Composition for dyeing the hair, comprising a heterocyclic oxidation base and a 2-amino-5-ethylphenol coupler

Abstract

Composition for dyeing the hair, comprising a heterocyclic oxidation base and a 2-amino-5-ethylphenol coupler The present invention relates to a composition for dyeing keratin fibres, comprising a particular heterocyclic oxidation base and a 2-amino-5-ethylphenol coupler. The invention also relates to a process for dyeing keratin fibres using this composition. Finally, the invention relates to the use of such a composition for dyeing keratin fibres, and in particular the hair.

Claims

1. A composition for dyeing keratin fibers, comprising: (A) at least one 2-amino-5-ethylphenol coupler, an addition salt thereof, or a solvate thereof, (B) at least one pyrazole heterocyclic oxidation base chosen from: A1) pyrazolopyridines according to formula (I) below, addition salts thereof, solvates thereof, or solvates of the salts thereof: ##STR00024## wherein: R.sub.1, R.sub.2, R.sub.3, R.sub.4, and R.sub.5, which may be identical or different, are chosen from a hydrogen atom; a halogen atom; a —NHSO.sub.3H radical; a hydroxyl radical; a (C.sub.1-C.sub.4)alkyl radical; a (C.sub.1-C.sub.4)alkoxy radical; a (C.sub.1-C.sub.4)alkylthio radical; mono(C.sub.1-C.sub.4)alkylamino; a di(C.sub.1-C.sub.4)alkylamino radical, wherein the two alkyl groups may form, together with the nitrogen atom to which they are attached, a ring that may be interrupted with at least one nitrogen, oxygen, or sulfur atom; a heterocycle; a nitro radical; a phenyl radical; a carbonyl radical; a (C.sub.1-C.sub.4)alkoxycarbonyl radical; a carboxamido radical; a cyano radical; an amino radical; a sulfonyl radical; a —CO.sub.2H radical, a —SO.sub.3H radical, a —PO.sub.3H.sub.2 radical, a —PO.sub.4H.sub.2 radical, or a group: ##STR00025## wherein R′″ is chosen from an oxygen or nitrogen atom, Q is chosen from an oxygen atom, a NH group, or NH(C.sub.1-C.sub.4)alkyl, and Y is chosen from a hydroxyl, amino, C.sub.1-C.sub.4 alkyl, (C.sub.1-C.sub.4)alkoxy, (C.sub.1-C.sub.4)alkylamino, or di(C.sub.1-C.sub.4)alkylamino radical; A2) pyrazolopyridine oxidation bases according to formula (II) below ##STR00026## wherein: Z.sub.1 and Z.sub.2, independently of each other, are chosen from: a covalent single bond; or a divalent radical chosen from: a —O(CH.sub.2).sub.p— radical, wherein p is chosen from an integer ranging from 0 to 6, or a —NR′.sub.6(CH.sub.2).sub.q(C.sub.6H.sub.4).sub.t— radical, wherein q is chosen from an integer ranging from 0 to 6, t is chosen from 0 or 1, and R′.sub.6 is chosen from a hydrogen atom or a C.sub.1-C.sub.6 alkyl radical optionally substituted with at least one hydroxyl group; Z.sub.1 may also be chosen from a divalent radical —S—, —SO—, or —SO.sub.2—, wherein R′.sub.1 is a methyl radical; R′.sub.1 and R′.sub.2, independently of each other, are chosen from: a hydrogen atom; a C.sub.1-C.sub.10 alkyl radical, which is optionally substituted and optionally interrupted with a heteroatom or a group chosen from O, N, Si, S, SO, or SO.sub.2; a halogen; a SO.sub.3H radical; a substituted or unsubstituted, saturated, unsaturated, or aromatic, 5- to 8-membered ring, optionally containing at least one heteroatom or group chosen from N, O, S, SO.sub.2, or —CO—, wherein the ring is optionally cationic and/or substituted with a cationic radical; or a —N.sup.+R.sub.19R.sub.18R.sub.19 group, wherein R.sub.17, R.sub.18, and R.sub.19 are linear or branched C.sub.1-C.sub.5 alkyls optionally substituted with at least one hydroxyl group; wherein when Z.sub.1 represents a covalent bond, then R.sub.1 optionally represents: an optionally substituted C.sub.1-C.sub.6 alkylcarbonyl radical; or a radical —O—CO—R, —CO—O—R, NR—CO—R′, or —CO—NRR′, wherein R and R′, independently of each other, are chosen from a hydrogen atom or an optionally substituted C.sub.1-C.sub.6 alkyl radical; wherein when Z.sub.2 represents a covalent bond, then R.sub.2 optionally represents: an optionally substituted C.sub.1-C.sub.6 alkylcarbonyl radical; or a radical —O—CO—R, —CO—O—R, NR—CO—R′, or —CO—NRR′, wherein R and R′, independently of each other, are chosen from a hydrogen