COMPOSITION FOR COLORING KERATIN FIBERS COMPRISING A PARTICULAR IMIDAZOLE COUPLER AND AN OXIDATION B

专利摘要:
The subject of the invention is a composition comprising: i) at least one imidazole coupler of formula (I), with R1, R2, and R3, as defined in the description; ii) at least one oxidation base preferably of heterocyclic and / or para-phenylenediamine type. The subject of the invention is also a process for dyeing keratin fibers using ingredients i) and ii); a kit comprising ingredients i) and ii); and the use of the ingredient i) associated with ii) to color the keratinous fibers and new couplers. The composition of the invention leads to particularly powerful, chromatic and low selective colorations. In addition, the increase in the color of the keratinous fibers treated with the composition of the invention is very satisfactory.
公开号:FR3020944A1
申请号:FR1454396
申请日:2014-05-16
公开日:2015-11-20
发明作者:Alain Lagrange；Boris Lalleman
申请人:LOreal SA；
IPC主号:

专利说明:

[0001] The invention relates to a composition comprising: i) at least one particular imidazole coupler; ii) at least one oxidation base; a method for staining keratin fibers using ingredients i) and ii) a kit comprising ingredients i) and ii) and the use of ingredient i) associated with ii) for dyeing keratinous fibers. For a long time, many people have been trying to change the color of their hair, and in particular to hide their white hair. It is known to dye keratinous fibers, in particular human keratinous fibers such as the hair to obtain so-called permanent dyes with dyeing compositions containing oxidation dye precursors, generally called oxidation bases such as orthoacids. or para-phenylenediamines, ortho- or para-aminophenols or heterocyclic compounds such as pyrazoles, pyrazolinones or pyrazolopyridines. These oxidation bases are colorless or weakly colored compounds which, when combined with oxidizing products, can give rise to colored compounds by a process of oxidative condensation. It is also known that the shades obtained with these oxidation bases can be varied by combining them with couplers or color modifiers, the latter being chosen in particular from aromatic meta-diamines, meta-aminophenols, meta-diphenols and certain heterocyclic compounds such as indole or pyridine compounds. The variety of molecules involved in the oxidation bases and couplers, allows to obtain a rich palette of 25 colors. The oxidation dyeing process therefore consists in applying to the keratin fibers a dye composition comprising oxidation bases or a mixture of oxidation bases and couplers with hydrogen peroxide as an oxidizing agent, let it diffuse, then rinse the fibers. However, the implementation of these dye compositions may have a number of disadvantages. Indeed, after application to the keratinous fibers, the obtained dye power may not be entirely satisfactory, or even low, and lead to a restricted range of colors. The colorations may also not be sufficiently stubborn against external agents such as light, shampoos, perspiration and also be too selective, that is to say that the color difference is too important along the same keratin fiber which is differently sensitized between its tip and its root. The imidazole compounds are known in the field of photography (see for example EP 0 321 190, US 5,834,164). One of the objects of the present invention is in particular to provide compositions for dyeing keratinous fibers, in particular human keratinous fibers such as the hair, which are in particular capable of leading to a wide color field with powerful colorations, little selective and tough against external agents (such as shampoos, light, perspiration or intemperleb). This object is achieved by the present invention which has for object a dyeing composition for keratinous fibers, in particular human keratinous fibers such as the hair, comprising: i) at least one imidazole coupler of formula (I): NINH (I ) as well as its acid or base salts, organic or inorganic, its optical isomers, geometric, its tautomers or its solvates such as hydrates, compound of formula (I) wherein: DR1 represents a) hydrogen atom (b) halogen; (c) (C1-C4) alkoxy or (d) phenoxy; R 2 and R 3, which are identical or different, represent: a) an aryl group, preferably C 6 -C 10, which is: optionally substituted with at least one atom or group chosen from: i) halogen, ii) hydroxy, iii) (C1 -C6) alkyl, iv) (C1-C4) alkoxy optionally substituted with hydroxy, carboxy or amino, v) (C1-C4) alkylthio, vi) trihalo (C1-C4) alkyl such as trifluoromethyl, vii) carboxy, viii) -C (O) O-M + with N14. representing a cationic counterion of a mineral or organic base, ix) -S (O) 2 -R with R representing a hydroxy, (C 1 -C 4) alkyl, or (di) (C 1 -C 4) (alkyl) amino group (x) (di) (Ci-C4) (alkyl) amino, xi) (C1-C4) alkylcarbonylamino such as methylcarbonylamino, xii) cyano, xiii) nitro, xiv) glucosyloxy and / or optionally fused to a monocyclic heterocycle, preferably comprising from 5 to 7 members and from 1 to 3 heteroatoms chosen from oxygen, sulfur and nitrogen, optionally substituted with at least one i) carbonyl group, ii) (di) (C1-C4) alkyl group amino, iii) acetamido, iv) -S (O) 2- R with R representing hydroxy, (C1-C4) alkyl, or (di) (Cr C4) (alkyl) amino, y) RS (0) 2 -N (R ') - with R as defined above and R' representing a hydrogen atom or a (C1-C4) alkyl group; preferably morpholinyl, piperidinyl, piperazinyl, or pyrrolydinyl, b) a 5- or 6-membered heterocycle group, comprising from 1 to 4 heteroatoms, chosen from oxygen, sulfur and nitrogen, said heterocycle being connected to the imidazole part of the compound (I) by a carbon atom and said heterocycle being optionally fused to a benzo group, and / or optionally substituted by a second 5- or 6-membered heterocyclic ring, or by a phenyl group optionally substituted by a trihalogeno group (C1- C4) alkyl such as trifluoromethyl or (C1-C4) alkoxy such as methoxy c) a linear, branched or cyclic (C1-C6) alkyl group, optionally substituted by at least one atom or group selected from i) halogeno, ii ) hydroxy, iii) cyano, iv) (di) (C1-C4) (alkypamino, y) (di) (C1-C4) (alkyl) amino (C1-C4) thio, (C1-C4) alkylphenyl, vi) (C1-C4) alkoxy, vii) (C1-C4) alkylthio, viii) morpholinyl or morpholino, ix) phenyl, x) piperazinyl or piperazino , xi) piperidinyl or piperidino, xii) thiophenyl, xiii) carboxy, ix) -C (O) O -M + with M + as defined above, x) amido H2N-C (O) -, xi) pyrimidinyl, xii) tetrahydrofuranyl (xiii) nitrophenyl; d) an aminocarbonyl group R4R5N-C (O) - with R4 and R5, which may be identical or different, represent a hydrogen atom, a (C1-C6) alkyl, phenyl or cycloalkyl group comprising from 5 to 7 chain members, such as cyclohexyl, or else R4 and R5 together with the nitrogen atom carrying them a heterocycloalkyl group comprising from 5 to 7 chain members, preferably 6 chain members, and optionally further comprising one or more additional heteroatoms, preferably heterocycloalkyl is selected from morpholino, piperazino and piperidino; or R2 represents a (hetero) aryl group comprising from 5 to 10 members and from 1 to 3 heteroatoms selected from O, S, N, optionally substituted by one or more halogen atoms or groups selected from hydroxy, nitro, cyano, ( C1-C4) alkyl, (C1-C4) alkoxy, (C1-C4) alkylthio, (poly) halo (C1-C4) alkyl such as trifluoromethyl, (di) (C1-C4) (alkyl) amino, imidazolyl, thiophenyl , methylenedioxy, ethylenedioxy, ROC (O) -, RmR-NC (O) -, R '"- C (O) -N (R") -, and R - S (O) p-, RRNS (O) with R '"and R- representing a hydrogen atom or a (C1-C4) alkyl group and p is 1 or where R3 represents a heteroaryl group comprising from 5 to 10 members, and from 1 to 3 heteroatoms chosen from O, S, N, optionally substituted with one or more atoms or groups selected from: i) halogen, ii) (C1-C4) alkyl, iii) (C1-C4) alkoxy, iv) carboxy, v) cyano, vi) (poly) halo (C1-C4) alkyl such as trifluoromethyl, vii) heterocycloalkyl having from 5 to 7 members and 1 with 3 atoms of nitrogen or oxygen such as piperidinyl, hexahydrodiazepinyl, viii) heteroaryl 'comprising from 5 to 6 members and from one to three atoms of oxygen, sulfur or nitrogen such as imidazolyl, furanyl, or ( C1-C4) alkoxyphenyl; ii) at least one oxidation base; it being understood that when I) the imidazole coupler of formula (I) represents 2,4-diphenylimidazole, then ii) the oxidation base is different from 1-dimethylamino-4-aniline. The invention also relates to a dyeing process using this composition. Another subject of the invention is the use of the compounds of formula (1) for the oxidation dyeing of keratinous fibers, in particular human keratinous fibers such as the hair. Finally, the invention also relates to novel imidazole compounds of formula (IA) and (IB) as defined below. The composition of the invention leads to particularly powerful, chromatic and low selective colorations. In addition, the increase in the color of the keratinous fibers treated with the composition of the invention is very satisfactory. The composition also makes it possible to obtain dyeing compositions leading to colorations that are well resistant to the various attacks that the hair can undergo, such as light, bad weather, washing, perspiration. The oxidation dyeing compositions according to the invention also make it possible to achieve shades in a very wide range of colors. By "rise" of the color of the keratin fibers, the meaning of the present invention is understood to mean the variation of coloring between strands of white hair without olorées and strands of colored hair.
[0002] Other objects, features, aspects and advantages of the present invention will become more apparent upon reading the description and examples which follow. In what follows, and unless otherwise indicated, the boundaries of a domain of values are within this range. The expression "at least one" is equivalent to the expression "one or more". a "hydrocarbon chain" is "unsaturated" when it comprises one or more double bonds and / or one or more triple bonds; by "optionally substituted" after the terms "aryl" or heteroaryl "it implies that the aryl or heteroaryl portion may be substituted by at least one substituent borne by a carbon atom, chosen from: a C1-C8 alkyl radical, preferably C1-C6, optionally substituted by one or more radicals chosen from hydroxyl, C1-C2 alkoxy, (poly) -hydroxyalkoxy C2-C4, acylamino, amino substituted by two identical or different alkyl radicals, in C1-C4, optionally carrying at least one hydroxyl group or, the two radicals being able to form, with the nitrogen atom to which they are attached, a heterocycle comprising from 5 to 7 members, preferably from 5 to 6 members, saturated or unsaturated optionally substituted optionally comprising another heteroate identical or different from nitrogen; a halogen atom such as chlorine, fluorine or bromine; a hydroxy group; a C1-C2 alkoxy radical; a C2-C4 (poly) -hydroxyalkoxy radical; an amino radical; - nitro, nitroso or cyano; a 5- or 6-membered heterocycloalkyl radical; a 5- or 6-membered optionally cationic heteroaryl radical, preferably imidazolyl, and optionally substituted by a (C1-C4) alkyl radical, preferably methyl; an amino radical substituted with one or two identical or different C 1 -C 6 alkyl radicals optionally carrying at least: i) a hydroxyl group; ii) an amino group optionally substituted with one or two C 1 -C 3 alkyl radicals optionally substituted, said alkyl radicals being able to form, with the nitrogen atom to which they are attached, an optionally substituted 5 to 7-membered heterocyclic ring, saturated or unsaturated, optionally comprising at least one other heteroatom different from or different from nitrogen; an acylamino radical (-N (R) -C (O) R ') in which the radical R is a hydrogen atom, a C 1 -C 4 alkyl radical optionally bearing at least one hydroxyl group and the R' radical; is a C 1 -C 2 alkyl radical; a carbamoyl radical ((R) 2 N-C (O) -) in which the radicals R, which may be identical or different, represent a hydrogen atom, a C 1 -C 4 alkyl radical which may optionally carry at least one hydroxyl group; a carboxylic acid or ester radical, (-O-C (O) R 1 or (-C (O) OR '), in which the radical R' is a hydrogen atom or a C 1 -C 4 alkyl radical which may carry at least one hydroxyl group and the radical R 'is a C1-C2 alkyl radical; the carboxylic radical which may be in acid or salified form (preferably with an alkali metal or an ammonium, substituted or unsubstituted); an alkylsulphonylamino radical (R'S (O) 2 -N (R) -) in which the radical R represents a hydrogen atom, a C 1 -C 4 alkyl radical optionally carrying at least one hydroxyl group and the radical R 'represents a C 1 -C 4 alkyl radical, a phenyl radical; an aminosulphonyl radical ((R) 2 N -S (O) 2 -) in which the radicals R, which may be identical or different, represent a hydrogen atom, an alkyl radical, C1-C4 optionally carrying at least one hydroxyl group, a cyano (CN) group, a (poly) haloalkyl group, preferentially trifluoromethyl (CF3); Substituted substituting "cyclic" or "heterocyclic" for a non-aromatic radical may be substituted by at least one substituent carried by a carbon atom selected from: - hydroxy, - C 1 -C 4 alkoxy, ( Poly) hydroxyalkoxy C2-C4 alkylcarbonylamino ((RC (O) -NR'-) in which the radical R 'is a hydrogen atom, a C1-C4 alkyl radical optionally carrying at least one hydroxyl group and the radical R is a C 1 -C 2 alkyl radical, amino substituted with two identical or different C 1 -C 4 alkyl groups optionally carrying at least one hydroxyl group, said alkyl radicals being able to form with the nitrogen atom to which they are attached, a 5- to 7-membered optionally substituted saturated or unsaturated heterocycle optionally comprising at least one other non-nitrogen heteroatom; -alkylcarbonyloxy ((RC (O) -O-) in which the radical R is a C 1 -C 4 alkyl radical, amino substituted with two identical or different C 1 -C 4 alkyl groups optionally bearing at least one hydroxyl group, alkyl radicals which can form, with the nitrogen atom to which they are attached, an optionally substituted 5 to 7-membered saturated or unsaturated heterocycle optionally comprising at least one other heteroatom which is different from or different from nitrogen; -alkoxycarbonyl ((RO -C (O) -) in which the radical R is a C1-C4 alkyl radical, amino substituted with two identical or different C1-C4 alkyl groups optionally bearing at least one hydroxyl group, said alkyl radicals being able to form with 1 nitrogen atom to which they are attached, an optionally substituted 5 to 7-membered heterocyclic ring, saturated or unsaturated, optionally comprising at least one other heteroatom different from or not nitrogen; heterocyclic, or a non-aromatic portion of an aryl or heteroaryl radical, may also be substituted with one or more groups 0x0; an "aryl" radical represents a mono- or polycyclic