WO2016198656A1 - Hair dyeing process involving a dyeing step using a dye and a titanium salt, and a revealing step using an alkaline agent comprising not more than one amine function - Google Patents

Hair dyeing process involving a dyeing step using a dye and a titanium salt, and a revealing step using an alkaline agent comprising not more than one amine function Download PDF

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Publication number
WO2016198656A1
WO2016198656A1 PCT/EP2016/063380 EP2016063380W WO2016198656A1 WO 2016198656 A1 WO2016198656 A1 WO 2016198656A1 EP 2016063380 W EP2016063380 W EP 2016063380W WO 2016198656 A1 WO2016198656 A1 WO 2016198656A1
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chosen
acid
composition
preferentially
optionally
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PCT/EP2016/063380
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French (fr)
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Boris Lalleman
Alain Lagrange
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L'oreal
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/10—Preparations for permanently dyeing the hair
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/29—Titanium; Compounds thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/36—Carboxylic acids; Salts or anhydrides thereof
    • A61K8/365—Hydroxycarboxylic acids; Ketocarboxylic acids
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/4973—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with oxygen as the only hetero atom
    • A61K8/498—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with oxygen as the only hetero atom having 6-membered rings or their condensed derivatives, e.g. coumarin
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/80—Process related aspects concerning the preparation of the cosmetic composition or the storage or application thereof
    • A61K2800/88—Two- or multipart kits
    • A61K2800/884—Sequential application

Definitions

  • the present invention relates to a process for dyeing keratin fibres, in particular human keratin fibres such as the hair, comprising at least two steps in which said fibres are treated first with a cosmetic dye composition Ci) comprising a) one or more dyes, which are preferably natural, b) one or more titanium salts and b1 ) optionally one or more particular carboxylic acids, and said fibres are then treated with a cosmetic revealing composition Cii) comprising c) one or more alkaline agents each comprising not more than one amine function and d) optionally one or more chemical oxidizing agents; to a cosmetic composition comprising ingredients a), b), b1 ), c) and d) as defined previously; and to a multi-compartment device comprising ingredients a), b), b1 ), c) and d).
  • a cosmetic dye composition Ci comprising a) one or more dyes, which are preferably natural, b) one or more titanium salts and b1 ) optional
  • oxidation bases such as ortho- or para-phenylenediamines, ortho- or para-aminophenols and heterocyclic compounds.
  • oxidation bases are colourless or weakly coloured compounds, which, when combined with oxidizing products, may give rise to coloured compounds via a process of oxidative condensation.
  • couplers or colouring modifiers the latter being chosen in particular from aromatic meta-diamines, meta-aminophenols, meta- diphenols and certain heterocyclic compounds, such as indole compounds.
  • This oxidation dyeing process consists in applying to the keratin fibres bases or a mixture of bases and couplers with hydrogen peroxide (H 2 0 2 or aqueous hydrogen peroxide solution), as oxidizing agent, in leaving it to diffuse, and then in rinsing the fibres.
  • hydrogen peroxide H 2 0 2 or aqueous hydrogen peroxide solution
  • the colourings resulting therefrom are permanent, strong and resistant to external agents, especially to light, bad weather, washing, perspiration and rubbing.
  • dye keratin fibres and in particular human hair with dye compositions containing direct dyes.
  • the standard dyes that are used are, in particular, dyes of the nitrobenzene, anthraquinone, nitropyridine, azo, xanthene, acridine, azine or triarylmethane type, or natural dyes.
  • These dyes may be nonionic, anionic, cationic or amphoteric. These dyes are coloured or colouring molecules that have affinity for keratin fibres. These compositions containing one or more direct dyes are applied to keratin fibres for a time necessary to obtain the desired colouring, and are then rinsed out. The colourings that result therefrom are particularly chromatic colourings but are, however, only temporary or semi-permanent since the nature of the interactions that bind the direct dyes to the keratin fibre and their desorption from the surface and/or the core of the fibre are responsible for their weak dyeing power and their poor persistence with respect to light, washing or perspiration.