atom or an optionally substituted C.sub.1-C.sub.6 alkyl radical; R′.sub.3, R′.sub.4, and R′.sub.5, which may be identical or different, are chosen from: a hydrogen atom; a hydroxyl radical; a C.sub.1-C.sub.6 alkoxy radical; a C.sub.1-C.sub.6 alkylthio radical; an amino radical; a monoalkylamino radical; a C.sub.1-C.sub.6 dialkylamino radical, wherein the alkyl radicals may form, with the nitrogen atom to which they are attached, a saturated or unsaturated, aromatic or nonaromatic, 5- to 8-membered heterocycle, which may contain at least one heteroatom or group chosen from N, O, S, SO.sub.2, and CO, wherein the heterocycle is optionally cationic and/or substituted with a cationic radical; an optionally substituted C.sub.1-C.sub.6 alkylcarbonyl radical; a radical —O—CO—R, —CO—O—R, NR—CO—R′, or —CO—NRR′, wherein R and R′ independently of each other, are chosen from a hydrogen atom or an optionally substituted C.sub.1-C.sub.6 alkyl radical; a halogen; a —NHSO.sub.3H radical; an optionally substituted C.sub.1-C.sub.4 alkyl radical; a saturated, unsaturated or aromatic, optionally substituted carbon-based ring; or R′.sub.3, R′.sub.4, and R′.sub.5 optionally form in pairs a partially saturated or unsaturated ring, and X is chosen from an ion or group of ions making it possible to ensure the electronegativity of the derivative of formula (II); wherein least one of the groups R′.sub.1 or R′.sub.2 is chosen from a cationic radical; or A3) diamino-N,N-dihydropyrazolone derivatives according to formula (III) below, addition salts thereof, solvates thereof, or solvates of the salts thereof: ##STR00027## wherein: R″.sub.3 and R″.sub.4, which may be identical or different, are chosen from: a hydrogen atom; a linear or branched C.sub.1-C.sub.6 alkyl radical optionally substituted with at least one radical chosen from a OR″.sub.5 radical, a NR″.sub.6R″.sub.7 radical, a carboxyl radical, a sulfonic radical, a carboxamido CONR″.sub.6R″.sub.7 radical, a sulfonamido radical SO.sub.2NR″.sub.6R″.sub.7, a heteroaryl, an aryl optionally substituted with at least one (C.sub.1-C.sub.4)alkyl, hydroxyl, C.sub.1-C.sub.2 alkoxy, amino, or (di)alkyl(C.sub.1-C.sub.2)amino group; an aryl radical optionally substituted with at least one (C.sub.1-C.sub.4)alkyl, hydroxyl, C.sub.1-C.sub.2 alkoxy, amino, or (di)alkyl(C.sub.1-C.sub.2)amino; a 5- or 6-membered heteroaryl radical, optionally substituted with at least one radical chosen from (C.sub.1-C.sub.4)alkyl or (C.sub.1-C.sub.2)alkoxy; or R″.sub.3 and R″.sub.4 optionally form, together with the nitrogen atom to which they are attached, a 5- or 7-membered heterocycle, the carbon atoms of which is optionally replaced with an optionally substituted oxygen or nitrogen atom; R″.sub.5, R″.sub.6, and R″.sub.7, which may be identical or different, are chosen from: a hydrogen atom; a linear or branched C.sub.1-C.sub.4 alkyl radical optionally substituted with at least one radical chosen from hydroxyl, C.sub.1-C.sub.2 alkoxy, carboxamido CONR″.sub.8R″.sub.9, sulfonyl SO.sub.2R″.sub.8, aryl optionally substituted with a (C.sub.1-C.sub.4)alkyl, hydroxyl, C.sub.1-C.sub.2 alkoxy, amino, or (di)alkyl(C.sub.1-C.sub.2)amino, aryl optionally substituted with a (C.sub.1-C.sub.4)alkyl, hydroxyl, C.sub.1-C.sub.2 alkoxy, amino or (di)alkyl(C.sub.1-C.sub.2)amino; or R″.sub.6 and R″.sub.7, which may be identical or different, are optionally chosen from a carboxamido radical CONR″.sub.8R″.sub.9 or a sulfonyl radical SO.sub.2R″.sub.8; R″.sub.8 and R″.sub.9, which may be identical or different, are chosen from a hydrogen atom, a linear or branched C.sub.1-C.sub.4 alkyl radical optionally substituted with at least one hydroxyl or C.sub.1-C.sub.2 alkoxy; and R″.sub.1 and R″.sub.2 form, together with the nitrogen atom(s) to which they are attached, a saturated or unsaturated 5- to 7-membered heterocycle optionally substituted with at least one radical chosen from halogen atoms and amino, (di)alkyl(C.sub.1-C.sub.4)amino, hydroxyl, carboxyl, carboxamido and (C.sub.1-C.sub.2)alkoxy radicals, C.sub.1-C.sub.4 alkyl radicals optionally substituted with at least one hydroxyl, amino, (di)alkylamino, alkoxy, carboxyl, or sulfonyl radical.