group, hydrocarbon-based, condensed or not, comprising from 6 to 22 carbon atoms, and of which at least one ring is aromatic; particularly the aryl radical is phenyl, biphenyl, naphthyl, indenyl, anthracenyl, or tetrahydronaphthyl and more preferably phenyl or tetrahydronaphthyl; a "heteroaryl" radical represents a mono or polycyclic group, condensed or not, comprising from 5 to 22 members, from 1 to 6 heteroatoms chosen from nitrogen, oxygen, sulfur and selenium, and at least one cycle is aromatic; preferably heteroaryl is selected from acridinyl, benzimidazolyl, benzobistriazolylebenzopyrazolyle, benzopyridazinyle, benzoquinolyl, benzothiazolyl, benzotriazolylebenzoxazolyle, pyridinyl, tetrazolyl, dihydrothiazolyl, imidazopyridinyl, imidazolyl, indolyl, isoquinolyl, naphthoimidazolyle, naphthooxazolyle, naphthopyrazolyle, oxadiazolyl, oxazolyl, oxazolopyridyl, phenazinyl, phénooxazolyle pyrazinyl, pyrazolyl, pyrilyl, pyrazoyltriazyl, pyridyl, pyridinoimidazolyl, pyrrolyl, quinolyl, tetrazolyl, thiadiazolyl, thiazolyl, thiazolopyridinyl, thiazoylimidazolyl, thiopyrylyl, triazolyl, xanthyl and its ammonium salt; a "cyclic" radical is a "cycloalkyl" radical i.e. a non-aromatic, mono- or polycyclic hydrocarbon-based, condensed or not, containing from 5 to 22 carbon atoms, which may comprise from one to more unsaturations such as cyclohexyl or cyclopentyl; a "heterocyclic" radical is a non-aromatic mono or polycyclic radical, condensed or not, containing from 5 to 22 members, comprising from 1 to 6 heteroatoms chosen from nitrogen, oxygen, sulfur and morpholinyl selenium , thiomoropholinye, piperidinyl, piperazinyl, pyrrolidinyl, tetrahydrofuranyl, tetrahydrothophenyl, azepanyl, thioazepanyl preferentially morpholino; an "alkyl" radical is a linear or branched C1-C8 hydrocarbon radical, preferably C1-C6; especially C1-C4 such as methyl or ethyl; an "alkenyl" radical is a C2-C8 hydrocarbon radical, linear or branched, comprising one or more double bonds, conjugated or otherwise, in particular C4-C8, comprising a two or three double bonds, preferably a single double bond; the expression "optionally substituted" assigned to the alkyl radical implies that said alkyl radical may be substituted with one or more radicals chosen from i) hydroxyl, ii) C 1 -C 4 alkoxy, iii) acylamino, iv) amino optionally substituted by one or two identical or different C 1 -C 4 alkyl radicals, said alkyl radicals being capable of forming, with the nitrogen atom which carries them, a 5- to 7-membered heterocycle, optionally comprising another heteroatom different from or different from nitrogen, v) phenyl, vi) (C1-C8) alkoxycarbonyl, vii) (C1-C8) alkylcarbonyloxy, viii) HC (O) -O-; an "alkoxy" radical is an alkyloxy or alkyloxy radical for which the alkyl radical is a linear or branched C 1 -C 16, preferably C 1 -C 8, hydrocarbon radical; especially when C1-C4 such as methoxy or ethoxy, and when the alkoxy group is optionally substituted, it implies that the alkyl group is optionally substituted as defined above; a "(poly) haloalkyl" radical is an "alkyl" radical as defined above in which one or more hydrogen atoms are substituted or replaced by one or more halogen atoms such as the fluorine, chlorine or bromine, as polyhaloalkyl there may be mentioned trifluoromethyl group; an "alkylthio" radical is an alkyl-S- radical for which the alkyl radical is a hydrocarbon radical, linear or branched, C1-C8 preferentially C1-C6; especially when C1-C4 such as methylthio or ethylthio, and when the alkylthio group is optionally substituted, it implies that the alkyl group is optionally substituted as defined above; an anionic counterion is organic or mineral preferentially selected from halide anions such as Cl-, Br, r, and organic anions such as mesylates. In addition, unless otherwise indicated, the bounds defining the range of a range of values lie within this range of values. In a general manner, the term "compound addition salts" means the addition salts of these compounds with an acid, such as hydrochlorides, hydrobromides, sulphates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, dodecylbenzenesulfonates, phosphates and acetates, preferably hydrochlorides, citrates, succinates, tartrates, phosphates, lactates, or with a base such as ammonium salts, amine salts , sodium or potassium salts. The solvates of compounds more particularly represent the hydrates of such compounds and / or the combination of such compounds with a linear or branched C1-C4 alcohol such as methanol, ethanol, isopropanol or n-propanol. Preferably, the solvates are hydrates. The composition of the present invention is particularly useful for the oxidation dyeing of keratinous fibers, in particular of human keratinous fibers. i) the imidazole coupler (s) of formula (I), (IA) and (IB) The composition of the invention comprises one or more couplers of formula (I) as defined above. According to a particular embodiment, the coupler (s) of the invention are such that in formula (I), R 1 represents a hydrogen atom, or a halogen atom, preferably hydrogen. According to a particular embodiment, the coupler (s) of the invention are such that in formula (I), R2 represents a group chosen from a), c) d) and e): a) (C1-C6) alkyl, i) optionally substituted with one or more atoms or groups chosen from halogen, hydroxy, amino, carboxy, -C (O) -NH 2, heterocycloalkyl comprising from 5 to 7 members and from 1 to 3 heteroatoms chosen from 0, S and N such morpholino, piperazino, piperidino, pyrimidinyl, thiophenyl, and phenyl optionally substituted by a halogen atom, or (C1-C4) alkyl, (C1-C4) alkoxy, or nitro; and / or ii) optionally interrupted by an oxygen or sulfur atom; b) Ra-N (Rb) -C (O) - with Ra representing a (C1-C6) alkyl, phenyl, (C4-C7) cycloalkyl group such as cyclohexyl, and Rb represents a hydrogen atom or a group ( C1-C4) alkyl, or else Ra and Rb form together with the nitrogen atom which carry them a heterocycloalkyl group comprising from 5 to 7 members and from 1 to 3 heteroatoms chosen from 0, S and N such as morpholino, piperazino or piperidino; c) (hetero) aryl comprising from 5 to 10 members and from 1 to 3 heteroatoms selected from O, S, N, such as phenyl, naphthyl, furanyl, (benzo) thiophenyl, imidazolyl, tetrazolyl, pyridinyl, benzomorpholinyl or pyrimidyl, optionally substituted by one or more halogen atoms or groups selected from hydroxy, nitro, cyano, (C1-C4) alkyl, (C1-C4) alkoxy, (C1-C4) alkylthio, (poly) halo (C1-C4) alkyl such as trifluoromethyl, (di) (C 1 -C 4) (alkyl) amino, imidazolyl, thiophenyl, methylenedioxy, ethylenedioxy, R "-C (O) -, R '" O-C (O) -, R "" R " NC (O) -, R '"- C (O) - N (R") -, and R - S (O) p-, R "R" NS (O) p- with R "and R" represent a hydrogen atom or a (C1-C4) alkyl group and p is 1 or 2; e) heterocycloalkyl such as tetrahydrofuranyl, pyrrolidinyl, piperidinyl piperazino, or morpholino. According to an advantageous variant, R2 represents an aryl group such as phenyl or naphthyl optionally substituted with one or more halogen atoms or groups as defined above in c), preferably R2 represents a phenyl group.
[0003] According to another advantageous variant, R2 represents a heteroaryl group such as furanyl, (benzo) thiophenyl, benzomorpholinyl, benzodioxole, imidazolyl, imidazolylimidazolyl, tetrazolyl, thiazolyl, pyridinyl, pyrimidyl or indolyl; preferably R2 represents a pyridinyl group. According to yet another variant R2 represents a cycloalkyl group such as cyclohexyl. According to a particular embodiment, the coupler (s) of the invention are such that in formula (I), R 3 represents a group (a) (C 1 -C 6) alkyl optionally substituted by a cyano group; b) (C6-C10) aryl, such as phenyl or naphthyl, optionally substituted with one or more atoms or groups selected from: i) halogen, ii) hydroxy, iii) nitro, iv) (C1-C4) alkyl, v) (C1-C4) alkoxy, vi) (C4-C6) cyclohexyloxy, vii) (poly) hydroxy (C1-C4) alkoxy, viii) (di) (C1-C4) (alkyl) amino (C1-C4) alkoxy, ix) (C3-C7) cycloalkyloxy, x) methylene-dioxy, x1) ethylenedioxy, xii) glucosyloxy, xiii) diazepanyl, xiv) benzyloxy, x- R- S (O) 2 -N (R ') -, R representing a (C1-C6) alkyl group, and R 'representing a hydrogen atom or a (C1-C4) alkyl, xvi) (C1-C4) alkylthio, xvii) (poly) halogeno- (C1- C4) alkyl such as trifluoromethyl, xviii) (poly) halo (C1-C4) alkoxy such as trifluoromethoxy, xix) (di) (C1-C4) (alkyl) amino, xx) R "-C (O) -, xxi x) R "OC (0) -, xxi) R" -C (O) -N (R '") - with R" and R "representing an atom hydrogen, or a (C1-C4) alkyl group; C) heteroaryl comprising from 5 to 10 members, and from 1 to 3 heteroatoms selected from O, S, N, optionally substituted with one or more atoms or groups selected from: i) halogen, ii) (C1-C4) alkyl, iii) (C1-C4) alkoxy, iv) carboxy, v) cyano, vi) (poly) halo (C1-C4) alkyl such as trifluoromethyl, vii) heterocycloalkyl containing 5 to 7 members and 1 to 3 atoms nitrogen or oxygen such as piperidinyl, hexahydrodiazepinyl, viii) heteroaryl 'comprising from 5 to 6 members and from one to three atoms of oxygen, sulfur or nitrogen such as imidazolyl, furanyl, or (C1-C4) alkoxyphenyl. According to a particular embodiment of the invention, the coupler (s) are such that in formula (I), R3 represents a (a) (C1-C6) alkyl group optionally substituted by a cyano group. According to another particular embodiment of the invention, the coupler (s) are such that, in the formula (I), R 3 represents a group b) aryl optionally substituted with the atoms or groups i) to xxiv) as previously defined preferentially phenyl or naphthyl, more particularly phenyl.
[0004] According to another particular embodiment of the invention, the coupler (s) are such that in formula (I), R3 represents a group c), preferably heteroaryl c) is chosen from furanyl, thiophenyl, imidazolyl, pyrrolyl and indolyl, pyridinyl, (iso) quinoliny (e, (iso) thiazolyl, chromanyl, said heterocycle being optionally substituted by at least one atom or group selected from i) to viii) as defined above. Among the compounds of formula (I), there may be mentioned, by way of example, those for which: R 2 Phenyl Phenyl H Phenyl 4-methoxy-1-phenyl H Phenyl 4-methyl-1-phenyl H Phenyl 2-pyridyl H Phenyl 4-nitro-1-phenyl H 4-nitro-1-phenyl phenyl H 4-methoxy-1-3-pyridyl-6-methyl-phenyl 1-pyridyl HI 1.VC - / H Phenyl = ry R 1 R 1 H / H / N 'i, r NHH Phenyl NIH Phenyl H Phenyl FH Phenyl Phenyl H / Phenyl N Phenyl OH% H Phenyl H '/ I Phenyl HFF Phenyl HHF Phenyl H Phenyl H > HHO Phenyl / H Phenyl HH H Phenyl 1 Uucose H / H Phenyl H Phenyl FH 4-methoxy-1-4-methoxy-1-phenyl H - ## STR2 ## ## STR2 ## Phenyl H-Phenyl 11 --- z-, ## STR2 ## , Phenyl HH Phenyl H Phenyl H Phenyl H, 1: ii H Phenyl 0 H Phenyl H n Phenyl H k 0 ^ 1 H, - H H - 0 Phenyl Phenyl H Phenyl H Phenyl Phenyl H Phenyl H Phenyl H 0- H Phenyl a / - -. Phenyl Phenyl of phenyl Phenyl Phenyl HHH Phenyl H F H Phenyl HI 1H-H, -.-C.- C. N - Phenyl / H -F Phenyl HH,> -, 1 Phenyl, H. Phenyl, 1H, phenyl, phenyl, phenyl, phenyl HH, phenyl H, phenyl Phenyl H - Phenyl H - Phenyl H - Phenyl Phenyl Phenyl Cl - Phenyl Cl. , Phenyl CI Phenyl Br Phenyl - 1 Cl OH, R OH Cl R III Methyl Phenyl H Phenyl H Methyl-C H -CH 2 -HH Phenyl -CH 2 -CNH -CH 2 -OH - ° H - CH 2 -OH Phenyl Methyl: -CH 2 -CH 2 -NH 2 O 4, CH 2 CH 2 -CH 2 -OH 0, Ethyl CH 2 -CH 2 -OH CH 2 CH 2 -OH / H-CH 2 -OH Methyl HH-CH 2 -OH, H -CH 2 -CH 2 -CH 2 H -CH 2 -H 2 -CH 2 -OH R2 Rs Ethyl Phenyl Methyl 0-1-CH2-CH2-OH Phenyl H -CH2-OHH-CH2-OH Phenyl-CH2-CN H -CH2-OH -CH2- ## STR2 ## / H isopropyl H Methyl H Cyclohexyl Phenyl H -CH2-OH-H, Methyl terbu Methyl or H-CH 2 -O-OH-OH-CH 2 -CH 2 -NH 2 H isopropyl. , F-k,>. ## STR2 ## ## STR2 ## ## STR2 ## H -CH2-OHH Methyl N1-1H Ethyl H -CH2-CH2-Phenyl CH2-NH2 H -CH2-CH2-COOH Phenyl-CH2-CH2-Phenyl C (O) -NH2 1-1 propyl Phenyl H Phenyl H Methyl H, i. Phenyl H -CH 2 -OH (e) H -CH 2 -CH 2 -NH 2 H-methyl-F-n-propyl H -CH 2 -CH 2 -H 2 H -CH 2 -OH in .... Phenyl H Methyl, N H -CH 2 -CH 2 -OH titanium. H -CH 2 -OH methyl HCl. H -CH 2 -OH propyl --- F H Methyl Ni. Phenyl H -CH 2 -CH 2 -OH H -CH 2 -COOH Methyl H 2 -CH 2 -OH Phenyl H, phenyl H-12-OH, Methyl H Methyl H- Phenyl-phenyl H -CH 2 -CH 2 -OH H isopropyl Phenyl H Phenyl H Phenyl H / Phenyl H -CH 2 -OH H -CH 2 -OH Methyl HH .: ----, ----- '; ## STR2 ## Phenyl H Methyl NH H Phenyl H. ## STR2 ## wherein R 2 is phenyl, phenyl, phenyl, phenyl, phenyl, phenyl, phenyl and phenyl; ## STR2 ## wherein phenyl is phenylated, phenylated, phenylated, phenylated, phenylated, phenylated, phenylated, phenylated, phenylated, phenylated, phenylated, phenylated, and phenylated. e,, o H F. Phenyl, phenyl, phenyl, phenyl. ## STR2 ## wherein R 1 is phenyl; with which corresponds to the point of attachment of the group to the rest of the imidazole of formula (I); as well as their optical isomers, their tautomers, and their addition salts with an acid or a base; the following invention: - ..-.._._..._....__ _ ._. 4- (5-Phenyl-1H-2- (5-phenyl-1H-imidazol-2- (2-phenyl-3H-imidazol-4-yl) -imidazol-2-yl) -pyridine-2-yl) - phenol thiazole NNNN 0 2,5-Di-furan-2-yl-1H-2,5-bis (5-methyl-furan-2- (5-methyl-furan-2-yl) -2- (5-Nitro-furan-2-yl) -1H-imidazole imidazole-1H-1H-imidazole-N-N-Dimethyl- {5- [5- (5- (5-methyl-furan-2- 2- (2- (3,5-Dimethyl-1H-pyrrol-2-methyl-furan-2-yl) -1H-thiophen-2-yl-1H-yl) -5- (5-methyl-furan) -2-yl) -1H-imidazol-2-yl] -furan-2-imidazole imidazole-amine, "-ethyl-2- (diethyl) -5- 5-Methyl-furan-2-yl) -5- [5- (5-phenyl-1H-imidazol-2-yl) -furan-2-yl] -methanol-furan-2-yl) -1H-imidazol phenyl-1H-imidazol-2-yl-furan-2-yl} -amine-N, N-diethyl-5- (5-phenyl-1H-imidazol-2-yl) -furan-2-yl According to a particular embodiment, the coupler (s) of formula (I) are such that R 2 and R 3, which are identical or different, represent a heteroaryl group, and R 1 a hydrogen atom, and preferentially chosen among those of formula (IA): ## STR2 ## as well as its acid or base salts, organic or inorganic, its optical isomers, geometric, its tautomers or its solvates such as hydrates, compound of formula (IA) in which: Y1 and Y2, which are identical or different, represent a nitrogen atom or a group OR 'with R' representing a hydrogen atom or a (C1-C4) alkyl group; X 1 represents an oxygen, sulfur or NR 'atom with R' as defined above, preferably R 'represents a hydrogen atom, - X 2 represents an oxygen atom, or NR' with R 'such that defined above, preferably R 'represents a hydrogen atom; - Ri, represents a hydrogen atom or a group selected from (C1-C4) alkyl, NO2 and amino NRi-Ri "with R1- and R1", identical or different, represent a (C1-C4) alkyl group; R2a represents a hydrogen atom or a group chosen from (C1-C4) alkyl, and amino NR2-R2 "with R2" and R2-, which are identical or different, represent a (C1-C4) alkyl group or together form with the nitrogen atom carrying them a heterocycloalkyl group comprising from 5 to 7, preferably 5-membered, and optionally from 1 to 3 additional heteroatoms selected from 0, S, and N such as pyrrolidino, morpholino, piperazino, piperidino; .