  • the colourings obtained using ODPs are not strong enough or intense enough, and/or are not very persistent, especially in the case of hair fibres.
  • one or more dyes chosen in particular from direct dyes and natural dyes, preferably chosen from ortho-diphenols (ODPs);
  • Ti titanium
  • the Ti atom of the salt is of oxidation state 2, 3 or 4, denoted Ti(ll), Ti(lll) or Ti(IV), preferably Ti(IV);
  • A represents a saturated or unsaturated, cyclic or non-cyclic and aromatic or non- aromatic hydrocarbon-based group, which is monovalent when n has the value 0 or polyvalent when n is greater than or equal to 1 , comprising from 1 to 50 carbon atoms, which is optionally interrupted with one or more heteroatoms and/or optionally substituted, especially with one or more hydroxyl groups; preferably, A represents a monovalent (CrC 6 )alkyl group or a polyvalent (CrC 6 )alkylene group optionally substituted with one or more hydroxyl groups;
  • - n represents an integer between 0 and 10 inclusive; preferably, n is between 0 and 5, such as between 0 and 2; and then
  • composition Cii) contains several alkaline agents, then each of the alkaline agents comprises not more than one amine function, said process preferably comprising an intermediate rinsing step between the application of Ci) and Cii).
  • composition(s) used in the process of the invention are aqueous.
  • Another subject of the invention is a cosmetic composition, preferably an aqueous composition, for dyeing keratin fibres, containing ingredients a), b), b1 ), c) and d) as defined previously and optionally an organic solvent as defined below.
  • Another subject of the present invention relates to a multi-compartment device comprising ingredients a), b), c) and optionally d) distributed in several compartments.
  • the multi-compartment device or "kit” is suitable for performing the dyeing process according to the invention.
  • the process according to the invention has the advantage of dyeing human keratin fibres, with persistent dyeing results.
  • the dyeing process according to the invention can produce colourings that are resistant to washing, perspiration and light without impairing the fibres.
  • the resistance to perspiration is particularly good.
  • the dyeing process used can induce satisfactory "build-up” and/or intensity (power) of the colouring.
  • the process of the invention uses at least one composition Ci) comprising a) one or more dyes chosen in particular from oxidation dyes, direct dyes and dyes of natural origin, preferably chosen from ortho-diphenols or ODPs. a1 ) According to a first embodiment of the invention, the dye(s) are chosen from oxidation dyes.
  • oxidation dye precursors that may be used in the present invention are generally chosen from oxidation bases, optionally combined with one or more couplers.
  • the oxidation bases may preferably be chosen from para-phenylenediamines, bis(phenyl)alkylenediamines, para-aminophenols, ortho-aminophenols and heterocyclic bases, and the addition salts thereof.
  • the oxidation base(s) of the invention are chosen from para- phenylenediamines and heterocyclic bases.
  • para-phenylenediamines examples that may be mentioned include para-phenylenediamine, para-tolylenediamine, 2-chloro-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, 2,6-dimethyl- para-phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,5-dimethyl-para- phenylenediamine, ⁇ , ⁇ -dimethyl-para-phenylenediamine, N,N-diethyl-para- phenylenediamine, ⁇ , ⁇ -dipropyl-para-phenylenediamine, 4-amino-N,N-diethyl-3- methylaniline, N,N-bis(p-hydroxyethyl)-para-phenylenediamine, 4-N
  • para-phenylenediamine para-phenylenediamine, para- tolylenediamine, 2-isopropyl-para-phenylenediamine, 2-p-hydroxyethyl-para- phenylenediamine, 2-p-hydroxyethyloxy-para-phenylenediamine, 2,6-dimethyl-para- phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,3-dimethyl-para- phenylenediamine, N,N-bis(p-hydroxyethyl)-para-phenylenediamine, 2-chloro-para- phenylenediamine, 2-p-acetylaminoethyloxy-para-phenylenediamine and 2- methoxymethyl-para-phenylenediamine, and the addition salts thereof with an acid, are particularly preferred.