2. The composition according to claim 1, wherein the pyrazolopyridines of formula (I) are chosen from those according to the formula below: ##STR00028## wherein: R.sub.1, R.sub.2, and R.sub.3, which may be identical or different, are chosen from a hydrogen atom; a halogen atom; a hydroxyl radical; a (C.sub.1-C.sub.4)alkyl radical; a (C.sub.1-C.sub.4)alkylthio radical; a (C.sub.1-C.sub.4)alkoxy radical; a —NHSO.sub.3H radical; an amino radical; a (C.sub.1-C.sub.4)alkylamino radical; a di(C.sub.1-C.sub.4)alkylamino radical, wherein the two alkyl groups may form, together with the nitrogen atom to which they are attached, a ring that may be interrupted with at least one nitrogen, oxygen, or sulfur atom; a heterocycle; a sulfonamide radical; a carbonyl radical; a (C.sub.1-C.sub.4)alkoxycarbonyl radical; a carboxamido radical; or a group: ##STR00029## wherein R′″ is chosen from an oxygen or nitrogen atom, Q is chosen from an oxygen atom, an NH group, or NH(C.sub.1-C.sub.4)alkyl, and Y is chosen from a hydroxyl, amino, C.sub.1-C.sub.4 alkyl, (C.sub.1-C.sub.4)alkoxy, (C.sub.1-C.sub.4)alkylamino, or di(Ci-C4)alkylamino radical.