[0005] Preferably, the couplers of formula (I) or (IA) are chosen from the following couplers: ## STR1 ## ## STR1 ## R1a = R2a = methyl GHIF: with R1a = R2a = ethyl According to another particular embodiment, the coupler (s) of formula (I) are such that R2 represents a heteroaryl group, R3 represents a phenyl group and R1 represents a hydrogen atom. and preferably chosen from those of formula (IB): R2b as well as its acid or base salts, organic or mineral, its optical isomers, geometric, its tautomers or its solvates such as hydrates, compound of formula (IB) in which: X1 represents an oxygen, sulfur or NR 'atom with R' as defined above, preferably R 'represents a hydrogen atom, - Y1 represents a nitrogen atom or a group OR' with R 'representing a hydrogen atom or a group selected from (C1-C4) alkyl,; Rib represents a hydrogen atom or a group chosen from (C1-C4) alkyl, hydroxy (C1-C4) alkyl, cyano, 503M, and amino NR-R "with R1" and R1-, identical or different, represent a (C1-C4) alkyl group, with M representing a hydrogen atom, a cationic counterion such as ammonium, or alkali or alkaline earth metal such as Na, or K; - R2b represents a (C1-C4) alkyl group, preferably the couplers of formula (I) or (IB) are chosen from the following couplers: i, EN, te, / NH 0 S-- / N / - HN o NHN di / 0 N lei Na JKLM - N, R1 0 NH / 0 NI l 0 NI N1 --- / 0 R / 0 OH / P / NN 2 NN i NHN with Rib = R2b = PQR methyl with R113 = R2b = ethyl A number of compounds of formula (I) are commercial products or can be obtained according to synthetic methods known in the field of heterocycle synthesis, see for example US 5,834,164 and EP 0 321 190, J. Org.
[0006] Chem. 72, 4551-4553 (2007) or Ullmann's Encyclopedia of Industrial Chemistry, imidazole and derivative ", K. Ebel, H. Koehler, AO Gamer, R. Jackh, published online 15/06/2000, VViley-VCH Verlag GmbH & Co. KGaA, VVeinheim D01: 10, 1002/14356007, a13_661.
[0007] Couplers (IA) and (IB) are new and can be synthesized by conventional methods known to those skilled in the art. For example, there may be mentioned a synthetic route using an alpha (tio) ketone activated by a nucleofug GP leaving group, optionally in a basic medium: X NH 3 H NR - HGP R 1 - H2X (I) With GP representing a leaving group or nucleofuge such as halogen, in particular bromine, X representing an oxygen or sulfur atom, R1, R2 and R3 are as defined above. Preferably, R 1 represents a hydrogen atom, and R 2 and R 3 represent a (hetero) aryl group, as indicated in the synthesis scheme below: ## STR2 ## Argin NH 2 Ar 2 -H 2 Ar 2 -H 2 Ar 2 -H 2 (IA) or (IB) With Ari represents a (hetero) aryl group preferably chosen from: phenyl and Ar2 representing a heteroaryl group preferably chosen from xi Rib and R2b in which X, X1, Y1, Y2, R2a, Ri b and R2b are as defined previously preferably X represents an oxygen atom. It is also possible to mention a synthetic route using (thio) glyoxal, preferably glyoxal, in the presence of (thio) aldehyde and NH3 or of a source of NH3 such as ammonium carboxylic acetate (Radziszewski type reaction): NH3 or source of NH 3 x such that RC (O) O, NH 4 + (R 3 X With X, identical or different, representing an oxygen or sulfur atom, R 1, R 2 and R 3 are as defined above and R represents a group ( C1-C6) alkyl such as methyl The reaction is preferably carried out in a polar protic solvent such as those chosen from alcohols such as ethanol or methanol, in particular methanol, and preferably R1 represents a hydrogen atom, R2 and R3 represent a (hetero) aryl group as specified in the synthesis scheme below: Ari X (IA) or (IB) With Ari and Ar2, X and R as defined above, the reaction is preferably carried out with ammonium acetate representing a methyl group e, in a polar protic solvent such as methanol. This last synthesis scheme is inspired by that described in J. Org. Chem. In the composition of the present invention, the coupler (s) of formula (I), (IA) and (IB) as defined above, are generally present in an amount ranging from 0.001 to 20. about% by weight of the total weight of the dye composition, preferably from 0.005 to 6%. ii) the oxidation base (s): X X Ar 2 H R-C (O) O, NH 4 + + Ar 2 The composition of the invention comprises one or more oxidation bases ii). In particular, the oxidation bases are chosen from para-phenylenediamines, bis-phenylalkylenediamines, para-aminophenols, ortho-aminophenols, heterocyclic bases and their addition salts. Preferably, the oxidation base (s) of the invention are chosen from para-phenylenediamines and heterocyclic bases. Among the para-phenylenediamines, there may be mentioned, for example, para-phenylenediamine, paratoluylenediamine, 2-chloro-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-diethyl paraphenylenediamine, 2,5-dimethyl-para-phenylenediamine, N, N-dimethyl-para-phenylenediamine, N, N-diethyl-para-phenylenediamine, N, N-dipropyl-para-phenylenediamine, 4-amino-N, N-diethyl-3-methylaniline, N, N- bis- (3-hydroxyethyl) paraphenylenediamine, 4-N, N-bis (3-hydroxyethyl) amino-2-methylaniline, 4-N, N-bis- (3-hydroxyethyl) amino 2-chloroaniline, 2β-hydroxyethyl paraphenylenediamine, 2-fluoro-para-phenylenediamine, 2-isopropyl-para-phenylenediamine, N- (β-hydroxypropyl) para-phenylenediamine, 2-hydroxymethyl-para-phenylenediamine, 2-methoxymethyl-para-phenylenediamine, N, N-dimethyl-3-methyl-para-phenylenediamine, N, N- (ethyl, p-hydroxyethyl) paraphony Nylenediamine, N- (3,4-dihydroxypropyl) paraphenylenediamine, N- (4'-aminophenyl) paraphenylenediamine, N-phenyl paraphenylenediamine, 2β-hydroxyethyloxy para-phenylenediamine, 2β-acetylaminoethyloxy-para-phenylenediamine, N- (3-methoxyethyl) paraphenylenediamine, 4-aminophenylpyrrolidine, 2-thienyl paraphenylenediamine, hydroxyethylamino 5-amino toluene, 3-hydroxy-1- (4'-aminophenyl) pyrrolidine and their addition salts with an acid. Among the para-phenylenediamines mentioned above, paraphenylenediamine, paratoluylenediamine, 2-isopropyl paraphenylenediamine, 2β-hydroxyethyl paraphenylenediamine, 2β-hydroxyethyloxy paraphenylenediamine, 2,6-dimethyl paraphenylenediamine, 2,6-diethyl paraphenylenediamine, 2,3-dimethyl paraphenylenediamine, N, N-bis (β-hydroxyethyl) paraphenylenediamine, 2-chloro-para-phenylenediamine, 2β-acetylaminoethyloxy-para-phenylenediamine, and their acid addition salts are particularly preferred. Among the bis-phenylalkylenediamines, N, N'-bis- (3-hydroxyethyl) N, N'-bis- (4'-aminophenyl) -1,3-diamino propanol, N, may be mentioned by way of example. N, N'-bis- (3-hydroxyethyl) N, N'-bis- (4'-aminophenyl) ethylenediamine, N, N'-bis- (4-aminophenyl) tetramethylenediamine, N, N'-bis- ( 3-hydroxyethyl) N, N'-bis (4-aminophenyl) tetramethylenediamine, N, N'-bis (4-methylaminophenyl) tetramethylenediamine, N, N'-bis (ethyl) N, N ' -bis- (4'-amino, 3'-methylphenyl) ethylenediamine, 1,8-bis (2,5-diamino phenoxy) -3,6-dioxaoctane, and their addition salts. Among para-aminophenols, para-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluoro phenol, 4-amino-3-chlorophenol, 4- amino 3-hydroxymethyl phenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol, 4-amino 2- (f3 hydroxyethyl aminomethyl) phenol, 4-amino-2-fluoro phenol, and their addition salts with an acid. Among the ortho-aminophenols, mention may be made, for example, of 2-amino phenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol and 5-acetamido-2-aminophenol, and their addition salts.
[0008] Among the heterocyclic bases, it is possible in particular to pyridine derivatives, pyrimidine derivatives and pyrazole derivatives. Among the pyridine derivatives, mention may be made of the compounds described for example in patents GB 1 026 978 and GB 1 153 196, such as 2,5-diaminopyridine, 2- (4-methoxyphenyl) amino 3-amino pyridine, 3,4-diamino pyridine, and their addition salts. Other pyridinic oxidation bases useful in the present invention are the 3-amino pyrazolo [1,5-4-pyridines oxidation bases or their addition salts described for example in the patent application FR 2801308. A by way of example, mention may be made of pyrazolo [1,5-a] pyridin-3-ylamine; 2-acetylamino pyrazolo [1,5-a] pyridin-3-ylamine; 2-morpholin-4-yl-pyrazolo [1,5-a] pyridin-3-ylamine; 3-amino-pyrazolo [1,5-a] pyridin-2-carboxylic acid; 2-methoxypyrazolo [1,5-a] pyridin-3-ylamino; (3-Amino-pyrazolo [1,5-a] pyridin-7-yl) -methanol; 2- (3-Amino-pyrazolo [1,5-a] pyridin-5-yl) -ethanol; 2- (3-Amino-pyrazolo [1,5-a] pyridin-7-yl) -ethanol; (3-amino-pyrazolo [1,5-a] pyridin-2-yl) -methanol; 3,6-diamino-pyrazolo [1,5-a] pyridine; 3,4-diamino-pyrazolo [1,5-a] pyridine; pyrazolo [1,5-a] pyridine-3,7-diamine; 7-morpholin-4-yl-pyrazolo [1,5-a] pyridin-3-ylamine; pyrazolo [1,5-a] pyridine-3,5-diamine; 5-morpholin-4-yl-pyrazolo [1,5-a] pyridin-3-ylamine; 2 - [(3-Amino-pyrazolo [1,5-a] pyridin-5-yl) - (2-hydroxyethyl) amino] ethanol; 2 - [(3-Amino-pyrazolo [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-amino-pyrazolo [1,5-a] pyridin-6-ol; 3-amino-pyrazolo [1,5-a] pyridin-7-ol; 213-hydroxyethoxy-3-aminopyrazolo [1,5-a] pyridine; 2- (4-dimethylpiperazinium-1-yl) -3-amino-pyrazolo [1,5-a] pyridine; as well as their addition salts. More particularly, the oxidation bases according to the invention are chosen from 3-aminopyrazolo- [1,5-4-pyridines preferably substituted in position 2 by: a) a (di) (C1-C6) (alkyl) group amino alkyl groups which may be substituted by one or more hydroxy, amino, or imidazolium groups; b) a heterocycloalkyl group comprising from 5 to 7 members, and from 1 to 3 heteroatoms, cationic or otherwise, optionally substituted with one or more (C1-C6) alkyl groups such as di (C1-C4) alkylpiperazinium; c) a (C1-C6) alkoxy group optionally substituted with one or more hydroxyl groups such as p-hydroxyalkoxy and their addition salts. Among the pyrimidine derivatives, mention may be made of the compounds described, for example, in DE 2359399; JP 88-169571; JP 05-63124; EP 0770375 or patent application VVO 96/15765 such as 2,4,5,6-tetraaminopyrimidine, 4-hydroxy 2,5,6-triaminopyrimidine, 2-hydroxy 4,5,6-triaminopyrimidine, 2 , 4-dihydroxy-5,6-diaminopyrimidine, 2,5,6-triaminopyrimidine and their addition salts and tautomeric forms, when tautomeric equilibrium exists. Among the pyrazole derivatives, mention may be made of the compounds described in DE 3843892, DE 4133957 and patent applications VVO 94/08969, VVO 94/08970, FR-A2 733 749 and DE 195 43 988, such as 4,5-diamino 1-methyl pyrazole, 4,5-diamino 1- (3-hydroxyethyl) pyrazole, 3,4-diamino pyrazole, 4,5-diamino 1- (4'-chlorobenzyl) pyrazole, 4,5-diamino 1,3-dimethyl pyrazole, 4,5-diamino-3-methyl-1-phenyl pyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 4-amino-1,3-dimethyl-5-hydrazino pyrazole, 1-Benzyl-4,5-diamino-3-methyl-pyrazole, 4,5-diamino-3-tert-butyl-1-methyl-pyrazole, 4,5-diamino-1-tert-butyl-3-methyl-pyrazole, 4,5- diamino 1- (3-hydroxyethyl) 3-methyl pyrazole, 4,5-diamino-1-ethyl-3-methyl-pyrazole, 4,5-diamino-1-ethyl-3- (4'-methoxyphenyl) pyrazole, 4,5 1-ethyl-3-hydroxymethyl pyrazole, 4,5-diamino-3-hydroxymethyl-1-methyl pyrazole, 4,5-diamino-3-hydroxymethyl-1-isopropyl pyrazole, 4,5-diamino-3-methyl ethyl 1-isopropyl pyrazole, 4-amino 5- (2'-aminoethyl) amino 1,3-dimethyl pyrazole, 3,4,5-triamino pyrazole, 1-methyl 3,4,5-triamino pyrazole, 3,5-diamino-1-methyl-4-methylamino pyrazole, 3,5-diamino 4- (3-hydroxyethyl) amino-1-methyl pyrazole, and their addition salts. Preferably the heterocyclic oxidation bases of the invention are selected from 4,5-diaminopyrazoles such as 4,5-diamino 1- (3-hydroxyethyl) pyrazole. 4-5-Diamino 1- (3-methoxyethyl) pyrazole can also be used. The oxidation base (s) present in the composition of the invention are generally present in an amount ranging from 0.001 to 20% by weight of the total weight of the dyeing composition, preferably ranging from 0.005 to 6%. Additional Couplers: The composition according to the invention may also contain one or more additional couplers conventionally used for dyeing keratinous fibers different from those of formula (1) as defined above. Among these couplers, there may be mentioned meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalenic couplers, heterocyclic couplers and their addition salts. By way of example, mention may be made of 1,3-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene, 4-chloro-1,3-dihydroxybenzene and 1-hydroxy-3-aminobenzene. methyl-5-aminophenol, 2-methyl-5-hydroxyethylaminophenol, 2,4-diamino-1- (11-hydroxyethyloxy) benzene, 2-amino-4- (11-hydroxyethylamino) -1-methoxybenzene, 1,3 diamino benzene, 1,3-bis- (2,4-diaminophenoxy) propane, 3-ureido aniline, 3-ureido 1-dimethylamino benzene, sesamol, thymol, 1-11-hydroxyethylamino-3, 4-methylenedioxybenzene, α-naphthol, 2-methyl-1-naphthol, 6-hydroxyindole, 4-hydroxyindole, 4-hydroxy-N-methylindole, 2-amino-3-hydroxypyridine, 6-hydroxybenzomorpholine 3,5-diamino-2,6-dimethoxypyridine, 1-N- (11-hydroxyethyl) amino-3,4-methylene dioxybenzene, 2,6-bis (11-hydroxyethylamino) -toluene 6-hydroxyindoline, 2,6-dihydroxy-4-methylpyridine, 1-H-3-methylpyrazole-5-one, 1-phenyl-3-methylpyrazole 5-o 2,6-dimethyl pyrazolo [1,5-b] -1,2,4-triazole, 2,6-dimethyl [3,2-c] -1,2,4-triazole, 6- methyl pyrazolo benzimidazole, their addition salts with an acid, and mixtures thereof. In general, the addition salts of the oxidation bases and couplers that can be used in the context of the invention are chosen especially from the addition salts with an acid such as hydrochlorides, hydrobromides, sulphates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates. In the composition of the present invention, the coupler or couplers are generally present in total amount with the coupler or couplers of formula (1) ranging from 0.001 to 20% by weight of the total weight of the dyeing composition, preferably ranging from 0.005 at 6%. Additional dyes: According to a particular embodiment of the invention, the composition also contains one or more direct dyes, synthetic or natural, chosen from ionic or nonionic species, preferably cationic or nonionic. As examples of suitable direct dyes, mention may be made of azo direct dyes; (poly) methine dyes such as cyanines, hemicyanins, and styryls; carbonyls; azinic; nitro (hetero) aryl; tri (hetero) aryl methanes; porphyrins; phthalocyanines and natural direct dyes, alone or in mixtures. Among the natural direct dyes that may be used according to the invention, lawsone, juglone, alizarin, purpurine, carminic acid, kermesic acid, purpurogalline, protocatechaldehyde, indigo, isatin , curcumin, spinulosin, apigenidine, orceins. It is also possible to use the extracts or decoctions containing these natural dyes, and in particular poultices or extracts made from henna.