  • bis(phenyl)alkylenediamines examples that may be mentioned include ⁇ , ⁇ '- bis(p-hydroxyethyl)-N,N'-bis(4'-aminophenyl)-1 ,3-diaminopropanol, N,N'-bis(p- hydroxyethyl)-N,N'-bis(4'-aminophenyl)ethylenediamine, N,N'-bis(4- aminophenyl)tetramethylenediamine, N,N'-bis(p-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 and 1 ,8-bis(2,5-diaminophenoxy)
  • para-aminophenols examples that may be mentioned include para- aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 4-amino-3-chlorophenol, 4-amino-3-hydroxymethylphenol, 4-amino-2-methylphenol, 4-amino-2- hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol, 4-amino-2-(p-hydroxyethyl-aminomethyl)phenol and 4-amino-2-fluorophenol, and the addition salts thereof with an acid.
  • ortho-aminophenols examples that may be mentioned include 2- aminophenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol and 5-acetamido-2- aminophenol, and the addition salts thereof.
  • heterocyclic bases mention may be made in particular of pyridine derivatives, pyrimidine derivatives and pyrazole derivatives.
  • pyridine derivatives mention may be made of the compounds described for example in patents GB 1 026 978 and GB 1 153 196, for instance 2,5-diaminopyridine, 2- (4-methoxyphenyl)amino-3-aminopyridine and 3,4-diaminopyridine, and the addition salts thereof.
  • pyridine oxidation bases that are useful in the present invention are the 3- aminopyrazolo[1 ,5-a]pyridine oxidation bases or the addition salts thereof, described, for example, in patent application FR 2 801 308.
  • Examples that may be mentioned include pyrazolo[1 ,5-a]pyrid-3-ylamine, 2- acetylaminopyrazolo[1 ,5-a]pyrid-3-ylamine, 2-(morpholin-4-yl)pyrazolo[1 ,5-a]pyrid-3- ylamine, 3-aminopyrazolo[1 ,5-a]pyridine-2-carboxylic acid, 2-methoxypyrazolo[1 ,5- a]pyrid-3-ylamine, (3-aminopyrazolo[1 ,5-a]pyrid-7-yl)methanol, 2-(3-aminopyrazolo[1 ,5- a]pyrid-5-yl)ethanol, 2-(3-aminopyrazolo[1 ,5-a]pyrid-7-yl)ethanol, (3-aminopyrazolo[1 ,5- a]pyrid-2-yl)
  • oxidation bases according to the invention are chosen from 3- aminopyrazolo[1 ,5-a]pyridines preferably substituted in position 2 with:
  • a cationic or non-cationic 5- to 7-membered heterocycloalkyl group comprising from 1 to 3 heteroatoms, optionally substituted with one or more (CrC 6 )alkyl groups such as di(CrC 4 )alkylpiperazinium;
  • pyrimidine derivatives mention may be made of the compounds described, for example, in patents DE 2359399, JP 88169571 , JP 05-63124 and EP 0 770 375 or patent application WO 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 the addition salts thereof, and the tautomeric forms thereof, when a tautomeric equilibrium exists.
  • 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 the addition salts thereof, and the tautomeric forms thereof
  • the heterocyclic oxidation bases of the invention are chosen from 4,5-diaminopyrazoles such as 4,5-diamino-1 -(p-hydroxyethyl)pyrazole. Use may also be made of 4,5-diamino-1 -(p- methoxyethyl)pyrazole.
  • Use will preferably be made of a 4,5-diaminopyrazole and even more preferentially of 4,5-diamino-1 -(p-hydroxyethyl)pyrazole and/or a salt thereof.