3. The composition according to claim 1, wherein the pyrazolopyridines of formula (I) are chosen from: pyrazolo[1,5-a]pyridin-3-ylamine; 2-acetylaminopyrazolo[1,5-a]pyridin-3-ylamine; 2-morpholin-4-ylpyrazolo[1,5-a]pyridin-3-ylamine; 3-aminopyrazolo[1,5-a]pyridine-2-carboxylic acid; 2-methoxypyrazolo[1,5-a]pyridin-3-ylamino; (3-aminopyrazolo[1,5-a]pyridin-7-yl)methanol; 2-(3-aminopyrazolo[1,5-a]pyridin-5-yl)ethanol; 2-(3-aminopyrazolo[1,5-a]pyridin-7-yl)ethanol; (3-aminopyrazolo[1,5-a]pyridin-2-yl)methanol; 3,6-diaminopyrazolo[1,5-a]pyridine; 3,4-diaminopyrazolo[1,5-a]pyridine; pyrazolo[1,5-a]pyridine-3,7-diamine; 7-morpholin-4-ylpyrazolo[1,5-a]pyridin-3-ylamine; pyrazolo[1,5-a]pyridine-3,5-diamine; 5-morpholin-4-ylpyrazolo[1,5-a]pyridin-3-ylamine; 2-[(3-aminopyrazolo[1,5-a]pyridin-5-yl)(2-hydroxyethyl)amino]ethanol; 2-[(3-aminopyrazolo[1,5-a]pyridin-7-yl)(2-hydroxyethyl)amino]ethanol; 3-aminopyrazolo[1,5-a]pyridin-5-ol; 3-aminopyrazolo[1,5-a]pyridin-4-ol; 3-aminopyrazolo[1,5-a]pyridin-6-ol; 3-aminopyrazolo[1,5-a]pyridin-7-ol; 2-methoxy-6,7-dimethylpyrazolo[1,5-a]pyridin-3-amine; 2-[(3-aminopyrazolo[1,5-a]pyridin-2-yl)oxy]ethanol; 4-ethyl-2-methoxy-7-methylpyrazolo[1,5-a]pyridin-3-amine hydrochloride; 1-(3-aminopyrazolo[1,5-a]pyridin-2-yl)pyrrolidin-3-ol; 2,2′-[(3-aminopyrazolo[1,5-a]pyridin-2-yl)imino]diethanol; 2-[(3-aminopyrazolo[1,5-a]pyridin-2-yl)amino]ethanol; N2-(2-pyridin-3-ylethyl)pyrazolo[1,5-a]pyridine-2,3-diamine; or addition salts thereof, solvates thereof, or solvates of the salts thereof.

4. The composition according to claim 1, wherein the pyrazolopyridine oxidation bases are chosen from compounds according to formula (II) below: ##STR00030## wherein: Z.sub.1 is chosen from: a covalent single bond; or a divalent radical chosen from: a —O(CH.sub.2).sub.p— radical, wherein p is chosen from an integer ranging from 0 to 6, or a —NR′.sub.6(CH.sub.2).sub.q(C.sub.6H.sub.4).sub.t— radical, wherein q is chosen from an integer ranging from 0 to 6, t is chosen from 0 or 1, and R′.sub.6 is chosen from a hydrogen atom or a C.sub.1-C.sub.6 alkyl radical optionally substituted with at least one hydroxyl group; or a radical —S—, —SO—, or —SO.sub.2—, wherein R′.sub.1 is a methyl radical; R′.sub.1 is chosen from: a hydrogen atom; a C.sub.1-C.sub.10 alkyl radical, which is optionally substituted and optionally interrupted with a heteroatom or a group chosen from O, N, Si, S, SO, or SO.sub.2; a halogen; a SO.sub.3H radical; a substituted or unsubstituted, saturated, unsaturated, or aromatic, 5- to 8-membered ring, optionally containing at least one heteroatom or group chosen from N, O, S, SO.sub.2, or —CO—, wherein the ring is optionally cationic and/or substituted with a cationic radical; or a —N.sup.+R.sub.19R.sub.18R.sub.19 group, wherein R.sub.17, R.sub.18 and R.sub.19 are linear or branched C.sub.1-C.sub.5 alkyls optionally substituted with at least one hydroxyl group; wherein when Z.sub.1 represents a covalent bond, then R.sub.1 optionally represents: an optionally substituted C.sub.1-C.sub.6 alkylcarbonyl radical; a radical —O—CO—R, —CO—O—R, NR—CO—R′, or —CO—NRR′, wherein R and R′, independently of each other, are chosen from a hydrogen atom or an optionally substituted C.sub.1-C.sub.6 alkyl radical; wherein when Z.sub.2 represents a covalent bond, then R.sub.2 optionally represents: an optionally substituted C.sub.1-C.sub.6 alkylcarbonyl radical; or a radical —O—CO—R, —CO—O—R, NR—CO—R′, or —CO—NRR′, wherein R and R′, independently of each other, are chosen from a hydrogen atom or an optionally substituted C.sub.1-C.sub.6 alkyl radical; R′.sub.3, R′.sub.4, and R′.sub.5, which may be identical or different, are chosen from: a hydrogen atom; a hydroxyl radical; a C.sub.1-C.sub.6 alkoxy radical; a C.sub.1-C.sub.6 alkylthio radical; an amino radical; a monoalkylamino radical; a C.sub.1-C.sub.6 dialkylamino radical, wherein the alkyl radicals may form, with the nitrogen atom to which they are attached, a saturated or unsaturated, aromatic or nonaromatic, 5- to 8-membered heterocycle, which optionally contain at least one heteroatom or group chosen from N, O, S, SO.sub.2, and CO, wherein the heterocycle is optionally cationic and/or substituted with a cationic radical; an optionally substituted C.sub.1-C.sub.6 alkylcarbonyl radical; a radical —O—CO—R, —CO—O—R, NR—CO—R′, or —CO—NRR′, wherein R and R′, independently of each other, are chosen from a hydrogen atom or an optionally substituted C.sub.1-C.sub.6 alkyl radical; a halogen; a —NHSO.sub.3H radical; an optionally substituted C.sub.1-C.sub.4 alkyl radical; a saturated, unsaturated or aromatic, optionally substituted carbon-based ring; or R′.sub.3, R′.sub.4, and R′.sub.5 optionally form in pairs a partially saturated or unsaturated ring.