[0009] The direct dye (s) more particularly represent from 0.001 to 10% by weight of the total weight of the composition, and preferably from 0.005 to 6% by weight relative to the total weight of the composition. iii) the fat (s): According to a preferred embodiment of the invention, the composition of the invention comprises one or more fatty substances. The term "fatty substance" means an organic compound which is insoluble in water at ordinary room temperature (25 ° C.) and at atmospheric pressure (760 mmHg) (solubility less than 5% and preferably greater than 1%, more preferably at 0.1%). They have in their structure at least one hydrocarbon chain comprising at least 6 carbon atoms or a chain of at least two siloxane groups. In addition, the fatty substances are generally soluble in organic solvents under the same conditions of temperature and pressure, such as for example chloroform, ethanol, benzene, liquid petrolatum or decamethylcyclopentasiloxane. These fatty substances are neither polyoxyethylenated nor polyglycerolated. They are different from fatty acids because salified fatty acids are generally soluble soaps in aqueous media. The fatty substances are chosen in particular from hydrocarbons and from 06-016 or more than 16 carbon atoms and in particular alkanes, oils of animal origin, oils of vegetable origin, synthetic glycerides, natural triglycerides, fluorinated oils of synthetic origin, fatty alcohols, fatty acid esters and / or fatty alcohol esters different from natural or synthetic glycerides, non-silicone waxes, silicones. It is recalled that for the purposes of the invention, the alcohols, esters and fatty acids more particularly have one or more linear or branched hydrocarbon groups, saturated or unsaturated, comprising 6 to 30 carbon atoms, which are optionally substituted, in particular by one or more hydroxyl groups (in particular 1 to 4). If unsaturated, these compounds may comprise one to three carbon-carbon double bonds, conjugated or otherwise. As for the alkanes at 06-016, the latter are linear, branched, possibly cyclic. By way of example, mention may be made of hexane, dodecane, undecane and tridecane, and isoparaffins such as isohexadecane and isodecane. The linear or branched hydrocarbons having more than 16 carbon atoms may be chosen from paraffin oils, petroleum jelly, liquid petroleum jelly, polydecenes and hydrogenated polyisobutene such as Parleamo.
[0010] Among the animal oils there may be mentioned perhydrosqualene. Among triglycerides of plant or synthetic origin, mention may be made of liquid triglycerides of fatty acids containing from 6 to 30 carbon atoms, for instance triglycerides of heptanoic or octanoic acids or else, for example, sunflower, corn, soy, squash, grape seed, sesame, hazelnut, apricot, macadamia, arara, sunflower, castor, avocado, jojoba oil, shea butter oil triglycerides of caprylic / capric acids such as those sold by Stearineries Dubois or those sold under the names Miglyol® 810, 812 and 818 by the company Dynamit Nobel; Among the fluorinated oils, mention may be made of perfluoromethylcyclopentane and perfluoro-1,3-dimethylcyclohexane, sold under the names "FLUTECO PC1" and "FLUTECO P03" by BNFL Fluorochemicals; perfluoro-1,2-dimethylcyclobutane; perfluoroalkanes such as dodecafluoropentane and tetradecafluorohexane, sold under the names "PF 50500" and "PF 50600" by the company 3M, or bromoperfluorooctyl sold under the name "FORALKYLO" by the company Atochem; nonafluoro-methoxybutane and nonafluoroethoxyisobutane; perfluoromorpholine derivatives, such as 4-trifluoromethyl perfluoromorpholine sold under the name "PF 50520" by the company 3M. The fatty alcohols that can be used in the cosmetic compositions of the invention are saturated or unsaturated, linear or branched, and contain from 6 to 30 carbon atoms and more particularly from 8 to 30 carbon atoms. For example, cetyl alcohol, stearyl alcohol and their mixture (cetylstearyl alcohol), octyldodecanol, 2-butyloctanol, 2-hexyldecanol, 2-undecylpentadecanol, oleic alcohol or linoleic alcohol may be mentioned; . The wax or waxes that may be used in the cosmetic composition are chosen in particular from carnauba wax, candelilla wax, and alfa wax, paraffin wax, ozokerite, vegetable waxes such as olive wax, rice wax, hydrogenated jojoba wax or absolute waxes of flowers such as the essential wax of blackcurrant flower sold by the company BERTIN (France), animal waxes such as beeswax, or modified beeswax (cerabellina); other waxes or waxy raw materials that can be used according to the invention are, in particular, marine waxes, such as the one sold by SOPHIM under the reference M82, and polyethylene or polyolefin waxes in general. With regard to fatty acid esters and / or fatty alcohols, there may be mentioned in particular saturated or unsaturated aliphatic or monohydric acid esters, linear or branched in Cl-026 and saturated or unsaturated aliphatic mono or polyalcohols, linear or branched in Cl-026, the total carbon number of the esters being more particularly greater than or equal to 10. Among the monoesters, mention may be made of dihydroabiethyl behenate; octyldodecyl behenate; isoketyl behenate; cetyl lactate; alkyl lactate at 0-12-015; isostearyl lactate; lauryl lactate; linoleyl lactate; oleyl lactate; (iso) stearyl octanoate; isocetyl octanoate; octyl octanoate; cetyl octanoate; decyl oleate; isocetyl isostearate; isocetyl laurate; isocetyl stearate; isodecyl octanoate; isodecyl oleate; isononyl isononanoate; isostearyl palmitate; methyl ricinoleate acetyl; myristyl stearate; octyl isononanoate; 2-ethylhexyl isononate; octyl palmitate; octyl pelargonate; octyl stearate; octyldodecyl erucate; oleyl erucate; ethyl and isopropyl palmitates, ethyl-2-hexyl palmitate, 2-octyldecyl palmitate, alkyl myristates such as isopropyl, butyl, cetyl, 2-octyldodecyl myristate; , styryl, hexyl stearate, butyl stearate, isobutyl stearate; dioctyl malate, hexyl laurate, 2-hexyldecyl laurate. Still within the context of this variant, it is also possible to use the esters of di or tricarboxylic acids at 04-022 and of alcohols at Cl-022 and the esters of mono- or di-tricarboxylic acids and di-, tri-alcohols. tetra or pentahydroxy in 02-026.
[0011] These include: diethyl sebacate; diisopropyl sebacate; diisopropyl adipate; di-propyl adipate; dioctyl adipate; diisostearyl adipate; dioctyl maleate; glyceryl undecylenate; octyldodecyl stearoyl stearate; pentaerythrityl monoricinoleate; pentaerythrityl tetraisononanoate; pentaerythrityl tetrapelargonate; pentaerythrityl tetraisostearate; pentaerythrityl tetraoctanoate; propylene glycol dicaprylate; propylene glycol dicaprate, tridecyl erucate; triisopropyl citrate; triisotearyl citrate; glyceryl trilactate; glyceryl trioctanoate; trioctyldodecyl citrate; trioleyl citrate, propylene glycol dioctanoate; neopentyl glycol diheptanoate; diethylene glycol diisanonate; and polyethylene glycol distearates. Among the esters mentioned above, it is preferred to use ethyl, isopropyl, myristyl, cetyl, stearyl palmitates, ethyl-2-hexyl palmitate, 2-octyldecyl palmitate, sodium myristates and the like. alkyls such as isopropyl, butyl, cetyl, 2-octyldodecyl myristate, hexyl stearate, butyl stearate, isobutyl stearate; dioctyl malate, hexyl laurate, 2-hexyldecyl laurate and isononyl isononanate, cetyl octanoate. The composition may also comprise, as fatty ester, esters and diesters of 6-030 fatty acid sugars, preferably 0-12-022. It is recalled that "sugar" is understood to mean oxygenated hydrocarbon compounds which have several alcohol functions, with or without an aldehyde or ketone function, and which contain at least 4 carbon atoms. These sugars can be monosaccharides, oligosaccharides or polysaccharides. Suitable sugars include, for example, sucrose (or sucrose), glucose, galactose, ribose, fucose, maltose, fructose, mannose, arabinose, xylose, lactose, and their derivatives. especially alkyls, such as methyl derivatives such as methylglucose. The esters of sugars and of fatty acids may be chosen in particular from the group comprising the esters or mixtures of esters of sugars described above and of linear or branched, saturated, linear or branched, 0-12-030 fatty acids, preferably or unsaturated. If unsaturated, these compounds may comprise one to three carbon-carbon double bonds, conjugated or otherwise. The esters according to this variant may also be chosen from mono-, di-, tri- and tetraesters, polyesters and mixtures thereof. These esters may be for example oleate, laurate, palmitate, myristate, behenate, cocoate, stearate, linoleate, linolenate, caprate, arachidonates, or mixtures thereof, such as in particular the mixed oleo-palmitate, oleostearate and palmitostearate esters. More particularly, the mono- and di-esters are used, and especially the mono- or dioleate, stearate, behenate, oleopalmitate, linoleate, linolenate, oleostearate, sucrose, glucose or methylglucose. By way of example, mention may be made of the product sold under the name Glucate® DO by the company Amerchol, which is a methylglucose dioleate. Mention may also be made, by way of examples, of esters or mixtures of esters of fatty acid sugar: the products sold under the names F160, F140, F110, F90, F70, SL40 by the company Crodesta, respectively denoting sucrose palmito-stearates of 73% monoester and 27% di- and tri-ester, 61% monoester and 39% di-, tri- and tetraester, 52% monoester and 48% monoester; % di-, tri- and tetraester, 45% monoester and 55% di-, tri- and tetraester, 39% monoester and 61% di-, tri-, and tetra. -ester, and sucrose mono-laurate; the products sold under the name Ryoto Sugar Esters, for example referenced B370 and corresponding to sucrose behenate formed from 20% monoester and 80% di-triester-polyester; the sucrose mono-dipalmito-stearate marketed by Goldschmidt under the name Tegosoft® PSE. The silicones that can be used in the cosmetic composition (A) of the present invention are volatile or cyclic, linear or branched, volatile or non-organic group-modified silicones having a viscosity of 5 × 10 -6 to 2.5 m 2 / s at 25 ° C and preferably 1.10-5 to 1 m2 / s. The silicones that can be used in accordance with the invention can be in the form of oils, waxes, resins or gums. Preferably, the silicone is chosen from polydialkylsiloxanes, in particular polydimethylsiloxanes (PDMS), and organomodified polysiloxanes comprising at least one functional group chosen from poly (oxyalkylene) groups, amino groups and alkoxy groups. Organopolysiloxanes are further defined in Walter Noll's "Chemistry and Technology of Silicones" (1968), Academie Press. They can be volatile or nonvolatile.
[0012] When they are volatile, the silicones are more particularly chosen from those having a boiling point of between 60 ° C. and 260 ° C., and even more particularly from: cyclic polydialkylsiloxanes containing from 3 to 7, preferably from 4 to 5 silicon atoms. It is, for example, octamethylcyclotetrasiloxane sold in particular under the name VOLATILE SILICONE @ 7207 by UNION CARBIDE or SILBIONE @ 70045 V2 by RHODIA, decamethylcyclopentasiloxane marketed under the name VOLATILE SILICONE @ 7158 by UNION CARBIDE, and SILBIONE @ 70045 V5 by RHODIA, as well as their mixtures.
[0013] Mention may also be made of cyclocopolymers of the dimethylsiloxane / methylalkylsiloxane type, such as the VOLATILE SILICONE @ FZ 3109 marketed by UNION CARBIDE, of the formula: ## STR3 ## with D ": - Si The cyclic polydialkylsiloxane mixtures with organic compounds derived from silicon, such as the mixture of octamethylcyclotetrasiloxane and tetramethylsilylpentaerythritol (50/50), and the mixture of octamethylcyclotetrasiloxane and dicyclohexane are also mentioned. oxy-1,1 '- (hexa-2,2,2', 2 ', 3,3'-trimethylsilyloxy) bis-neopentane (ii) linear volatile polydialkylsiloxanes having 2 to 9 silicon atoms and having a viscosity less than or equal to 5.10-6 m 2 / s at 25 ° C. It is, for example, decamethyltetrasiloxane marketed in particular under the name "SH 200" by Toray Silicone, silicones falling into this class are also described in art icle published in Cosmetics and Toiletries, Vol. 91, Jan. 76, p. 27-32 - TODD & BYERS "Volatile Silicone fluids for cosmetics". Non-volatile polydialkylsiloxanes, polydialkylsiloxane gums and resins, polyorganosiloxanes modified with the above organofunctional groups and mixtures thereof are preferably used. These silicones are more particularly chosen from polydialkylsiloxanes, among which may be mentioned mainly polydimethylsiloxanes with trimethylsilyl end groups. The viscosity of the silicones is measured at 25 ° C. according to the ASTM 445 Appendix C standard. Among these polydialkylsiloxanes, mention may be made, without limitation, of the following commercial products: SILBIONE® oils of the 47 and 70 047 series or the MIRASIL® oils Sold by RHODIA such as, for example, 70 047 V 500 000; the oils of the MIRASIL® series marketed by RHODIA; the oils of the 200 series of Dow Corning, such as DC200 having a viscosity of 60,000 mm 2 / s; - VISCASIL @ oils from GENERAL ELECTRIC and some oils from the SF 35 series (SF 96, SF 18) from GENERAL ELECTRIC.
[0014] Mention may also be made of polydimethylsiloxanes with dimethylsilanol end groups known under the name of dimethiconol (CTFA), such as the oils of the 48 series from the company RHODIA. In this class of polydialkylsiloxanes, mention may also be made of the products sold under the names "ABIL WAX® 9800 and 9801" by GOLDSCHMI DT, which are polydialkyl (C1-020) siloxanes. The silicone gums that can be used in accordance with the invention are in particular polydialkylsiloxanes, preferably polydimethylsiloxanes having high average molecular weights of between 200,000 and 1,000,000 used alone or in a mixture in a solvent. This solvent may be chosen from volatile silicones, polydimethylsiloxane (PDMS) oils, polyphenylmethylsiloxane (PPMS) oils, isoparaffins, polyisobutylenes, methylene chloride, pentane, dodecane, tridecane or their mixtures. More particularly useful products according to the invention are mixtures such as: - mixtures formed from a hydroxyl end-of-the-chain polydimethylsiloxane, or dimethiconol (CTFA) and a cyclic polydimethylsiloxane also called cyclomethicone (CTFA) such that the product Q2 1401 marketed by the company Dow Corning; mixtures of a polydimethylsiloxane gum and a cyclic silicone such as the product SF 1214 Silicone Fluid from the company General Electric, this product is an SF 30 gum corresponding to a dimethicone, having a number average molecular weight of 500,000 solubilized in oil SF 1202 Silicone Fluid corresponding to decamethylcyclopentasiloxane; mixtures of two PDMSs of different viscosities, and more particularly of a PDMS gum and a PDMS oil, such as the product SF 1236 from the company General Electric. The product SF 1236 is the mixture of an SE 30 gum defined above having a viscosity of 20 m 2 / s and an SF 96 oil with a viscosity of 5 × 10 -6 m 2 / s. This product preferably comprises 15% of SE 30 gum and 85% of an SF 96 oil. The organopolysiloxane resins used in accordance with the invention are crosslinked siloxane systems containing the units: R25iO2 / 2, R35iO1 / 2, R5iO3 Wherein R represents an alkyl having 1 to 16 carbon atoms. Among these products, those that are particularly preferred are those in which R denotes a C1-C4 lower alkyl group, more particularly methyl. Among these resins may be mentioned the product marketed under the name "Dow Corning 593" or those sold under the names "Silicone Fluid SS 4230 and SS 4267" by the company General Electric and which are silicones of dimethyl / trimethyl siloxane structure. Mention may also be made of the trimethylsiloxysilicate type resins sold in particular under the names X22-4914, X21-5034 and X21-5037 by the company Shin-Etsu.