  • Pyrazole derivatives that may also be mentioned include diamino-N,N- dihydropyrazolopyrazolones and in particular those described in patent application FR-A- 2 886 136, such as the following compounds and the addition salts thereof: 2,3-diamino- 6,7-dihydro-1 H,5H-pyrazolo[1 ,2-a]pyrazol-1 -one, 2-amino-3-ethylamino-6,7-dihydro- 1 H,5H-pyrazolo[1 ,2-a]pyrazol-1 -one, 2-amino-3-isopropylamino-6,7-dihydro-1 H,5H- pyrazolo[1 ,2-a]pyrazol-1 -one, 2-amino-3-(pyrrolidin-1 -yl)-6,7-dihydro-1 H,5H-pyrazolo[1 ,2- a]pyrazol-1 -one, 4,5-di
  • Use will preferably be made of 2,3-diamino-6,7-dihydro-1 H,5H-pyrazolo[1 ,2-a]pyrazol-1 - one and/or a salt thereof.
  • Heterocyclic bases that will preferentially be used include 4,5-diamino-1 -(p- hydroxyethyl)pyrazole and/or 2,3-diamino-6,7-dihydro-1 H,5H-pyrazolo[1 ,2-a]pyrazol-1 - one and/or a salt thereof.
  • the oxidation base(s) used in the context of the invention are generally present in an amount ranging from 0.001% to 10% by weight approximately, and preferably ranging from 0.005% to 5%, relative to the total weight of the dye composition.
  • the additional couplers that are conventionally used for the dyeing of keratin fibres are preferably chosen from meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalene-based couplers and heterocyclic couplers, and also the addition salts thereof.
  • Examples that may be mentioned include 1 ,3-dihydroxybenzene, 1 ,3-dihydroxy-2- methylbenzene, 4-chloro-1 ,3-dihydroxybenzene, 1 -hydroxy-3-aminobenzene, 2-methyl-5- aminophenol, 3-amino-2-chloro-6-methylphenol, 2-methyl-5-hydroxyethylaminophenol, 2,4-diamino-1 -(3-hydroxyethyloxy)benzene, 2-amino-4-(3-hydroxyethylamino)-1 - methoxybenzene, 1 ,3-diaminobenzene, 1 ,3-bis(2,4-diaminophenoxy)propane, 3- ureidoaniline, 3-ureido-1 -dimethylaminobenzene, sesamol, thymol, 1 - ⁇ - hydroxyethylamino-3,4-methylenedioxybenzene, a-napht
  • addition salts of the oxidation bases and couplers that may be used within the context of the invention are in particular chosen from the addition salts with an acid such as the hydrochlorides, hydrobromides, sulfates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates.
  • an acid such as the hydrochlorides, hydrobromides, sulfates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates.
  • the coupler(s) are generally present in a total amount ranging from 0.001 % to 10% by weight approximately of the total weight of the dye composition, and preferably ranging from 0.005% to 5% by weight relative to the total weight of the dye composition. a2) According to one embodiment of the invention, the dye(s) are chosen from dyes of natural origin.
  • the dyes of natural origin may be chosen especially from spinulosin, orceins, polyphenols or ortho-diphenols (also known as ODPs in the rest of the description) and all extracts rich in ODPs, curcumin, indole derivatives such as isatin or indole-2,3-dione, indigoids including indigo, phthalocyanines and porphyrins in particular complexed to a metal, glycosyl or non-glycosyl iridoids, chromene dyes, anthraquinone and benzoquinone dyes such as lawsone or henna, juglone, spinulosin, chromene or chroman dyes, such as neoflavanols and neoflavanones, flavanols, and indigoids such as indigo; and anthocyanidols.
  • Use may also be made of extracts or decoctions containing these natural dyes and especially plant
  • the dye(s) of natural origin according to the invention may or may not be salified. They may also be in aglycone form (without bonded sugar) or in the form of glycosylated compounds.
  • glycosyl radical means a radical derived from a monosaccharide or polysaccharide.
  • the dye(s) are chosen from ortho-diphenol(s): ODP(s) and polyphenols.
