyloxy)]dipropan-1-ol; 17 N,N′-(5-amino-3-iminopyridine-2,6(1H,3H)-diylidene)bis{2-[2-(dimethylamino)ethoxy]pyrazolo[1,5-a]pyridin-3-amine}; 18 N,N′-(5-amino-3-iminopyridine-2,6(1H,3H)-diylidene)bis{2-[3-(dimethylamino)propoxy]pyrazolo[1,5-a]pyridin-3-amine}; 19 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}; 20 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}; 22 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}; 23 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}; 24 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}; 25 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}; 26 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}; 27 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}; 28 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}; 29 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}; 30 N,N′-(5-amino-3-iminopyridine-2,6(1H,3H)-diylidene)bis(2-methoxypyrazolo[1,5-a]pyridin-3-amine); 31 N,N′-(5-amino-3-iminopyridine-2,6(1H,3H)-diylidene)bis(2-ethoxypyrazolo[1,5-a]pyridin-3-amine); 32 N,N′-(5-amino-3-iminopyridine-2,6(1H,3H)-diylidene)bis(2-propoxypyrazolo[1,5-a]pyridin-3-amine); 33 N,N′-(5-amino-3-iminopyridine-2,6(1H,3H)-diylidene)bis[2-(propan-2-yloxy)pyrazolo[1,5-a]pyridin-3-amine]; 34 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}; 35 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; 36 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}; 37 N,N′-(5-amino-3-iminopyridine-2,6(1H,3H)-diylidene)bis(2-tert-butoxypyrazolo[1,5-a]pyridin-3-amine); 38 N3,N3′-(5-amino-3-iminopyridine-2,6(1H,3H)diylidene)bis(N2,N2-dimethylpyrazolo[-1,5-a]pyridine-2,3-diamine); 39 N3,N3′-(5-amino-3-iminopyridine-2,6(1H,3H)diylidene)bis(N2,N2-diethylpyrazolo[1,5-a]pyridine-2,3-diamine); 40 2,2′,2″,2′″-[(5-amino-3-iminopyridine-2,6(1H,3H)-diylidene)bis(nitrilopyrazolo[1,5-a]pyridine-3,2-diylnitrilo)]tetraethanol; 41 N,N′-(5-amino-3-iminopyridine-2,6(1H,3H)diylidene)bis[2-(pyrrolidin-1-yl)pyrazolo[1,5-a]pyridin-3-amine]; 42 N,N′-(5-amino-3-iminopyridine-2,6(1H,3H)diylidene)bis[2-(piperidin-1-yl)pyrazolo[1,5-a]pyridin-3-amine]; 43 N,N′-(5-amino-3-iminopyridine-2,6(1H,3H)diylidene)bis[2-(morpholin-4-yl)pyrazolo-[1,5-a]pyridin-3-amine]; 44 N,N′-(5-amino-3-iminopyridine-2,6(1H,3H)diylidene)bis[2-(4-methylpiperazin-1-yl)pyrazolo[1,5-a]pyridin-3-amine]; 45 1,1′-[(5-amino-3-iminopyridine-2,6(1H,3H)diylidene)bis(nitrilopyrazolo[1,5-a]pyridine-3,2-diyl)]dipyrrolidin-3-ol; 46 1,1′-[(5-amino-3-iminopyridine-2,6(1H,3H)diylidene)bis(nitrilopyrazolo[1,5-a]pyridine-3,2-diyl)]dipyrrolidine-3,4-diol; 47 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; 48 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; 49 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}; 50 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}; 51 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}; 52 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}; 53 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}; 54 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}; 55 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}; 56 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}; 57 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}; 58 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}; 59 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}; 60 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}; 61 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; 62 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; 63 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; 64 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}; 65 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}; 66 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}; 67 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}; 68 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}; 69 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}; 70 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}; 71 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}; 72 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}; 73 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}; 74 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}; 75 N,N′-(5-amino-3-iminopyridine-2,6(1H,3H)-diylidene)bis(2-methoxy-6,7-dimethylpyrazolo[1,5-a]pyridin-3-amine); 76 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; 77 N,N′-(5-amino-3-iminopyridine-2,6(1H,3H)-diylidene)bis(6,7-dimethyl-2-propoxypyrazolo[1,5-a]pyridin-3-amine); 78 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]; 79 N,N′-(5-amino-3-iminopyridine-2,6(1H,3H)-diylidene)bis(2-tert-butoxy-6,7-dimethylpyrazolo[1,5-a]pyridin-3-amine); 80 N3,N3′-(5-amino-3-iminopyridine-2,6(1H,3H)-diylidene)bis(N2,N2,6,7-tetramethylpyrazolo[1,5-a]pyridine-2,3-diamine); 81 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); 82 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; 83 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]; 84 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]; 85 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]; 86 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]; 87 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; 88 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.