[0015] The organomodified silicones that may be used in accordance with the invention are silicones as defined above and comprising in their structure one or more organofunctional groups attached via a hydrocarbon-based group. In addition to the silicones described above, the organomodified silicones may be polydiarylsiloxanes, especially polydiphenylsiloxanes, and polyalkylarylsiloxanes functionalized with the organofunctional groups mentioned above. The polyalkylarylsiloxanes are especially chosen from polydimethyl / methylphenylsiloxanes, linear and / or branched polydimethyl / diphenylsiloxanes with a viscosity ranging from 1 × 10 -5 to 5 × 10 -2 m 2 / s at 25 ° C. Among these polyalkylarylsiloxanes, mention may be made by way of example of the products sold under the following names: SILBIONE® oils of the 70 641 series from RHODIA; - the RHODORSIL® 70 633 and 763 RHODIA series of oils; - DOW CORNING 556 COSMETIC GRAD FLUID oil from Dow Corning; the silicones of the PK series of BAYER, such as the product PK20; the silicones of the PN, PH series of BAYER, such as the PN1000 and PH1000 products; certain oils of the SF series of GENERAL ELECTRIC such as SF 1023, SF 1154, SF 1250 and SF 1265. Among the organomodified silicones, mention may be made of polyorganosiloxanes comprising: polyethyleneoxy and / or polypropyleneoxy groups optionally comprising C 6 alkyl groups; -C24 such as the products known as dimethicone copolyol marketed by the company Dow Corning under the name DC 1248 or the oils SILVVETO L 722, L 7500, L 77, L 711 of the company UNION CARBIDE and alkyl (C12) -methicone copolyol sold by the company Dow Corning under the name Q2 5200; substituted or unsubstituted amine groups such as the products sold under the name GP 4 Silicone Fluid and GP 7100 by the company Genesee or the products sold under the names Q2 8220 and Dow Corning 929 or 939 by the company Dow Corning. The substituted amino groups are, in particular, C1-C4 aminoalkyl groups; alkoxylated groups, such as the product marketed under the name "Silicone Copolymer F-755" by SVVS Silicones and Abil Wax® 2428, 2434 and 2440 by the company GOLDSCHMIDT. The fatty substances are advantageously chosen from C 6 -C 16 hydrocarbons or more than 16 carbon atoms and in particular alkanes, vegetable oils, fatty alcohols, fatty acid esters and / or alcohol esters. different fatty acids from triglycerides, silicones or their mixtures. Preferably, the fatty substance is an oil (a liquid compound at a temperature of 25 ° C. and at atmospheric pressure). Preferably, the fatty substance is chosen from liquid petrolatum, C6-C16 alkanes, polydecenes, liquid esters of fatty acid and / or fatty alcohol, liquid fatty alcohols or mixtures thereof. Better still, the fatty substance is chosen from petrolatum oil and C6-C16 alkanes, and polydecenes. The fatty substances are present in a content greater than 10% by weight, relative to the total weight of the composition.
[0016] The dye composition which comprises the coupler (s) (I) has a fat content preferably ranging from 10 to 80% by weight, and even more particularly ranging from 20 to 80% by weight, better still from 25 to 75% by weight. and most preferably 40 to 70% by weight relative to the total weight of the dyeing composition, more preferably between 50 and 60% by weight relative to the total weight of the dyeing composition. iv) The metal catalyst (s) According to one particular embodiment of the invention, the composition which comprises one or more couplers of formula (I) as defined previously further comprises one or more metal catalysts. "Metallic catalysts" are compounds which comprise in their structure one or more metals. The metals are selected from transition metals, rare earth metals and their alloys. In particular, the metals are selected from transition metals and rare earth metals. Among the transition metals, there may be mentioned manganese, iron, cobalt, copper, zinc, platinum, nickel, titanium, silver, zirconium, chromium, molybdenum, tungsten, platinum, gold, vanadium and among these especially manganese. Among the rare earth metals, mention may be made of cerium. Thus, the metal catalysts are especially catalysts based on transition metals and rare earth metals, and more particularly catalysts based on manganese, vanadium or cerium. The metal catalysts used may be in the form of metal salts, metal oxides, metal complexes and mixtures thereof. For the purposes of the present invention, the term "metal complexes" means systems in which the metal ion, that is to say the central atom, is bonded to one or more electron donors, called ligands, by through chemical bonds. As an example, mention may be made of porphyrins and phthalocyanines, in particular cationic phthalocyanines. Preferably, the metal catalysts used in the dyeing process are chosen from metal salts. For the purposes of the present invention, the term "metal salts" means salts derived from the action of an acid on a metal. Preferably, the metal catalysts used in the dyeing process are chosen from transition metal salts, such as manganese salts, and rare earth metal salts, such as cerium salts, and mixtures thereof. . The metal salts may be inorganic or organic salts. According to one variant, the metal salts are inorganic and may be chosen from halides, carbonates, sulphates and phosphates, in particular hydrated or non-hydrated halides. According to another preferred variant, the metal salts are of oxidation state II and have two ligands derived from C2-C10 carboxylic acid or (poly) hydroxyacid. By "carboxylic acid" is meant a carboxylic acid comprising a hydrocarbon chain, linear or branched, saturated or unsaturated, preferably linear and / or saturated, comprising from 1 to 10 carbon atoms, and comprising from 1 to 4 carboxyl groups -C (0) -OH, wherein at least one of said -C (O) -OH functions is in the form of carboxylate -C (O) -O- complexed with the metal atom, preferably M n (II). By "(poly) hydroxyacid" is meant any carboxylic acid which comprises a hydrocarbon chain, linear or branched, saturated or unsaturated, preferably saturated and / or linear, comprising from 1 to 10 carbon atoms and from 1 to 9 hydroxyl groups, and comprising from 1 to 4 carboxyl groups -C (O) -OH, at least one of said functions -C (O) -OH is in the form carboxylate -C (O) -O- complexed with the metal atom, preferably Mn (II).
[0017] More particularly, the metal salt is complexed by two carboxylate groups such as that of formula (II): Ra-C (O) -O-M-O-C (O) -Rb (II) and its solvates such as hydrates and their enantiomers Formula (II) in which: - M represents a metal (II) or metal2 + of oxidation state 2, - Ra and Rb, identical or different, represent a (poly) (hydroxy) (C1C6) alkyl group. In particular, the metal catalysts are chosen from organic acid salts of transition metals, especially of manganese, and inorganic salts of rare earth metals, in particular cerium. According to a particular embodiment of the invention, manganese is not an oxide but a manganese salt. The organic metal salts may be more particularly chosen from salts of organic acids such as citrates, lactates, glycolates, gluconates, acetates, propionates, fumarates, oxalates and tartrates, in particular gluconates. More preferably, the metal catalysts are chosen from manganese gluconate and cerium heptahydrate chloride, in particular manganese gluconate. Preferably, the metal catalyst (s) are chosen from the compounds of formula (II) and more particularly represents manganese gluconate. The metal catalysts may be present in a content ranging from 0.001% to 10% by weight, preferably in a content ranging from 0.001% to 1% by weight, better still ranging from 0.01% to 0.5% by weight relative to the total weight. of the composition.
[0018] The medium of the cosmetic compositions The compositions of the invention are cosmetic. Preferably, all the compositions used in the dyeing process of the invention are aqueous compositions. The composition comprising one or more couplers of formula (I) according to the invention is a cosmetic and preferably aqueous composition. By "aqueous composition" is meant a composition comprising more than 5% by weight of water, preferably more than 10% by weight of water, and even more advantageously more than 20% by weight of water.
[0019] Even more preferentially, the water concentration of the compositions of the invention may range from 10 to 90%, better still from 20 to 80%, of the total weight of the composition. The compositions of the invention may optionally comprise one or more organic solvents. As organic solvent, there may be mentioned, for example, linear or branched alkanols, 02-04, such as ethanol and isopropanol; polyols and polyol ethers such as 2-butoxyethanol, propylene glycol, glycerol, dipropylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and monomethyl ether, as well as aromatic alcohols such as benzyl alcohol or phenoxyethanol, and their mixtures.
[0020] The organic solvent or solvents, if present, represent a content usually ranging from 1 to 40% by weight, and preferably ranging from 5 to 30% by weight relative to the weight of the composition containing them.
[0021] Adjuvants: The dye composition of the invention comprising the coupler (s) of formula (I) of the invention may further contain additional ingredients. The dye composition in accordance with the invention may also contain various adjuvants conventionally used in compositions for dyeing hair, such as anionic, cationic, nonionic, amphoteric, zwitterionic surfactants or mixtures thereof, anionic polymers, cationic, nonionic, amphoteric, zwitterionic or their mixtures, inorganic or organic thickeners, and in particular anionic, cationic, nonionic and amphoteric polymeric associative thickeners, antioxidants, penetrating agents, sequestering agents, perfumes, buffers, dispersing agents, conditioning agents such as, for example, volatile or non-volatile silicones, modified or unmodified, film-forming agents, ceramides, preserving agents, opacifying agents.
[0022] The adjuvants above are generally present in an amount for each of them between 0.01 and 20% by weight relative to the weight of the composition. Of course, one skilled in the art will take care to choose this or these optional additional compounds such that the advantageous properties intrinsically attached to the oxidation dyeing composition according to the invention are not, or not substantially impaired by the addition or additions envisaged. The dye composition according to the invention may be in various forms, such as in the form of liquids, creams, gels, or in any other form suitable for dyeing keratinous fibers, and especially human hair.
[0023] PH The pH of the dyeing composition according to the invention is generally between 2 and 12 approximately, and preferably between Set 11 approximately. The composition of the invention which comprises the coupler (s) of formula (I) and the oxidation base (s) has a pH which preferably varies from 6.5 to 12, better still from 8 to 12. The pH can be adjusted to the desired value by means of additional acidifying or alkaline agents, such as those mentioned below usually used for dyeing keratinous fibers or else using conventional buffer systems.
[0024] Among the acidifying agents, mention may be made, by way of example, of mineral or organic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid, lactic acid, sulphonic acids. y) Alkaline agents: Preferably, the dye composition comprises one or more alkaline agents, organic or inorganic, preferably organic.
[0025] The alkaline agent (s) may be inorganic or organic. The inorganic alkaline agent (s) is (are) preferably chosen from ammonia, alkali carbonates or bicarbonates, such as sodium or potassium carbonates or bicarbonates, sodium or potassium hydroxides, or mixtures thereof.
[0026] The organic alkaline agent (s) is (are) preferably chosen from organic amines whose pKb at 25 ° C. is less than 12, and preferably less than 10, and even more advantageously less than 6. It should be noted that this is pKb corresponding to the highest basicity function. In addition, the organic amines do not comprise a fatty chain, alkyl or alkenyl, comprising more than ten carbon atoms. The organic alkaline agent (s) are, for example, chosen from alkanolamines, ethoxylated and / or oxypropylenated ethylene diamines, amino acids and compounds of the following formula (III): ## STR2 ## Formula (III) in which VV is a divalent C1-C6 alkylene radical optionally substituted by one or more hydroxyl groups or a C1-C6 alkyl radical, and / or optionally interrupted by one or more heteroatoms such as O, or NRu; Rx, Ry, Rz, Rt, R, and the same or different, represent a hydrogen atom, a C1-C6 alkyl or C1-C6 hydroxyalkyl, C1-C6 aminoalkyl.
[0027] Examples of amines of formula (III) are 1,3-diaminopropane, 1,3-diaminopropanol, spermine and spermidine. By alkanolamine is meant an organic amine comprising a primary, secondary or tertiary amine function, and one or more linear or branched C1-C8 alkyl groups carrying one or more hydroxyl radicals.
[0028] In particular, the organic amines chosen from alkanolamines, such as mono-, di- or tri-alkanolamines, comprising one to three identical or different C1-C4 hydroxyalkyl radicals are suitable in the embodiment of the invention.