  • ODP(s) means one or more compounds comprising one or more aromatic rings, at least one of which is a benzene ring substituted with at least two hydroxyl (OH) groups borne by two adjacent carbon atoms of said benzene group which is present in the structure of the ortho-diphenol(s).
  • the aromatic ring is more particularly a fused aryl or fused heteroaromatic ring, i.e. optionally comprising one or more heteroatoms, such as benzene, naphthalene, tetrahydronaphthalene, indane, indene, anthracene, phenanthrene, indole, isoindole, indoline, isoindoline, benzofuran, dihydrobenzofuran, chroman, isochroman, chromene, isochromene, quinoline, tetrahydroquinoline and isoquinoline, said aromatic ring comprising at least two hydroxyl groups borne by two adjacent carbon atoms of the aromatic ring.
  • the aromatic ring of the ortho-diphenol derivatives according to the invention is a benzene ring.
  • fused ring means that at least two saturated or unsaturated and heterocyclic or non-heterocyclic rings have a shared bond, i.e. at least one ring is placed side-by-side with another ring.
  • the dye(s) of the invention represent an ODP compound of formula (II), or an oligomer, tautomer, optical isomer or geometrical isomer thereof, and also salts or solvates thereof, such as
  • R 1 to R 4 which may be identical or different, represent: i) a hydrogen atom, ii) a halogen atom, or a group chosen from iii) hydroxyl, iv) carboxyl, v) (d- C 20 )alkyl carboxylate or (Ci-C 20 )alkoxycarbonyl, vi) optionally substituted amino, vii) optionally substituted linear or branched (C C 2 o)alkyl, viii) optionally substituted linear or branched (C 2 -C 20 )alkenyl, ix) optionally substituted cycloalkyl, x) (CrC 2 o)alkoxy, xi) (C 1 -C 2 o)alkoxy(C 1 -C 2 o)alkyl, xii) (CrC 20 )alkoxyaryl, xiii) aryl which may optionally be substituted,
  • the compound of formula (II) comprises from one to four rings.
  • a particular embodiment of the invention relates to one or more ODPs of formula (II), two adjacent substituents R 1 - R 2 , R 2 - R 3 or R 3 - R 4 of which cannot form, with the carbon atoms that bear them, a pyrrolyl radical.
  • R 2 and R 3 form a pyrrolyl or pyrrolidinyl radical fused to the benzene ring bearing the two hydroxyls.
  • saturated or unsaturated and optionally fused rings may also be optionally substituted
  • alkyf radicals are saturated, linear or branched, generally Ci-C 20 , particularly C Cio, hydrocarbon-based radicals, preferably Ci-C 6 alkyl radicals, such as methyl, ethyl, propyl, butyl, pentyl and hexyl;
  • alkenyf radicals are unsaturated and linear or branched C 2 -C 20 hydrocarbon- based radicals; preferably comprising at least one double bond, such as ethylene, propylene, butylene, pentylene, 2-methylpropylene and decylene;
  • aryf radicals are monocyclic or fused or non-fused polycyclic carbon-based radicals preferentially comprising from 6 to 30 carbon atoms, at least one ring of which is aromatic; preferentially, the aryl radical is chosen from phenyl, biphenyl, naphthyl, indenyl, anthracenyl and tetrahydronaphthyl;
  • alkoxy radicals are alkyl-oxy radicals with alkyl as defined previously, preferably C 1 -C 1 0 alkyl, such as methoxy, ethoxy, propoxy and butoxy;
  • the " ' alkoxyalkyf radicals are (Ci-C 2 o)alkoxy(Ci-C 2 o)alkyl radicals, such as methoxymethyl, ethoxymethyl, methoxyethyl, ethoxyethyl, etc.;