5. The composition according to claim 1, wherein the compounds of formulae (I) and (II) are chosen from: ##STR00031## 4-(3-Aminopyrazolo[1,5-a]pyridin-2-yl)-1,1-dimethylpiperazin-1-ium salt ##STR00032## 3-[2-(3-Aminopyrazolo[1,5-a]pyridin-2-ylamino)ethyl]-1-methyl-3H-imidazol-1-ium salt, 2-[(3-aminopyrazolo[1,5-a]pyridin-2-yl)oxy]ethanol, or addition salts thereof, solvates thereof, or solvates of the salts thereof.

6. The composition according to claim 1, wherein R″.sub.1 and R″.sub.2 form, together with the nitrogen atom(s) to which they are attached, an optionally substituted saturated or unsaturated 5- or 6-membered ring, optionally substituted with at least one C.sub.1-C.sub.4 alkyl radical, a hydroxyl, a (C.sub.1-C.sub.2)alkoxy, a carboxyl, a carboxamido, an amino, or a (di)(C.sub.1-C.sub.2)alkylamino.

7. The composition according to claim 1, wherein R″.sub.3 and R″.sub.4 are chosen from a hydrogen atom; a linear or branched C.sub.1-C.sub.6 alkyl radical optionally substituted with at least one hydroxyl, (C.sub.1-C.sub.2)alkoxy, amino or (di)(C.sub.1-C.sub.2)alkylamino; or a phenyl radical optionally substituted with at least one hydroxyl, amino, or (C.sub.1-C.sub.2)alkoxy.

8. The composition according to claim 1, wherein the diamino-N,N-dihydropyrazolone derivatives according to formula (III) are chosen from: 2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one; 2-amino-3-ethylamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one; 2-amino-3-isopropylamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one; 2-amino-3-(pyrrolidin-1-yl)-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one; 2-amino-3-(2-hydroxyethyl)amino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one; 2-amino-3-dimethylamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one; 2,3-diamino-5,6,7,8-tetrahydro-1H,6H-pyridazino[1,2-a]pyrazol-1-one; 2,3-diamino-6-hydroxy-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one; or addition salts thereof, solvates thereof, or solvates of the salts thereof.

9. The composition according to claim 1, further comprising at least one surfactant.

10. The composition according to claim 9, wherein the at least one surfactant is chosen from non-ionic surfactants.

11. The composition according to claim 1, further comprising at least one alkaline agent.

12. The composition according to claim 1, wherein the at least one pyrazole heterocyclic oxidation base is present in a total amount ranging from about 0.0001% to about 20% by weight, relative to the total weight of the composition.

13. The composition according to claim 1, wherein the at least one pyrazole heterocyclic oxidation base is present in a total amount ranging from about 0.005% to about 10% by weight, relative to the total weight of the composition.

14. The composition according to claim 1, further comprising at least one chemical oxidizing agent.

15. The composition according to claim 14, wherein the at least one chemical oxidizing agent is chosen from hydrogen peroxide.