[0029] Among compounds of this type, mention may be made of monoethanolamine (MEA), diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, N, N-dimethylethanolamine, 2-amino-2-methyl-1-propanol and triisopropanol. amine, 2-amino-2-methyl-1,3-propanediol, 3-amino-1,2-propanediol, 3-dimethylamino-1,2-propanediol, tris-hydroxymethylamino-methane. More particularly, the amino acids that can be used are of natural or synthetic origin, in their L, D, or racemic form, and comprise at least one acid function chosen more particularly from the carboxylic, sulphonic, phosphonic or phosphoric acid functions. Amino acids can be in neutral or ionic form. As amino acids that may be used in the present invention, mention may in particular be made of aspartic acid, glutamic acid, alanine, arginine, ornithine, citrulline, asparagine, carnitine and cysteine. , glutamine, glycine, histidine, lysine, isoleucine, leucine, methionine, N-phenylalanine, proline, serine, taurine, threonine, tryptophan, tyrosine and valine. Advantageously, the amino acids are basic amino acids comprising an additional amine function optionally included in a ring or in a ureido function. Such basic amino acids are preferably chosen from those of formula (IV): R-CH 2 -CH (NH 2) -C (O) -OH, as well as its salts; formula (IV) wherein R represents a group selected from imidazolyl, preferably imidazolyl-4-yl; aminopropyl; aminoethyl; - (CH 2) 2 N (H) -C (O) -NH 2; and - (CH2) 2-N (H) -C (NH) -NH2. The compounds corresponding to formula (IV) are histidine, lysine, arginine, ornithine, citrulline.
[0030] The organic amine may also be chosen from heterocyclic organic amines. In addition to the histidine already mentioned in the amino acids, mention may be made, in particular, of pyridine, piperidine, imidazole, triazole, tetrazole and benzimidazole. The organic amine may also be selected from amino acid dipeptides. As amino acid dipeptides that can be used in the present invention, mention may be made in particular of carnosine, anserin and balenine. The organic amine may also be selected from compounds having a guanidine function. As amines of this type which can be used in the present invention, mention may in addition be made of the arginine already mentioned as amino acid, creatine, creatinine, 1,1-dimethylguanidine, 1,1-diethylguanidine, glycocyamine, metformin, agmatine, n-amidinoalanine, 3-guanidinopropionic acid, 4-guanidinobutyric acid and 2 - ([amino (imino) methyl] amino) ethane-1 acid sulfonic. As hybrid compounds, mention may be made of the salts of the amines mentioned above with acids such as carbonic acid and hydrochloric acid.
[0031] In particular, guanidine carbonate or monoethanolamine hydrochloride can be used. Preferably, the alkaline agent (s) present in the composition of the invention are chosen from ammonia, alkanolamines, amino acids in neutral or ionic form, in particular basic amino acids, and preferably corresponding to those of formula ( III). Even more preferentially, the alkaline agent (s) are chosen from ammonia, alkanolamines, especially monoethanolamine (MEA). More preferably, the alkaline agent (s) are chosen from alkanolamines, in particular monoethanolamine (MEA). vi) Chemical oxidizing agents: According to one particular embodiment of the invention, the dye composition comprises at least one chemical oxidizing agent. The term "chemical oxidizing agent" means an oxidizing agent different from the oxygen in the air. Preferably, the composition of the invention contains one or more chemical oxidizing agents. The oxidizing agents conventionally used for the oxidation dyeing of keratinous fibers are, for example, hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulfates, peracids and enzymes. oxidases among which include peroxidases, 2-electron oxidoreductases such as uricases and 4-electron oxygenases such as laccases. Hydrogen peroxide is particularly preferred. More particularly, the chemical oxidizing agent (s) is (are) chosen from hydrogen peroxide, urea peroxide, alkali metal bromates, peroxygenated salts such as, for example, persulfates, perborates, peracids and their precursors and percarbonates of alkali or alkaline earth metals. The chemical oxidizing agent (s) is advantageously constituted by hydrogen peroxide. The concentration of chemical oxidizing agents may vary, more particularly from 0.1 to 50% by weight, and even more preferably from 0.5 to 20% by weight, better still from 1 to 15% by weight relative to the weight of the composition. . The oxidizing composition may also contain various adjuvants conventionally used in hair dyeing compositions and as defined above. In particular, the oxidizing composition of the process of the invention comprises at least one fatty substance. More particularly, the oxidizing composition has a fatty substance content ranging preferably from 10 to 90% by weight, and even more particularly from 20 to 80% by weight, better still from 20 to 50% by weight of the oxidizing composition.
[0032] The dyeing process Another object of the invention relates to a process for dyeing keratinous fibers, in particular human keratinous fibers such as the hair, comprising applying to said fibers the dyeing composition of the invention comprising the ingredients: , ii) and possibly iii) to vi) as defined above. The process of the present invention is a process in which the dye composition according to the present invention as defined above is applied to the fibers in the presence of at least one chemical oxidizing agent vi) as defined previously for a time sufficient to obtain the desired color. The color may be revealed at acidic, neutral or alkaline pH and the chemical oxidizing agent (s) may be added to the dyeing composition of the invention just at the time of use or they may be (Fri) t be implemented from an oxidizing composition containing (s), applied simultaneously or sequentially to the composition of the invention. According to a particular embodiment of the invention the composition which comprises the ingredients i), ii) and optionally iii) to vi) as described above is obtained by mixing at least two compositions, preferably two or three compositions.
[0033] According to a particular variant of the invention, the method uses the composition which is derived from the mixture of two compositions: a dye composition (A) comprising: at least i) an imidazole coupler of formula (I) as defined above; at least ii) an oxidation base as defined above; - optionally at least one alkaline agent v) as defined above; and a composition (B) comprising: at least one chemical oxidizing agent vi as defined above; at least one of the compositions (A) and (B) comprising: at least iii) a fatty substance as defined above, and o optionally at least iv) a metal catalyst as defined above, it being understood that the content of the substance of the composition according to the invention resulting from the mixture of the compositions (A) + (B) comprises at least 10%, in particular at least 15 (/), more particularly at least 20 (:) / 0, and preferably at least 25% by weight relative to the total weight of the composition. According to one variant, the above process uses a composition which is derived from the mixture of three compositions, the three compositions being aqueous or at least one of them being anhydrous. In a particular process of the invention, two aqueous compositions (B ') and (C') and an anhydrous composition (A ') are used, the anhydrous composition (A') comprising at least iii) a fatty substance such as defined above, - the composition (B ') comprising: at least i) an imidazole coupler of formula (I) as defined above; and o at least ii) an oxidation base as defined above; - The composition (C ') comprising: at least vi) a chemical oxidizing agent as defined above: it being understood that: - optionally at least v) an alkaline agent as defined above; which is included in the compositions (A ') and / or (B') and preferably only in the composition (B '); optionally at least iv) a metal catalyst as defined above being present in at least one of the three compositions (A '), (B') or (C '), - these three compositions being such that the fat content of the composition resulting from the mixture of the three compositions (A ') + (B') + (C ') comprises at least 10%, in particular at least 15 (:) / 0, more particularly at least 20 (:) / 0, and preferably at least 25% by weight relative to the total weight of the composition resulting from the mixture of (A ') + (B') + (C '). The mixture obtained according to the preceding methods is then applied to the keratinous fibers. After a residence time of about 3 to 50 minutes, preferably about 5 to 30 minutes, the keratinous fibers are rinsed, washed with shampoo, rinsed again and then dried. The ready-to-use composition which is finally applied to the keratin fibers may be in various forms, such as in the form of liquids, creams, gels or in any other form suitable for dyeing keratinous fibers, and including human hair.
[0034] The kit: The invention also relates to a multi-compartment device or "kit" of dyeing comprising a first compartment containing the composition (A) as defined above in the dyeing process, and at least a second compartment containing the composition (B) as defined previously in the process, the compositions of the compartments being intended to be mixed before application, the composition after mixing of (A) + (B) is with a quantity of fat which represents at least 10%, in particular at least 15%, more particularly at least 20%, and preferably at least 25% by weight relative to the total weight of the composition resulting from the mixture of (A) + (B). According to one variant, the multi-compartment device of the invention is such that in a first compartment contains a dye composition comprising the ingredients i) to v) as defined above and a second compartment contains at least vi) a chemical oxidizing agent such as previously defined. These devices or kits may be equipped with means for delivering the desired mixture onto the hair, such as the devices described in patent FR-2 586 913 in the name of the applicant. From these devices, it is possible to dye the keratinous fibers from a process which comprises mixing a dye composition comprising at least i) a coupler of formula (I) as defined above and at least ii) an oxidation base with at least vi) a chemical oxidizing agent, and the application of the mixture obtained on the keratin fibers for a time sufficient to develop the desired coloration.
[0035] The examples which follow serve to illustrate the invention without, however, being limiting in nature.
[0036] EXAMPLES Staining compositions The coloring composition is produced at the time of use, by mixing the following three compositions: 6.7 g of the composition A + 2.7 g of the composition B + g of the composition C. Each of the The compositions are specified in the following tables: Ingredient composition Amount (g%) Petrolatum oil 64.5 Octy1-2-dodecanol 11.5 Modified hectorite distearyl dimethyl ammonium 3 Propylene carbonate 1 Sorbinate mono-laurate oxyethylenated (40E) Glycol Distearate 8 Oxyethylenated Lauryl Alcohol (20E) 1 10 Composition B Ingredients Amidazole coupler of the invention 3, 4, 5 or 6 20.10-3 mol% rc) N or imidazole coupler excluding the invention 1b: N oxidation base 2a, 2b, 2c, or 2d * 20.10-3 mol% Free monoethanolamine 0.14g Sodium metabisulfite 0.7g L-ascorbic acid 0.25g Propylene glycol 6.2g Ethanol 15.1g Hexylene glycol 3g Dipropylene glycol 3 g Benzyl alcohol 6 g Agent pH Qsp pH = 7 Deionized water Bases *: 2a HO / N - -NE-I2 / / HO, H2SO4 N, N bis (hydroxyethyl) -p-phenylenediamine sulfate 2b, HCl NH2 / N / - N, CI NN 1- [4- (3-AMINOPYRAZOLO [1,5-A] PYRIDIN-2-YL) -1,1-DIMETHYLPIPERAZIN-1-IUM CHLORIDE HYDROCHLORIDE 2c NH2 _ (:) _ OH HYDROXYETHOXY AMINOPYRAZOLOPYRIDINE HCL 2d N 2 I NH2 NN H2SO4 1-HYDROXYETHYL 4,5-DIAMINO PYRAZOLE SULFATE marketed under the name JAROCOL AHP by VIVIMED Composition C (oxidizing agent) Ingredients Quantity (g%) Hydrogen peroxide in 50% solution 12 Vaseline oil 20 Cetylstearyl alcohol (C16 / C18 30/70) 8 Cetylstearyl alcohol oxyethylenated (330E) 3 Tetra-sodium pyrophosphate, 10H20 0.03 Sodium crystalline hexahydroxystannate 0.04 Diethylene triamine pentaacetic acid, pentasodium salt in 40% aqueous solution 0.15 Poly-dimethyl diallyl ammonium chloride in 1 40% unstabilized water 0.5 Poly [dimethyliminio] -1,3-propane dichloride 0.25 diyl (dimethyliminio) -1,6-hexanediyl] in solution 60% aqueous Amides of protected oxyethylenated (40E) rapeseed acids 1.3 Vitamin E 0.1 Glycerol 0.5 Phosphoric acid qsp pH = 2.2 Deionized water QSP 100 Natural Caucasian hair strands (BN) with 90% white hair are treated with coloring composition mixture of A + B + C which is then left for 35 minutes at room temperature or 30 minutes at 40 ° C.
[0037] At the end of this exposure time, the locks are washed with iN0A POST shampoo, rinsed and then dried with a helmet. The coloration obtained is measured using a MINOLTA CM-3600D spectro-colorimeter. Colorimetric results Example 1 imidazole couplers of the invention 3 4 5 6 - / HO M 0 / 0 N eg s / N - il b NN 4- (5-Phenyl-1H-imidazol-2-yl) -2- (5-phenyl-1H-2- (2-phenyl) -3H-2,5-di-furan-2-yl-pyridine imidazol -2-yl) -imidazol-4-yl) -1H-imidazole phenol thiazole The couplers 1b, 3 to 6 of the invention are applied in combination with the heterocyclic base 2a, 2b, 2c and 2d for 30 minutes. at 40 ° C. It appears that the keratin fibers treated with the compositions of the invention are of varied and very powerful color. In addition, the rise in color is very satisfactory (Table 2) and significantly better than that of the coupler (lb) outside the invention. Table 1 Results Color L * (D65) b * (D65) AE * mounted D65) Untreated wicks (reference) 68.62 0.52 14.39 - Coupler lb (comparative) + base 2a matt gray 55.62 0, 1 14.01 13.02 + base 2c pink 51.82 8.09 10.99 18.74 Table 2 Results Color L * (D65) D65) b * (D65) AE * ab (D65) mounted Drills untreated BN 68.62 0.52 14.39 Coupler 3 + base 2a matt gray 52.51 -0.48 15.94 16.22 + base 2b purplish blue 34.89 4.25 -12.77 43.47 + base 2c purple 32,64 11,7 -6,37 43,02 + base 2d pink 50,29 20,98 2,94 29,76 Coupler 4 + base 2a matte gray 51,66 0,66 15,69 17,01 + base 2b matt light 58,14 -7,02 13,61 12,93 + base 2c beige 47,46 8,48 8,36 23,4 + base 2d light pink 54,72 16,21 9 21,64 Coupler 5 + base 2a matt gray 53,02 0,45 16,77 15,78 + base 2c pearly 45,09 3,25 8,82 24,33 Coupler 6 + base 2a matte gray 42,73 -0,11 11,23 26,09 + base 2b Blue gray 36,22 -5,41 -3,24 37,36 + base 2c black 31,33 2,83 2,96 39,07 + base 2d purple 35,84 9,87 -4 , 05 38.75 Example 2 0 - N / NNF / H 5- (4-methoxyphenyl) 1) -2-phenyl-1H-imidazole 4-methyl-2-phenylimidazole 53458-08-5 212-571-5 The couplers 7 and 8 of the invention are applied in combination with a heterocyclic base 2b, 2c and 2d to reason of 35 minutes at 27 ° C: It appears that the colorations obtained after treatment of keratin fibers have a rise in color on the fibers very satisfactory.
[0038] Table 3 Description Color L * (D65) a * (D65) b * (D65) AE * ab (D65) mounted Unstained references BN 60.4 0.75 13.95 For dye 7 in combination with violet base 2b 30.9 -1.58 -10.3 38.3 in coupling with the base 2c blue 34.5 12.5 -4.06 33.6 in coupling with the base 2d. 48.6 18.3 4.33 23.2 mother of pearl For dye 8 in combination with the base 2b red 42.4 21.7 17 27.7 in combination with the base 2c brown 48.1 7.09 4.78 16.6 in combination with the base 2d brown mother-of-pearl 51.3 15.8 11.55 17.8