24. The process as claimed in claim 17, wherein the compound(s) of formula (I), (I′), (II) or (II′) are present in an amount ranging from 0.01% to 15% by weight.

25. The process as claimed in claim 17, wherein the compound(s) of formula (I), (I′), (II) or (II′) are present in an amount ranging from 0.05% 10% by weight.

26. The process as claimed in claim 17, wherein the composition (1) comprises one or more hydrotropic solvent(s) in particular selected from alcohol ethers, aliphatic esters, aliphatic ethers, aromatic ethers, alkanols bearing aryl substituents, lactones, or mixtures thereof.

27. The process as claimed in claim 17, wherein the composition (1) comprises one or more hydrotropic solvent(s) in particular selected from alcohol ethers, aliphatic esters, aliphatic ethers, aromatic ethers, alkanols bearing aryl substituents, lactones or mixtures thereof selected from: alcohol ethers, in particular 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, in particular of C.sub.6-C.sub.10, of a C.sub.1-C.sub.6 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; lactones and mixtures thereof, with: ##STR00028## wherein 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, a linear or branched C.sub.1-C.sub.6 alkyl or a linear or branched C.sub.1-C.sub.2 hydroxyalkyl.

28. The process as claimed in claim 17, wherein the composition (1) comprises one or more solvent(s) other than hydrotropic solvent(s) selected from i) C.sub.1-C.sub.4 lower alkanols; ii) polyols or iii) polyol ethers; in an amount between approximately 1% and 95% by weight relative to the total weight of the composition (1).

29. The process as claimed in claim 17, wherein the composition (1) comprises one or more solvent(s) other than the hydrotropic solvent(s) selected from C.sub.1-C.sub.4 lower alkanols; in an amount between approximately 5% and 80% by weight relative to the total weight of the composition (1).

30. The process as claimed in claim 17, wherein composition (1) comprises a solvent other than the hydrotropic solvents and composition (2) comprises one or more hydrotropic solvents selected from alkanols bearing aryl substituents.

31. The process as claimed in claim 17, wherein the composition (2) comprises one or more optionally associative, optionally substantive anionic, cationic, nonionic, amphoteric or zwitterionic polymers, or blends thereof.

32. The process as claimed in claim 31, wherein the polymer(s) are selected from (poly)hydroxy(C.sub.1-C.sub.4)alkylcellulose nonionic cellulose ethers.

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

34. The process as claimed in claim 17, wherein i) the mixture of the compositions (1) and (2) as defined in any one of claims 1 to 13 is applied to the keratin fibers for a leave-on time of between 10 and 30 minutes and at a temperature between 25 and 55° C., and ii) the fibers are optionally rinsed, shampooed and/or dried.

35. The process as claimed in claim 33, wherein said dyeing process which carries out step i) and optionally step ii) is repeated from 1 to 6 times.

36. 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 selected from dyes of azomethine type comprising two pyrazolopyridine units of formulae (I) and (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′)—; 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; a group selected 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 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) 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 selected from: i) hydrotropic solvents; ii) anionic, cationic, nonionic, amphoteric or zwitterionic surfactants or mixtures thereof; iii) anionic, cationic, nonionic, amphoteric or zwitterionic, optionally associative, optionally substantive, polymers, or blends thereof; wherein composition (2) does not comprise any dye (I) or (II).

Description

EXAMPLES

Example 1: Synthesis of the Dye Having the Following Formula

[0409] ##STR00025##

[0410] 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.

[0411] 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.

[0412] The spectrometric analyses show that the compound obtained corresponds to the above structure.

Example 2

[0413] The Following Compositions were Produced:

[0414] Composition (1)

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

[0415] Composition (2)

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

[0416] 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.

[0417] The mixture is applied to locks of natural hair containing 90% gray hairs.

[0418] 1st Application:

[0419] 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.

[0420] The 2nd, 3rd, 4th and 5th applications are carried out in an identical manner to the first.

[0421] A gradual* coloring is then obtained, which, after several consecutive applications, tends toward a natural dark gray.

[0422] *Gradual means that, after each application, a significant darkening and/or uptake of color is obtained after each application.

[0423] 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°).

[0424] 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.

[0425] 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 (ΔE) according to the following equation:

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

[0426] 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.

[0427] The higher the value of ΔE, the greater the gain in color build-up.

[0428] The results are indicated in the table below.

TABLE-US-00003 Dye of example (1) L a b ΔE 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

[0429] 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.