  • cycloalkyl' radicals are C 4 -C 8 cycloalkyl radicals, preferably cyclopentyl and cyclohexyl radicals; the cycloalkyl radicals may be substituted cycloalkyl radicals, in particular substituted with alkyl, alkoxy, carboxylic acid, hydroxyl, amine and ketone groups;
  • alkyl' or “alkenyl' radicals when they are “optionally substituted', may be substituted with at least one atom or group borne by at least one carbon atom chosen from: i) halogen; ii) hydroxyl; iii) (d-C 2 )alkoxy; iv) (CrCi 0 )alkoxycarbonyl; v) (poly)hydroxy(C 2 -C 4 )alkoxy; vi) amino; vii) 5- or 6-membered heterocycloalkyl; viii) optionally cationic 5- or 6-membered heteroaryl, preferably imidazolium, optionally substituted with a (CrC 4 )alkyl radical, preferably methyl; ix) amino substituted with one or two identical or different CrC 6 alkyl radicals optionally bearing at least: a) one hydroxyl group, b) one amino group optionally substituted with one or two optionally substituted (CrC 3 )al
  • glycosyf radical means a radical derived from a mono- or polysaccharide
  • radicals "containing one or more silicon atoms" are preferably polydimethylsiloxane, polydiphenylsiloxane, polydimethylphenylsiloxane or stearoxy dimethicone radicals;
  • heterocyclic radicals are radicals comprising, in at least one ring, one or more heteroatoms chosen in particular from O, N and S, preferably O or N, optionally substituted in particular with one or more alkyl, alkoxy, carboxyl, hydroxyl, amine or ketone groups.
  • These rings may comprise one or more oxo groups on the carbon atoms of the heterocycle; mention may in particular be made, among the heterocyclic radicals that may be used, of furyl, pyranyl, pyrrolyl, imidazolyl, pyrazolyl, pyridyl or thienyl groups; even more preferably, the heterocyclic groups are fused groups, such as benzofuryl, chromenyl, xanthenyl, indolyl, isoindolyl, quinolyl, isoquinolyl, chromanyl, isochromanyl, indolinyl, isoindolinyl, coumarinyl or isocoumarinyl groups, it being possible for these groups to be substituted, in particular with one or more OH groups.
  • the heterocyclic radicals that may be used, of furyl, pyranyl, pyrrolyl, imidazolyl, pyrazolyl, pyridyl or thi
  • the salts of the dyes of the invention may be salts of acids or of bases.
  • the acids may be mineral or organic.
  • the acid is hydrochloric acid, which results in chlorides.
  • the dye composition used in the process for dyeing keratin fibres comprises, as dye, one or more natural dyes.
  • the dye(s) a) of the invention are chosen from:
  • anthocyanidins for instance cyanidin, delphinidin and petunidin
  • anthocyanins or anthocyans for instance myrtillin
  • hydroxystilbenes for example 3,3',4,5'-tetrahydroxystilbene, optionally oxylated (for example glucosylated),
  • proanthocyanidins and especially the proanthocyanidins A1 , A2, B1 , B2, B3 and C1 , - chroman and chromene compounds,
  • the dye(s) a) are chosen from the following ODPs:
  • anthocyanidins for instance cyanidin, delphinidin and petunidin
  • anthocyanins or anthocyans for instance myrtillin
  • hydroxystilbenes for example 3,3',4,5'-tetrahydroxystilbene, optionally oxylated (for example glucosylated),
  • proanthocyanidins and especially the proanthocyanidins A1 , A2, B1 , B2, B3 and C1 ,
  • the ODP(s) are chosen from haematein, brazilein, gallic acid, tannic acid, haematoxylin and brazilin, and mixtures thereof.