权利要求:
Claims (22)
[0001]
REVENDICATIONS1. as well as its acid or base salts, organic or inorganic, its optical isomers, geometric, its tautomers or its solvates such as hydrates, compound of formula (I) in which: D R1 represents a) hydrogen atom (b) halogen, (c) (C1-C4) alkoxy or (d) phenoxy; particularly R 1 represents a hydrogen atom, or halogen, preferably hydrogen; R2 and R3, which may be identical or different, represent: a) an aryl group, preferably a C6-C10 group, which is: optionally substituted by at least one atom or group of groups chosen from: i) halogen, ii) hydroxy, iii) ( C1-C6) alkyl, iv) (C1-C4) alkoxy optionally substituted with hydroxy, carboxy or amino, v) (C1-C4) alkylthio, vi) trihalo (C1-C4) alkyl such as trifluoromethyl, vii) carboxy , viii) -C (O) O-M + with M + representing a cationic counterion of a mineral or organic base, ix) -S (O) 2 -R with R representing a hydroxy group, (C1-C4) alkyl or (di) (C1-C4) (alkyl) amino, x) C4) (alkyl) amino, x1) (C1-C4) alkylcarbonylamino such as methylcarbonylamino, xii) cyano, xiii) nitro, xiv) glucosyl and optionally fused to a monocyclic heterocycle, preferably comprising from 5 to 7 members and from 1 to 3 heteroatoms selected from oxygen, sulfur and nitrogen, optionally substituted with at least one i) carbonyl group, ii) (di ) (C1- C4) (alkyl) amino, iii) acetamido, iv) -S (O) 2 -R where R is hydroxy, (C1-C4) alkyl, or (di) (CiC4) (alkypamino, v) RS (0) ) 2-N (R ') - with R as defined above and R' representing a hydrogen atom or a (C1-C4) alkyl group; Preferably morpholinyl, piperidinyl, piperazinyl, or pyrrolydinyl, b) a 5- or 6-membered heterocyclic group, comprising from 1 to 4 heteroatoms, selected from oxygen, sulfur and nitrogen, said heterocycle being connected to the part imidazole of the compound (I) by a carbon atom and 1. Composition comprising: I) at least one imidazole coupler of formula (I) R2 R3ledit heterocycle being optionally fused to a benzo group, and / or optionally substituted by a second heterocycle to 5 or 6 members, or with a phenyl group optionally substituted with a trihalo (C 1 -C 4) alkyl group such as trifluoromethyl or (C 1 -C 4) alkoxy such as methoxy c) a linear (C 1 -C 6) alkyl group, branched, or cyclic, optionally substituted by at least one atom or group selected from i) halo, ii) hydroxy, iii) cyano, iv) (di) (C1-C4) (alkyl) amino, (di) (C1-C4) ( alkyl) amino (C1-C4) thio, (C1-C4) alkylphenyl, vi) (C1-C4) alkoxy, vii) (C1-C4) alkylt h, viii) morpholinyl or morpholino, ix) phenyl, x) piperazinyl or piperazino, xi) piperidinyl or piperidino, xii) thiophenyl, xiii) carboxy, ix) -C (O) O "M + with M + as previously defined, x amido H2N-C (O) -, xi) pyrimidinyl, xii) tetrahydrofuranyl, xiii) nitrophenyl; d) an aminocarbonyl group R4R5N-C (O) - with R4 and R5, which may be identical or different, represent a hydrogen atom, a (C1-C6) alkyl, phenyl or cycloalkyl group comprising from 5 to 7 chain members, such as cyclohexyl, or else R4 and R5 form together with the nitrogen atom which carries them a heterocycloalkyl group, comprising from 5 to 7 chain members, preferably 6 chain members, and optionally further comprising one or more additional heteroatoms, preferably said heterocycloalkyl group; is selected from morpholino, piperazino and piperidino; or R2 represents a (hetero) aryl group comprising from 5 to 10 members and from 1 to 3 heteroatoms selected from O, S, N, optionally substituted by one or more halogen atoms or groups selected from hydroxy, nitro, cyano, ( C1-C4) alkyl, (C1-C4) alkoxy, (C1-C4) alkylthio, (poly) halo (C1-C4) alkyl such as trifluoromethyl, (di) (C1-C4) (alkyl) amino, imidazolyl, thiophenyl , methylenedioxy, ethylenedioxy, R "-C (O) -, R" OC (O) -, R "R" NC (O) -, C (O) -N (R ") -, and R - S ( 0) p-, RRNS (O) p- with R "and R- representing a hydrogen atom or a (C1-C4) alkyl group and p is 1 or 2; or R3 represents a heteroaryl group comprising from 5 to 10 members, and from 1 to 3 heteroatoms chosen from 0, S, N, optionally substituted by one or more atoms or groups chosen from: i) halogen, ii) (C1-C4) alkyl, iii) (C 1 -C 4) alkoxy, iv) carboxy, v) cyano, vi) (poly) halo (C 1 -C 4) alkyl such as trifluoromethyl, vii) heterocycloalkyl comprising from 5 to 7 members and from 1 to 3 atoms nitrogen or oxygen such as piperidinyl, hexahydrodiazepinyl, viii) heteroaryl 'comprising from 5 to 6 members and from one to three atoms of oxygen, sulfur or nitrogen such as imidazolyl, furanyl, or (C1-C4) alkoxyphenyl; ii) at least one oxidation base; it being understood that when i) the imidazole coupler of formula (I) represents 2,4-diphenylimidazole, then ii) the oxidation base is different from 1-dimethylamino-4-aniline.
[0002]
2. Composition according to the preceding claim wherein the coupler i) are such that in the formula (I), R2 represents an aryl group such as phenyl or naphthyl optionally substituted with one or more halogen atoms or groups as defined previously in c), preferably R2 is phenyl.
[0003]
3. Composition according to claim 1 wherein the coupler (s) i) are such that in formula (I), R2 represents a heteroaryl group such as furanyl, (benzo) thiophenyl, benzomorpholinyl, benzodioxole, imidazolyl, imidazolylimidazolyl, tetrazolyl, thiazolyl, pyridinyl, pyrimidyl, indolyl; preferably R2 represents a pyridinyl group.
[0004]
4. Composition according to claim 1 wherein the coupler i) are such that in formula (I), R2 represents a cycloalkyl group such as cyclohexyl.
[0005]
5. Composition according to any one of the preceding claims wherein the coupler or couplers i) are such that in formula (I), R3 represents a group: a) (C1-CB) alkyl optionally substituted with a cyano group; b) (C6-C10) aryl such as phenyl or naphthyl, optionally substituted by one or more atoms or groups selected from: i) halogen, ii) hydroxy, iii) nitro, iv) (C1-C4) alkyl, v) ( C1-C4) alkoxy, vi) (C4-C6) cyclohexyloxy, vii) (poly) hydroxy (C1-C4) alkoxy, viii) (di) (C1-C4) (alkyl) amino (C1-C4) alkoxy, ix (C3-C7) cycloalkyloxy, x) methylene-dioxy, x1) ethylenedioxy, xii) glucosyloxy, xiii) diazepanyl, xiv) benzyloxy, xv) R- S (O) 2 -N (R ') -, R representing a (C 1 -C 8) alkyl group, and R 'representing a hydrogen atom or a (C 1 -C 4) alkyl, xvi) (C 1 -C 4) alkylthio, xvii) (poly) halogeno (C 1 -C 4) group alkyl such as trifluoromethyl, xviii) (poly) halo (C1-C4) alkoxy such as trifluoromethoxy, xix) (di) (C1-C4) (alkyl) amino, xx) R - C (O) -; xxi) R "OC (O) -, xxiii) R" R "NC (O) -, xxiv) R" - C (O) -N (R ") - with R" and R "representing an atom hydrogen, or a (C1-C4) alkyl; C) heteroaryl group comprising from 5 to 10 members, and from 1 to 3 heteroatoms selected from 0, S, N, optionally substituted with one or more atoms or groups selected from: i) halogen, ii) (C1-C4) alkyl, iii) (C1-C4) alkoxy, iv) carboxy, v) cyano, vi) (poly) halo (C1-C4) alkyl such as trifluoromethyl, vii) heterocycloalkyl comprising 5 to 7 chain members and 1 to 3 nitrogen or oxygen atoms such as piperidinyl, hexahydrodiazepinyl, viii) heteroaryl 'comprising from 5 to 6 members and from one to three atoms of oxygen, sulfur or nitrogen such as imidazolyl, furanyl, or (C1-C4) alkoxyphenyl.
[0006]
6. Composition according to the preceding claim wherein the coupler i) are such that in the formula (I), R3 represents a group b) aryl optionally substituted by the atoms or groups i) to xxiv) as defined in the claim Preferentially phenyl or naphthyl, more particularly phenyl.
[0007]
7. Composition according to claim 5 wherein the coupler i) are such that in the formula (I), R3 represents a group c) heteroaryl preferably selected from furanyl, thiophenyl, imidazolyl, pyrrolyl, indolyl, pyridinyl, (iso) quinolinyl, (iso) thiazolyl, chromanyl, said heterocycle being optionally substituted by at least one atom or group selected from i) to viii) as defined in claim 5.
[0008]
8. Composition according to any one of claims 1, 3, 5 and 7 wherein the coupler or couplers of formula (I) are such that R2 and R3, identical or different, represent a heteroaryl group, and R1 an atom of hydrogen; preferably chosen from those of formula (IA): -N a (IA) as well as its acid or base salts, organic or inorganic, its optical isomers, geometric, its tautomers or its solvates such as hydrates, composed of formula (IA) in which: Y1 and Y2, which are identical or different, represent a nitrogen atom or a CR 'group with R' representing a hydrogen atom or a (C1-C4) alkyl group; X 1 represents an oxygen, sulfur or NR 'atom with R' as defined above, preferably R 'represents a hydrogen atom, - X 2 represents an oxygen atom, or NR' with R 'such that defined above, preferably R 'represents a hydrogen atom; - Ri, represents a hydrogen atom or a group selected from (C1-C4) alkyl, NO2 and amino NRi "Ri" with R1 "and R1", identical or different, represent a (C1-C4) alkyl group; R2a represents a hydrogen atom or a group chosen from (C1-C4) alkyl, and amino NR2 "R2" with R2 "and R2", which may be identical or different, represent a (C1-C4) alkyl group or together form with the nitrogen atom carrying them a heterocycloalkyl group comprising from 5 to 7, preferably 5-membered, and optionally from 1 to 3 additional heteroatoms selected from 0, S, and N such as pyrrolidino, morpholino, piperazino, piperidino; .
[0009]
9. Composition according to any one of claims 1, 3, 5 and 6 wherein the coupler (s) of formula (I) are such that R2 represents a heteroaryl group, R3 represents a phenyl group and R1 represents a hydrogen atom and preferably chosen from those of formula (IB): R2b as well as its acid or base salts, organic or inorganic, its optical isomers, geometric, its tautomers or its solvates such as hydrates, compound of formula (IB) in which - Xi represents an oxygen atom, sulfur or NR 'with R' as defined above, preferably R 'represents a hydrogen atom, - Yi represents a nitrogen atom or a group CR' with R ' representing a hydrogen atom or a group selected from (C1-C4) alkyl,; Rib represents a hydrogen atom or a group chosen from (C1-C4) alkyl, hydroxy (C1-C4) alkyl, cyano, SO3M, and amino NR-R "with Ri" and Ri, which are identical or different, represent a (C1-C4) alkyl group, with M representing a hydrogen atom, a cationic counterion such as ammonium, or alkali or alkaline earth metal such as Na, or K; - R2b represents a (C1-C4) alkyl group .
[0010]
10. Composition according to any one of the preceding claims wherein the coupler or couplers i) are chosen from the compounds of formula (I), for which: R R 4 H phenyl phenyl H phenyl 4-methoxy-1-phenyl H phenyl 4 1-phenyl-phenyl-phenyl-2-pyridyl-phenyl-4-nitro-1-phenyl-4-nitro-1-phenyl phenyl-4-methoxy-1-3-pyridyl-6-phenyl methyl-1-pyridyl H Phenyl H, phenyl, phenyl, phenyl, phenyl, phenyl, phenyl, phenyl, phenyl, phenyl, phenyl, phenyl, phenyl, phenyl, phenyl, phenyl, phenyl 7- FFH Phenyl O-- H i -. H 0 H 4-methoxy-1-4-methoxy-1-phenyl phenyl H - O HH OH -OH H., 7-HH HH Phenyl FFH 3 HF Phenyl H Phenyl HH - i ----- CN H Phenyl H phenyl phenyl phenyl phenol HH phenyl) phenyl phenyl phenyl NHH phenyl phenyl phenyl Phenyl Phenyl H - Phenyl - (1HH) Phenyl Phenyl H Phenyl HH Phenyl ## STR2 ## wherein: ## STR2 ## Phenyl H Phenyl H Phenyl H Phenyl H: Phenyl H 0, Phenyl H 1, Phenyl H, H Phenyl HHHH H, Phenyl Phenyl H Phenyl H Phenyl H, Phenyl H Phenyl HHH CH, H Phenyl H; /..., (1), ## STR2 ## X Phenyl H, I, C H Phenyl H Phenyl H Phenyl Cl Phenyl P Cl H 7 Br .-- - ,, - - -) Phenyl Br / CI OH RT R2 Fe Methyl Phenyl H -, -. Phenyl H Methyl H -CH 2 -OH Phenyl H -CH 2-CN-H -CH 2 -OH -OH H Phenyl H - Phenyl H Phenyl - N H, Phenyl, Phenyl Cl Phenyl Ci 1 N, Br Phenyl - Cl Cl Phenyl o . ## STR2 ## Phenyl H Methyl H -CH 2 -CH 2 -phenyl OH H -CH 2 -OH H -CH 2 -OH Phenyl-CH 2-CN-CH 2 -OH Phenyl Methyl CH 3 ## STR2 ## wherein ## STR1 ## ## STR2 ## ## STR1 ## -CH 2 -CH 2 -NH 2 -4 -CH 2 -CH 2 -OH-H; H Methyl H Methyl-OH H Methyl H Methyl H -CH 2 -CH 2 -OH H 2 H 2 H 2 -H 2 -propyl H Methyl H Cyclohexyl Phenyl H-propyl Phenyl H-Phenyl H Methyl H -isr-Phenyl H -CH 2 H.sub.2 H.sub.2 H.sub.2 H.sub.2 H.sub.2 H.sub.2 H.sub.2 H.sub.2 H.sub.2 H.sub.2 H.sub.2 H.sub.2 H.sub.2 H.sub.2 H.sub.2 H.sub.2 H.sub.2 H.sub.2 H.sub.2 H.sub.2 H. . Methyl H -H 2 -CH 2 -CH 2 -Phyl-C-12-NH 2 H -CH 2 -CH 2 -phenyl-COOH H -CH 2 -CH 2 -phenyl C (O) -NH 2 H -CH 2 -COOH H Methyl H Phenyl H-phenyl H -CH 2 -CH 2 -NH 2 H n -Hexyl Phenyl H n -propyl methyl -CH 2 -CH 2 -OH H -CH 2 -HH Phenyl HH Methyl -CH 2 -CH 2 -OH H -CH 2 Methyl HH propyl H Methyl -CH2-CH2-OH H-C112-CH2-OH HH Isopropyl Phenyl Phenyl H Phenyl H Phenyl H F, C H2 -OH H el, H Methyl Methyl HH Methyl Phenyl Phenyl Phenyl Phenyl, Phenyl, Phenyl, Phenyl, Phenyl, Phenyl and Phenyl - CH, H phenyl H -CH 2 -OH H -CH 2 -OH -H-methyl-phenyl-phenyl H-phenyl-phenyl H-phenyl-phenyl-1-methyl ',', H o H -, -----, .. HH. ## STR2 ## wherein: ## STR2 ## Phenyl H ## STR2 ## ## STR2 ## ## STR2 ## o 1-1 H, rik N H H \. Phenyl phenyl H phenyl H phenyl N H H Phenyl N H -CF 3 O / with which corresponds to the point of attachment of the group to the rest of the imidazole of formula (I); as well as the compounds of the following formulas: ## STR2 ## where R 1 = R 2 = R 2 = methyl, I n, NHN: Rib = R2b = methyl PR 0: Rib = R2b = ethyl as well as their optical isomers, their tautomers, and their addition salts with an acid or a base.
[0011]
11. Composition according to any one of the preceding claims, in which the oxidation base (s) ii) are chosen from para-phenylenediamines, bis-phenylalkylenediamines, para-aminophenols, ortho-aminophenols, heterocyclic bases and their salts. addition; preferably chosen from para-phenylenediamine bases and heterocyclic bases such as 3-aminopyrazolo [1,5-a] pyridine bases and pyrazole derivatives.
[0012]
12. Composition according to any one of the preceding claims wherein the oxidation base (s) ii) are chosen from: - 3-aminopyrazolo- [1,5-4-pyridines preferably substituted in position 2 by: a) a (di) (C1-C6) (alkyl) amino group wherein the alkyl groups may be substituted by one or more hydroxy, amino, or imidazolium groups; b) a heterocycloalkyl group comprising from 5 to 7 members, and from 1 to 3 heteroatoms, cationic or otherwise, optionally substituted with one or more (C1-C6) alkyl groups such as di (C1-C4) alkylpiperazinium; c) a (C1-C6) alkoxy group optionally substituted by one or more hydroxyl groups such as 13-hydroxyalkoxy and also their addition salts; di or triaminopyrazole preferably chosen from 4,5-diamino-1-methyl pyrazole, 4,5-diamino-1- (13-hydroxyethyl) pyrazole, 3,4-diamino pyrazole, 4,5-diamino 1 (4,5'-chlorobenzyl) pyrazole, 4,5-diamino-1,3-dimethyl pyrazole, 4,5-diamino-3-methyl-1-phenyl pyrazole, 4,5-diamino-1-methyl-3-phenyl pyrazole, 4-amino-1,3-dimethyl-5-hydrazino pyrazole, 1-IDenzyl-4,5-diamino-3-methyl-pyrazole, 4,5-diamino-3-tert-butyl-1-methyl pyrazole, 4,5-diamino 1-tert-butyl 3-methyl pyrazole, 4,5-diamino-1- (13-hydroxyethyl) 3-methyl pyrazole, 4,5-diamino-1-ethyl-3-methyl-pyrazole, 4,5-diamino-1- ethyl 3- (4'-methoxyphenyl) pyrazole, 4,5-diamino-1-ethyl-3-hydroxymethyl pyrazole, 4,5-diamino-3-hydroxymethyl-1-methyl pyrazole, 4,5-diamino-3-hydroxymethyl-1 isopropyl pyrazole, 4,5-diamino-3-methyl-1-isopropyl pyrazole, 4-amino-5- (2'-aminoethyl) amino-1,3-dimethyl pyrazole, 3,4,5-triamino pyrazole, methyl 3,4,5-tria mino pyrazole, 3,5-diamino-1-methyl-4-methylamino pyrazole, 3,5-diamino 4- (p-hydroxyethyl) amino-1-methyl pyrazole, and their addition salts.
[0013]
13. Composition according to any one of the preceding claims which comprises iii) at least one fatty substance, the fatty substance content preferably ranging from 10 to 80% by weight, and even more particularly ranging from 20 to 80% by weight, more preferably 25 to 75% by weight, and most preferably 40 to 70% by weight relative to the total weight of the dye composition, more preferably between 50 and 60% by weight relative to the total weight of the dye composition.
[0014]
14. Composition according to any one of the preceding claims, characterized in that iii) the fatty substance or bodies are liquid at 25 ° C and at atmospheric pressure, preferably selected from C6-C16 hydrocarbons, hydrocarbons with more than 16 carbon atoms, triglycerides, fatty alcohols, fatty acid esters and / or fatty alcohol esters other than triglycerides, or mixtures thereof and preferably from liquid petroleum jelly, polydecenes, liquid fatty alcohols, esters of fatty acids and / or liquid fatty alcohols, or mixtures thereof and even more preferentially, among liquid petroleum jelly and octy1-2-dodecanol.
[0015]
15. Composition according to any one of the preceding claims, which comprises iv) one or more metal catalysts, preferably selected from metal salts of oxidation state 11 and which has two ligands derived from carboxylic acid C2-C10 or (Poly) hydroxy acid, especially the metal salts are complexed by two carboxylate groups such as those of formula (II): Ra-C (O) -O-M-O-C (O) -Rb (II) and their solvates such as hydrates and their enantiomers Formula (II) in which: - M represents a metal (11) or metal2 + of oxidation state 2, - Ra and Rb, which may be identical or different, represent a (poly) (hydroxy) group (C1-C6) alkyl; more particularly, the metal catalysts are chosen from organic acid salts of transition metals, in particular of manganese, and inorganic salts of rare earth metals, in particular cerium.
[0016]
16. Composition according to any one of the preceding claims, characterized in that it comprises v) one or more alkaline agents, preferably inorganic, organic or hybrid and especially selected from ammonia, alkali carbonates or bicarbonates such as sodium or potassium carbonates or bicarbonates, sodium or potassium hydroxides, organic amines chosen from alkanolamines, oxyethylenated and / or oxypropylenated ethylenediamines, amino acids and compounds of formula (III) or mixtures thereof Rx Rz N - W - NR (Rt formula (III) in which W is a divalent C 1 -C 6 alkylene radical optionally substituted by one or more hydroxyl groups or a C 1 -C 6 alkyl radical, and / or optionally interrupted by one or more heteroatoms such that 0, or NR '; Rx, Ry, Rz, Rt, R' and the same or different, represent a hydrogen atom, a C1-C6 alkyl or hydroxyalkyl radical; C1-C6, C1-C6 aminoalkyl, particularly e) the alkalinizing agent (s) are chosen from alkanolamines, and more particularly monoethanolamine, and amino acids in neutral or ionic form.
[0017]
17. Composition according to any one of the preceding claims, which comprises vi) one or more chemical oxidizing agents, particularly chosen from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates. and persulfates, peracids and oxidase enzymes, among which mention may be made of peroxidases, 2-electron oxidoreductases such as uricases and 4-electron offleases such as laccases; preferably the chemical oxidizing agent is hydrogen peroxide.
[0018]
18. Compound of formula (IA) or (IB) as defined in claims 8 or 9, preferably the compounds are chosen from those of formula A to R as defined in claim 10, as well as their optical isomers, their tautomers, and their addition salts with an acid or a base.
[0019]
19. A process for dyeing keratinous fibers, in particular human keratinous fibers such as the hair, comprising applying to said fibers the composition according to any one of claims 1 to 17.
[0020]
20. Method according to the preceding claim, wherein the composition is derived from the mixture of either: i) two compositions: a composition (A) comprising: at least one imidazolyl coupler i) as defined in any one of claims 1 to 10 and 18; at least one oxidation base ii) as defined in any one of claims 1, 11 or 12; - optionally at least one alkaline agent y) as defined in claim 16; and a composition (B) comprising: - at least vi) a chemical oxidizing agent as defined in claim 17; at least one of compositions (A) and (B) comprising: o at least iii) a fatty substance as defined in claim 14, and at least optionally at least iv) a metal catalyst as defined in claim 15, it being understood that the fat content of the composition resulting from the mixing of the compositions (A) + (B) preferably comprises at least 10%, in particular at least 15%, more particularly at least 20%, and preferably at least 25% by weight. weight relative to the total weight of the composition; ii) three compositions: two aqueous compositions (B ') and (C') and an anhydrous composition (A '), the anhydrous composition (A') comprising at least iii) a fatty substance as defined in claim 14 ; the composition (B ') comprising: at least i) an imidazole coupler of formula (I) as defined in any one of claims 1 to 10 and 18; at least one oxidation base ii) as defined in any one of claims 1, 11 or 12; and the composition (C ') comprising at least vi) a chemical oxidizing agent as defined in claim 17; it being understood that: at least v) an alkaline agent as defined in claim 16; which is included in the compositions (A ') and / or (B') and preferably only in the composition (B '); optionally at least iv) a metal catalyst as defined in claim 15, is included in at least one of the compositions (A '), (B') or, - these three compositions being such that the fat content of the composition resulting from the mixture of the three compositions (A ') + (B') + (C ') preferably comprises at least 10%, in particular at least 15%, more particularly at least 20%, and preferably at least 25% by weight relative to the total weight of the composition resulting from the mixture of (A ') + (B') + (C '). 30
[0021]
21. A multi-compartment device comprising a first compartment containing the composition (A) as defined in the preceding claim and at least a second compartment containing the composition (B) as defined in the preceding claim, the compartment compositions being intended for Before being applied, to give a composition after admixture of (A) + (B), the amount of which in terms of fat content preferably represents at least 10%, in particular at least 15%, more particularly at least 20%, and preferably at least 25% by weight relative to the total weight of the composition resulting from the mixture of (A) + (B).
[0022]
22. Use of at least one imidazole coupler of formula (I) as defined according to any one of claims 1 to 10 and 18 for the oxidation dyeing of keratinous fibers.