16. A method for dyeing keratin fibers, comprising applying to the keratin fibers a dye composition, the dye composition comprising: (A) at least one 2-amino-5-ethylphenol coupler, an addition salt thereof, or a solvate thereof, (B) at least one pyrazole heterocyclic oxidation base chosen from: A1) pyrazolopyridines according to formula (I) below, addition salts thereof, solvates thereof, or solvates of the salts thereof: ##STR00033## wherein: R.sub.1, R.sub.2, R.sub.3, R.sub.4, and R.sub.5, which may be identical or different, are chosen from a hydrogen atom, a halogen atom; a —NHSO.sub.3H radical, a hydroxyl radical, a (C.sub.1-C.sub.4)alkyl radical, a (C.sub.1-C.sub.4)alkoxy radical, a (C.sub.1-C.sub.4)alkylthio radical, mono(C.sub.1-C.sub.4)alkylamino, a di(C.sub.1-C.sub.4)alkylamino radical, wherein the two alkyl groups may form, together with the nitrogen atom to which they are attached, a ring that may be interrupted with at least one nitrogen, oxygen, or sulfur atom, a heterocycle, a nitro radical, a phenyl radical, a carbonyl radical; a (C.sub.1-C.sub.4)alkoxycarbonyl radical, a carboxamido radical, a cyano radical, an amino radical, a sulfonyl radical, a —CO.sub.2H radical, a —SO.sub.3H radical, a —PO.sub.3H.sub.2 radical, a —PO.sub.4H.sub.2 radical, or a group: ##STR00034## wherein R′″ is chosen from an oxygen or nitrogen atom, Q is chosen from an oxygen atom, a NH group, or NH(C.sub.1-C.sub.4)alkyl, and Y is chosen from a hydroxyl, amino, C.sub.1-C4 alkyl, (C.sub.1-C.sub.4)alkoxy, (C.sub.1-C.sub.4)alkylamino, or di(Ci-C4)alkylamino radical; A2) pyrazolopyridine oxidation bases according to formula (II) below ##STR00035## wherein: Z.sub.1 and Z.sub.2, independently of each other, are chosen from: a covalent single bond; or a divalent radical chosen from: a —O(CH.sub.2).sub.p— radical, wherein p is chosen from an integer ranging from 0 to 6, or a —NR′.sub.6(CH.sub.2).sub.q(C.sub.6H.sub.4).sub.t— radical, wherein q is chosen from an integer ranging from 0 to 6 and t is chosen from 0 or 1, and R′.sub.6 is chosen from a hydrogen atom or a C.sub.1-C.sub.6 alkyl radical optionally substituted with at least one hydroxyl group; Z.sub.1 may also be chosen from a divalent radical —S—, —SO—, or —SO.sub.2—, wherein R′.sub.1 is a methyl radical; R′.sub.1 and R′.sub.2, independently of each other, are chosen from: a hydrogen atom; a C.sub.1-C.sub.10 alkyl radical, which is optionally substituted and optionally interrupted with a heteroatom or a group chosen from O, N, Si, S, SO, or SO.sub.2; a halogen; a SO.sub.3H radical; a substituted or unsubstituted, saturated, unsaturated, or aromatic, 5- to 8-membered ring, optionally containing at least one heteroatom or group chosen from N, O, S, SO.sub.2, or —CO—, wherein the ring is optionally cationic and/or substituted with a cationic radical; or a —N.sup.+R.sub.19R.sub.18R.sub.19 group, wherein R.sub.17, R.sub.18, and R.sub.19 are linear or branched C.sub.1-C.sub.5 alkyls optionally substituted with at least one hydroxyl group; wherein when Z.sub.1 represents a covalent bond, then R.sub.1 optionally represents: an optionally substituted C.sub.1-C.sub.6 alkylcarbonyl radical; or a radical —O—CO—R, —CO—O—R, NR—CO—R′, or —CO—NRR′, wherein R and R′, independently of each other, are chosen from a hydrogen atom or an optionally substituted C.sub.1-C.sub.6 alkyl radical; wherein when Z.sub.2 represents a covalent bond, then R.sub.2 optionally represents: an optionally substituted C.sub.1-C.sub.6 alkylcarbonyl radical; or a radical —O—CO—R, —CO—O—R, NR—CO—R′, or —CO—NRR′, wherein R and R′, independently of each other, are chosen from a hydrogen atom or an optionally substituted C.sub.1-C.sub.6 alkyl radical; R′.sub.3, R′.sub.4, and R′.sub.5, which may be identical or different, are chosen from: a hydrogen atom; a hydroxyl radical; a C.sub.1-C.sub.6 alkoxy radical; a C.sub.1-C.sub.6 alkylthio radical; an amino radical; a monoalkylamino radical; a C.sub.1-C.sub.6 dialkylamino radical, wherein the alkyl radicals may form, with the nitrogen atom to which they are attached, a saturated or unsaturated, aromatic or nonaromatic, 5- to 8-membered heterocycle, which may contain at least one heteroatom or group chosen from N, O, S, SO.sub.2, and CO, wherein the heterocycle is optionally cationic and/or substituted with a cationic radical; an optionally substituted C.sub.1-C.sub.6 alkylcarbonyl radical; a radical —O—CO—R, —CO—O—R, NR—CO—R′, or —CO—NRR′, wherein R and R′ independently of each other, are chosen from a hydrogen atom or an optionally substituted C.sub.1-C.sub.6 alkyl radical; a halogen; a —NHSO.sub.3H radical; an optionally substituted C.sub.1-C.sub.4 alkyl radical; a saturated, unsaturated or aromatic, optionally substituted carbon-based ring; or R′.sub.3, R′.sub.4, and R′.sub.5 optionally form in pairs a partially saturated or unsaturated ring, and X is chosen from an ion or group of ions making it possible to ensure the electronegativity of the derivative of formula (II); wherein least one of the groups R′.sub.1 or R′.sub.2 is chosen from a cationic radical; or A3) diamino-N,N-dihydropyrazolone derivatives according to formula (III) below, addition salts thereof, solvates thereof, or solvates of the salts thereof: ##STR00036## wherein: R″.sub.3 and R″.sub.4, which may be identical or different, are chosen from: a hydrogen atom; a linear or branched C.sub.1-C.sub.6 alkyl radical optionally substituted with at least one radical chosen from a OR″.sub.5 radical, a NR″.sub.6R″.sub.7 radical, a carboxyl radical, a sulfonic radical, a carboxamido CONR″.sub.6R″.sub.7 radical, a sulfonamido radical SO.sub.2NR″.sub.6R″.sub.7, a heteroaryl, an aryl optionally substituted with at least one (C.sub.1-C.sub.4)alkyl, hydroxyl, C.sub.1-C.sub.2 alkoxy, amino, or (di)alkyl(C.sub.1-C.sub.2)amino group; an aryl radical optionally substituted with at least one (C.sub.1-C.sub.4)alkyl, hydroxyl, C.sub.1-C.sub.2 alkoxy, amino, or (di)alkyl(C.sub.1-C.sub.2)amino; a 5- or 6-membered heteroaryl radical, optionally substituted with at least one radical chosen from (C.sub.1-C.sub.4)alkyl or (C.sub.1-C.sub.2)alkoxy; or R″.sub.3 and R″.sub.4 optionally form, together with the nitrogen atom to which they are attached, a 5- or 7-membered heterocycle, the carbon atoms of which is optionally replaced with an optionally substituted oxygen or nitrogen atom; R″.sub.5, R″.sub.6, and R″.sub.7, which may be identical or different, are chosen from: a hydrogen atom; a linear or branched C.sub.1-C.sub.4 alkyl radical optionally substituted with at least one radical chosen from hydroxyl, C.sub.1-C.sub.2 alkoxy, carboxamido CONR″.sub.8R″.sub.9, sulfonyl SO.sub.2R″.sub.8, aryl optionally substituted with a (C.sub.1-C.sub.4)alkyl, hydroxyl, C.sub.1-C.sub.2 alkoxy, amino, or (di)alkyl(C.sub.1-C.sub.2)amino, aryl optionally substituted with a (C.sub.1-C.sub.4)alkyl, hydroxyl, C.sub.1-C.sub.2 alkoxy, amino or (di)alkyl(C.sub.1-C.sub.2)amino; or R″.sub.6 and R″.sub.7, which may be identical or different, are optionally chosen from a carboxamido radical CONR″.sub.8R″.sub.9 or a sulfonyl radical SO.sub.2R″.sub.8; R″.sub.8 and R″.sub.9, which may be identical or different, are chosen from a hydrogen atom, a linear or branched C.sub.1-C.sub.4 alkyl radical optionally substituted with at least one hydroxyl or C.sub.1-C.sub.2 alkoxy; and R″.sub.1 and R″.sub.2 form, together with the nitrogen atom(s) to which they are attached, a saturated or unsaturated 5- to 7-membered heterocycle optionally substituted with at least one radical chosen from halogen atoms and amino, (di)alkyl(C.sub.1-C.sub.4)amino, hydroxyl, carboxyl, carboxamido and (C.sub.1-C.sub.2)alkoxy radicals, C.sub.1-C.sub.4 alkyl radicals optionally substituted with at least one hydroxyl, amino, (di)alkylamino, alkoxy, carboxyl, or sulfonyl radicals.