  • the dye(s) of the invention are chosen from anthraquinone dyes, and preferably natural dyes, chosen from those of formulae (A1) and (A2) below:
  • R 1 and R 8 which may be identical or different, represent a hydrogen atom or a hydroxyl group or alkyl such as methyl;
  • R 2 represents a hydrogen atom or a hydroxyl group, carboxyl group -C(0)OH or carboxylate group -C(0)0 " , CTwith Q + representing an alkali metal or alkaline-earth metal such as potassium or calcium;
  • R 3 represents i) a hydrogen atom, ii) a hydroxyl group or iii) an optionally substituted aryl group, preferably a phenyl group optionally substituted with one or more groups chosen from a) hydroxyl, b) amino, c) (d-C 6 )alkyl optionally substituted with one or more groups chosen from hydroxyl, carboxyl and (CrC 4 )alkylcarbonylamino;
  • R 4 represents a hydrogen atom or a hydroxyl group
  • R 5 represents a hydrogen atom, or a hydroxyl, carboxyl or carboxylate group -C(0)0 " , CTwith Q + as defined previously;
  • R 6 represents a hydrogen atom, a hydroxyl group, -O " , Q + with Q + as defined previously, carboxyl or carboxylate group -C(0)0 " , CTwith Q + as defined previously;
  • R 7 represents a hydrogen atom or a glycosyl radical, preferably glucose
  • M represents a metal, preferably from column IIIA of the Periodic Table of the Elements, such as aluminium;
  • G represents a hydroxyl group, a water molecule or a ligand such as alkoxy or (di)(alkyl)amino.
  • the dyes of the invention are of formula (A1) and in particular, taken together or separately:
  • R 1 represents a hydroxyl or (CrC 4 )alkyl group
  • R 2 , R 4 and R 8 which may be identical or different, represent a hydrogen atom or a hydroxyl group
  • ⁇ R 3 represents a hydrogen atom, a hydroxyl group or a phenyl group optionally substituted with one or more groups chosen from hydroxyl, carboxyl and (C C 4 )alkylcarbonylamino such as:
  • R 5 and R 6 which may be identical or different, represent a hydrogen atom or a hydroxyl group, carboxyl group -C(0)OH or carboxylate group -C(0)0 " , Q + with Q + representing an alkali metal or alkaline-earth metal such as potassium or calcium; and
  • R 7 represents a hydrogen atom.
  • the dye(s) of the invention are of formula (A2) and in particular, taken together or separately:
  • R 1 represents a (CrC 4 )alkyl group
  • R 2 represents a carboxyl or carboxylate group -C(0)0 " , Q + with Q + representing an alkali metal or alkaline-earth metal such as potassium or calcium;
  • R 3 and R 8 represent a hydroxyl group
  • ⁇ R 4 represents a hydrogen atom or a hydroxyl group, preferably hydrogen
  • ⁇ R 6 represents a hydroxyl group or -O " , Q + with Q + as defined previously;
  • R 7 represents a glycosyl radical such as glucose.
  • the dye(s) of the invention are chosen from the following anthraquinones and extracts containing them:
  • carmine Cosmetic lake, cochineal, natural red 4, C.I. 75470 or E120, the aluminium salt of carminic acid
  • the dye(s) are chosen from benzoquinones and naphthoquinones, in particular juglone and lawsone.
  • benzoquinones and naphthoquinones in particular juglone and lawsone.
  • those derived from leaves of shrubs of the genus Lawsonia from the family of Lythraceae which is based on the principle of dyeing with the active agent lawsone: 2-hydroxy-1 ,4- naphthoquinone from henna.
  • Lawsone [83-72-7] (CI Natural Orange 6; CI 75420), also known as isojuglone, may be found in henna shrubs (Lawsonia alba, Lawsonia inermis).
  • henna is in powder form.
  • the henna powder may be screened to obtain particles with upper limit sizes corresponding to the orifices or mesh sizes of the screen particularly between 35 and 80 mesh (US).
  • the size of the henna powder particles is fine.
  • a particle size of less than or equal to 500 mm is more particularly intended.
  • the powder is constituted of fine particles with a size inclusively between 50 and 300 mm and more particularly between 10 and 200 mm. It is understood that said henna particles preferentially have a moisture content of between 0 to 10% by weight, relative to the total weight of the powders.