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同族专利:

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WO2015173321A1|2015-11-19|

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FR3020944B1|2017-10-13|

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FR2730924A1|1995-02-27|1996-08-30|Oreal|KERATINIC FIBER OXIDATION DYE COMPOSITION COMPRISING A DIAMINOPYRAZOLE DERIVATIVE AND A HETEROCYCLIC COUPLER AND DYEING METHOD|

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US5834164A|1995-05-18|1998-11-10|Konica Corporation|Silver halide photographic light sensitive material comprising a coupler capable of chelation and method for forming images by the use thereof|

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JPH10250231A|1997-03-14|1998-09-22|Konica Corp|Optical recording medium and optical recording method|

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FR2974509A1|2011-04-29|2012-11-02|Oreal|COLORING COMPOSITION USING A PARTICULAR PHENOLIC COUPLER IN BODY-RICH MEDIA, METHODS AND DEVICE|FR3060340A1|2016-12-20|2018-06-22|L'oreal|CAPILLARY COLORING COMPOSITION COMPRISING OXIDATION DYE, OXIDIZING AGENT, NITROGENIC HETEROCYCLIC COMPOUND, AND POLYPHOSPHORIC DERIVATIVE|FR2855406B1|2003-06-02|2006-08-04|Oreal|NOVEL IMIDAZOLE COMPOUNDS AND THE USE THEREOF FOR THE DYING OF KERATIN FIBERS|WO2019194220A1|2018-04-06|2019-10-10|日本曹達株式会社|arylsulfonamide compound and pest control agent|

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CN111057043B|2019-11-29|2021-11-02|深圳市贝加电子材料有限公司|Imidazole compound, preparation method and application thereof, organic weldable protective agent containing imidazole compound and surface treatment method|

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US11180473B2|2020-03-27|2021-11-23|Landos Biopharma, Inc.|PLXDC2 ligands|

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优先权:

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申请号 | 申请日 | 专利标题

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FR1454396A|FR3020944B1|2014-05-16|2014-05-16|COMPOSITION FOR COLORING KERATIN FIBERS COMPRISING A PARTICULAR IMIDAZOLE COUPLER AND AN OXIDATION BASE|FR1454396A| FR3020944B1|2014-05-16|2014-05-16|COMPOSITION FOR COLORING KERATIN FIBERS COMPRISING A PARTICULAR IMIDAZOLE COUPLER AND AN OXIDATION BASE|

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PCT/EP2015/060634| WO2015173321A1|2014-05-16|2015-05-13|Composition for dyeing keratin fibres, comprising a particular imidazole coupler and an oxidation base|