17. A multi-compartment device for dyeing keratin fibers, comprising: at least one first compartment comprising a dye composition, wherein the dye composition comprises: (A) at least one 2-amino-5-ethylphenol coupler, an addition salt thereof, or a solvate thereof, (B) at least one pyrazole heterocyclic oxidation base chosen from: A1) pyrazolopyridines according to formula (I) below, addition salts thereof, solvates thereof, or solvates of the salts thereof: ##STR00037## wherein: R.sub.1, R.sub.2, R.sub.3, R.sub.4, and R.sub.5, which may be identical or different, are chosen from a hydrogen atom, a halogen atom, a —NHSO.sub.3H radical, a hydroxyl radical, a (C.sub.1-C.sub.4)alkyl radical, a (C.sub.1-C.sub.4)alkoxy radical, a (C.sub.1-C.sub.4)alkylthio radical, mono(C.sub.1-C.sub.4)alkylamino, a di(C.sub.1-C.sub.4)alkylamino radical, wherein the two alkyl groups may form, together with the nitrogen atom to which they are attached, a ring that may be interrupted with at least one nitrogen, oxygen, or sulfur atom, a heterocycle; a nitro radical; a phenyl radical, a carbonyl radical, a (C.sub.1-C.sub.4)alkoxycarbonyl radical, a carboxamido radical, a cyano radical, an amino radical, a sulfonyl radical, a —CO.sub.2H radical, a —SO.sub.3H radical, a —PO.sub.3H.sub.2 radical, a —PO.sub.4H.sub.2 radical, or a group: ##STR00038## wherein R′″ is chosen from an oxygen or nitrogen atom, Q is chosen from an oxygen atom, a NH group, or NH(C.sub.1-C.sub.4)alkyl, and Y is chosen from a hydroxyl, amino, C.sub.1-C.sub.4 alkyl, (C.sub.1-C.sub.4)alkoxy, (C.sub.1-C.sub.4)alkylamino, or di(C.sub.1-C.sub.4)alkylamino radical; A2) pyrazolopyridine oxidation bases according to formula (II) below ##STR00039## wherein: Z.sub.1 and Z.sub.2, independently of each other, are chosen from: a covalent single bond; or a divalent radical chosen from: a —O(CH.sub.2).sub.p— radical, wherein p is chosen from an integer ranging from 0 to 6, or a —NR′.sub.6(CH.sub.2).sub.q(C.sub.6H.sub.4).sub.t— radical, wherein q is chosen from an integer ranging from 0 to 6 and t is chosen from 0 or 1, and R′.sub.6 is chosen from a hydrogen atom or a C.sub.1-C.sub.6 alkyl radical optionally substituted with at least one hydroxyl group; Z.sub.1 may also be chosen from a divalent radical —S—, —SO—, or —SO.sub.2—, wherein R′.sub.1 is a methyl radical; R′.sub.1 and R′.sub.2, independently of each other, are chosen from: a hydrogen atom; a C.sub.1-C.sub.10 alkyl radical, which is optionally substituted and optionally interrupted with a heteroatom or a group chosen from O, N, Si, S, SO, or SO.sub.2; a halogen; a SO.sub.3H radical; a substituted or unsubstituted, saturated, unsaturated, or aromatic, 5- to 8-membered ring, optionally containing at least one heteroatom or group chosen from N, O, S, SO.sub.2, or —CO—, wherein the ring is optionally cationic and/or substituted with a cationic radical; or a —N.sup.+R.sub.19R.sub.18R.sub.19 group, wherein R.sub.17, R.sub.18 and R.sub.19 are linear or branched C.sub.1-C.sub.5 alkyls optionally substituted with at least one hydroxyl group; wherein when Z.sub.1 represents a covalent bond, then R.sub.1 optionally represents: an optionally substituted C.sub.1-C.sub.6 alkylcarbonyl radical; or a radical —O—CO—R, —CO—O—R, NR—CO—R′, or —CO—NRR′, wherein R and R′, independently of each other, are chosen from a hydrogen atom or an optionally substituted C.sub.1-C.sub.6 alkyl radical; wherein when Z.sub.2 represents a covalent bond, then R.sub.2 optionally represents: an optionally substituted C.sub.1-C.sub.6 alkylcarbonyl radical; or a radical —O—CO—R, —CO—O—R, NR—CO—R′, or —CO—NRR′, wherein R and R′, independently of each other, are chosen from a hydrogen atom or an optionally substituted C.sub.1-C.sub.6 alkyl radical; R′.sub.3, R′.sub.4 and R′.sub.5, which may be identical or different, are chosen from: a hydrogen atom; a hydroxyl radical; a C.sub.1-C.sub.6 alkoxy radical; a C.sub.1-C.sub.6 alkylthio radical; an amino radical; a monoalkylamino radical; a C.sub.1-C.sub.6 dialkylamino radical, wherein the alkyl radicals may form, with the nitrogen atom to which they are attached, a saturated or unsaturated, aromatic or nonaromatic, 5- to 8-membered heterocycle, which may contain at least one heteroatom or group chosen from N, O, S, SO.sub.2, and CO, wherein the heterocycle is optionally cationic and/or substituted with a cationic radical; an optionally substituted C.sub.1-C.sub.6 alkylcarbonyl radical; a radical —O—CO—R, —CO—O—R, NR—CO—R′, or —CO—NRR′, wherein R and R′ independently of each other, are chosen from a hydrogen atom or an optionally substituted C.sub.1-C.sub.6 alkyl radical; a halogen; a —NHSO.sub.3H radical; an optionally substituted C.sub.1-C.sub.4 alkyl radical; a saturated, unsaturated or aromatic, optionally substituted carbon-based ring; or R′.sub.3, R′.sub.4, and R′.sub.5 optionally form in pairs a partially saturated or unsaturated ring, and X is chosen from an ion or group of ions making it possible to ensure the electronegativity of the derivative of formula (II); wherein least one of the groups R′.sub.1 or R′.sub.2 is chosen from a cationic radical; or A3) diamino-N,N-dihydropyrazolone derivatives according to formula (III) below, addition salts thereof, solvates thereof, or solvates of the salts thereof: ##STR00040## wherein: R″.sub.3 and R″.sub.4, which may be identical or different, are chosen from: a hydrogen atom; a linear or branched C.sub.1-C.sub.6 alkyl radical optionally substituted with at least one radical chosen from a OR″.sub.5 radical, a NR″.sub.6R″.sub.7 radical, a carboxyl radical, a sulfonic radical, a carboxamido CONR″.sub.6R″.sub.7 radical, a sulfonamido radical SO.sub.2NR″.sub.6R″.sub.7, a heteroaryl, an aryl optionally substituted with at least one (C.sub.1-C.sub.4)alkyl, hydroxyl, C.sub.1-C.sub.2 alkoxy, amino, or (di)alkyl(C.sub.1-C.sub.2)amino groups; an aryl radical optionally substituted with at least one (C.sub.1-C.sub.4)alkyl, hydroxyl, C.sub.1-C.sub.2 alkoxy, amino, or (di)alkyl(C.sub.1-C.sub.2)amino; a 5- or 6-membered heteroaryl radical, optionally substituted with at least one radical chosen from (C.sub.1-C.sub.4)alkyl or (C.sub.1-C.sub.2)alkoxy; or R″.sub.3 and R″.sub.4 optionally form, together with the nitrogen atom to which they are attached, a 5- or 7-membered heterocycle, the carbon atoms of which may be replaced with an optionally substituted oxygen or nitrogen atom; R″.sub.5, R″.sub.6, and R″.sub.7, which may be identical or different, are chosen from: a hydrogen atom; a linear or branched C.sub.1-C.sub.4 alkyl radical optionally substituted with at least one radical chosen from hydroxyl, C.sub.1-C.sub.2 alkoxy, carboxamido CONR″.sub.8R″.sub.9, sulfonyl SO.sub.2R″.sub.8, aryl optionally substituted with a (C.sub.1-C.sub.4)alkyl, hydroxyl, C.sub.1-C.sub.2 alkoxy, amino, or (di)alkyl(C.sub.1-C.sub.2)amino, aryl optionally substituted with a (C.sub.1-C.sub.4)alkyl, hydroxyl, C.sub.1-C.sub.2 alkoxy, amino or (di)alkyl(C.sub.1-C.sub.2)amino; or R″.sub.6 and R″.sub.7, which may be identical or different, are optionally chosen from a carboxamido radical CONR″.sub.8R″.sub.9 or a sulfonyl radical SO.sub.2R″.sub.8; R″.sub.8 and R″.sub.9, which may be identical or different, are chosen from a hydrogen atom, a linear or branched C.sub.1-C.sub.4 alkyl radical optionally substituted with at least one hydroxyl or C.sub.1-C.sub.2 alkoxy; and R″.sub.1 and R″.sub.2 form, together with the nitrogen atom(s) to which they are attached, a saturated or unsaturated 5- to 7-membered heterocycle optionally substituted with at least one radical chosen from halogen atoms and amino, (di)alkyl(C.sub.1-C.sub.4)amino, hydroxyl, carboxyl, carboxamido and (C.sub.1-C.sub.2)alkoxy radicals, C.sub.1-C.sub.4 alkyl radicals optionally substituted with at least one hydroxyl, amino, (di)alkylamino, alkoxy, carboxyl, or sulfonyl radicals.

18. The composition according to claim 1, wherein the at least one 2-amino-5-ethylphenol coupler is present in a total amount ranging from about 0.0001% to about 20% by weight, relative to the total weight of the composition.

19. The composition according to claim 1, wherein the at least one 2-amino-5-ethylphenol coupler is present in a total amount ranging from about 0.005% to about 10% by weight, relative to the total weight of the composition.

20. The composition according to claim 1, wherein the at least one 2-amino-5-ethylphenol coupler is present in a total amount ranging from about 0.01% to about 6% by weight, relative to the total weight of the composition.

Description

EXAMPLES

(1) In the examples that follow, all the amounts are given as percentages by weight relative to the total weight of the composition. Unless otherwise indicated, the amounts are indicated in g % of Active Material (unless otherwise mentioned).

(2) TABLE-US-00001 Dye composition formula A formula B formula C DIETHYLENETRIAMINEPENTAACETICACID, 0.8 0.8 0.8 PENTASODIUM SALT AMMONIUM HYDROXIDE 4.6 4.6 4.6 POWDERED SODIUM METABISULFITE 0.71 0.71 0.71 PURE MONOETHANOLAMINE 1.2 1.2 1.2 (NON-TREATED ANATASE) TITANIUM OXIDE COATED 0.15 0.15 0.15 WITH POLYDIMETHYLSILOXANE (98/2) (CI: 77891) 2,3-DIAMINO-6,7-DIHYDRO-1H,5H-PYRAZOLO[1,2- — 3 × 10.sup.−3 mol — A]PYRAZOL-1-ONE DIMETHANESULFONATE 2-[(3-AMINOPYRAZOLO[1,5-A]PYRIDIN-2- 3 × 10.sup.−3 mol — — YL)OXY]ETHANOL HYDROCHLORIDE 2-AMINO-5-ETHYLPHENOL HCL (A158) 3 × 10.sup.−3 mol 3 × 10.sup.−3 mol 3 × 10.sup.−3 mol 4-(3-AMINOPYRAZOLO[1,5-a]PYRIDIN-2-YL)-1,1- — — 3 × 10.sup.−3 mol DIMETHYLPIPERAZIN-1-IUM CHLORIDE HYDROCHLORIDE GLYCOL DISTEARATE 2 2 2 CETYLSTEARYL ALCOHOL (50/50 C16/C18) 11.5 11.5 11.5 FRAGRANCE 0.75 0.75 0.75 POLY[(DIMETHYLIMINO)-1,3- 3 3 3 PROPANEDIYL(DIMETHYLIMINO)-1,6-HEXANEDIYL DICHLORIDE] DIMETHYLDIALLYL AMMONIUM CHLORIDE/ACRYLIC 1.52 1.52 1.52 ACID COPOLYMER (80/20) CARBOXYVINYL POLYMER SYNTHESIZED IN AN 0.4 0.4 0.4 ETHYL ACETATE/CYCLOHEXANE MIXTURE WATER qs 100 qs 100 qs 100 PROPYLENE GLYCOL 10 10 10 NATURAL LAURIC ACID 3 3 3 OXYETHYLENATED LAURYL ALCOHOL (12OE) 7 7 7 OXYETHYLENATED DECYL ALCOHOL (3 OE) 9 9 9 OXYETHYLENATED OLEOCETYL ALCOHOL (30 OE) 4 4 4 VITAMIN C: ASCORBIC ACID 0.25 0.25 0.25

(3) TABLE-US-00002 Oxidizing composition Ox1 DIETHYLENETRIAMINEPENTAACETIC ACID 0.06 HYDROGEN PEROXIDE 6 DISODIUM TIN HEXAHYDROXIDE 0.04 TETRASODIUM PYROPHOSPHATE•10 H.sub.2O 0.02 WATER Qs 100 g GLYCEROL 0.5 (50% LINEAR 70/30 C13/C15) ALKYL 0.85 ETHER CARBOXYLIC ACID MONOETHANOL- AMIDE (2 OE) CETYLSTEARYL ALCOHOL/OXYETHYLENATED 2.85 CETYLSTEARYL ALCOHOL (30 OE) MIXTURE PHOSPHORIC ACID qs pH = 2.2 ± 0.2

(4) The dye formulas A, B and C are mixed with the oxidizing formula Ox1 according to the ratio 1+1.5.

(5) The mixtures thus obtained are applied to natural hair containing 90% grey hairs. After a leave-on time of 35 minutes, the locks are rinsed with clear water, then washed with a shampoo. Finally, the locks are dried.

(6) After drying, the colouration obtained is evaluated using a Minolta CM2600D spectrocolorimeter (illuminant D65, angle 10°, specular component included) in the CIELab system. In this system, L* represents the lightness: the lower the value of L*, the more powerful the colouration obtained. C* represents the chromaticity and is obtained via the equation: C*=(a*.sup.2+b*.sup.2).sup.1/2

(7) The higher the value of C*, the more chromatic the colouration obtained. The results are reported in the table below.

(8) TABLE-US-00003 composition L* a* b* C* Shade A + Ox1 27.36 9.99 −9.11 13.52 Strong Violet B + Ox1 65.25 2.11 42.96 43.01 Strong Yellow C + Ox1 43.22 −12.34 10.16 15.99 Strong Green

Comparative Example

(9) a) Dye Compositions

(10) The dye compositions A1 and A2 were prepared from the ingredients of which the contents are indicated in the table below in g % of active material (unless otherwise mentioned).

(11) TABLE-US-00004 A1 A2 (invention) (comparative) AMMONIUM HYDROXIDE 4.6 4.6 TITANIUM DIOXIDE 0.15 0.15 PENTASODIUM PENTETATE 0.8 0.8 ETHANOLAMINE 1.2 1.2 LAURIC ACID 3 3 2-AMINO-5-ETHYLPHENOL 3.12 × 10.sup.−3 mol 3.12 × 10.sup.−3 mol HCL 1-HYDROXYETHYL 4,5- 3.12 × 10.sup.−3 mol DIAMINOPYRAZOLE SULFATE 2-[(3-AMINOPYRAZOLO[1,5- 3.12 × 10.sup.−3 mol A]PYRIDIN-2-YL)OXY]ETH- ANOL HYDROCHLORIDE ASCORBIC ACID 0.25 0.25 POLYQUATERNIUM-22 1.5 1.5 PROPYLENE GLYCOL 10 10 GLYCOL DISTEARATE 2 2 DECETH-3 9 9 CETEARYL ALCOHOL 11.5 11.5 HEXADIMETHRINE CHLORIDE 3 3 LAURETH-12 7 7 SILICA DIMETHYL SILYLATE 1.2 1.2 OLETH-30 4 4 SODIUM METABISULFITE 0.7 0.7 CARBOMER 0.4 0.4 WATER qs 100 qs 100

(12) Compositions A1 and A2 are mixed with the oxidizing composition Ox1 in a 1:1.5 weight ratio.

(13) The mixture is thus obtained, A1+Ox1 and A2+Ox1, are applied to locks of natural hair containing 90% grey hairs.

(14) After a leave-on time of 35 minutes, the locks are rinsed with clear water, then washed with a shampoo. Finally, the locks are dried.

(15) The colorimetric measurements are performed using a Minolta CM2006D spectrocolorimeter (illuminant D65, angle 10°, specular component included) in the CIELab system. In this system, L* represents the lightness: the lower the value of L*, the more powerful the colouration obtained.

(16) TABLE-US-00005 L* A1 + Ox1 (invention) 26.4 A2 + Ox1 (comparative) 31.0
The composition according to the invention A1+Ox1 has a lower value of L*, thus a more powerful colouration, compared with comparative composition A2+Ox1.