  • the dye(s) are chosen from indole derivatives such as isatin or indole-2,3-dione and indigo, preferably isatin.
  • the dye(s) are derived from the plants Isatis tinctoria, Calanthe discolor or Couroupita guianensis.
  • At least one cosmetic composition comprises at least one natural dye c) chosen from naphtoquinone dyes, such as lawsone or henna, juglone, spinulosin, preferably lawsone or henna, and/or from indole derivatives such as isatin or indole-2,3-dione, indigoids including indigo, preferably indigo.
  • naphtoquinone dyes such as lawsone or henna, juglone, spinulosin, preferably lawsone or henna
  • indole derivatives such as isatin or indole-2,3-dione, indigoids including indigo, preferably indigo.
  • At least one cosmetic composition comprises at least two natural dyes c), wherein preferably at least one dye is chosen from naphtoquinone dyes, such as lawsone or henna, juglone, spinulosin, preferably lawsone or henna, and/or from indole derivatives such as isatin or indole-2,3- dione, indigoids including indigo, preferably indigo ; or mixture thereof, better still said at least two natural dyes c) are chosen from naphtoquinone dyes such as lawsone or henna, juglone, spinulosin, preferably lawsone or henna, and indole derivatives such as isatin or indole-2,3-dione, indigoids including indigo, preferably indigo.
  • naphtoquinone dyes such as lawsone or henna, juglone, spinulosin, preferably lawsone or henna
  • the dye(s) are curcumine or curcumin.
  • This is a compound that is naturally present in curry, which is a polyphenol whose chemical name is (1 £,6£)-1 ,7-bis(4-hydroxy-3-methoxyphenyl)-1 ,6-heptadiene-3,5-dione, and also the tautomeric forms thereof.
  • the dye(s) of the invention are chosen from natural porphyrins and phthalocyanines, in particular those complexed with a metal, especially chlorophyllin and in particular that complexed with copper or magnesium, preferably copper chlorophyllin.
  • the dye(s) are chosen from glycosyl or non-glycosyl iridoids.
  • the dye(s) of the invention are chosen from (seco)iridoid glycoside or non-glycosyl (seco)iridoid (also known as aglycone), extracted from plants such as Rubiaceae, Euphorbiaceae, Valerianaceae, Cornaceae, Gentianaceae, Caprifoliaceae, Oleaceae, Ericaceae, Loganiaceae, etc., preferably Rubiaceae.
  • the dye(s) of the invention are derived from extracts of the following plants: Veronica persica; Genipa americana; Apodytes dimidiata; Randia canthioides; Tarenna attenuata and preferably Genipa americana.
  • the dye(s) a) are chosen from chromene or chroman dyes.
  • chromene or chroman dyes means dyes which comprise in their structure at least one bicycle of formula (B) below:
  • the dye(s) a) of the invention are of formula (B) and are preferentially chosen from neoflavonols and neoflavanones, particularly chosen from the dyes of the following formulae:
  • ⁇ X represents a group: // /
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 which may be identical or different, represent a hydrogen atom, a hydroxyl group, an optionally substituted alkyl group, an optionally substituted alkoxy group or an optionally substituted acyloxy group;
  • Rn , Ri2, Ri3, Ri 6, ig and R 20 which may be identical or different, represent a hydrogen atom or a CrC 4 alkyl radical
  • Ri4, Ri5, Ri7 and R 18 which may be identical or different, represent a hydrogen atom, a hydroxyl radical or a Ci-C 4 alkoxy radical.
  • the alkyl radicals mentioned in the preceding definitions of the substituents are saturated and linear or branched hydrocarbon-based radicals, generally C C-20, particularly CrC 10 , preferably CrC 6 , hydrocarbon-based radicals, such as methyl, ethyl, propyl, butyl, pentyl and hexyl.
  • the alkoxy radicals are alkyl-oxy radicals with the alkyl radicals as defined above and preferably the alkoxy radicals are C 1 -C 10 alkoxy radicals, such as methoxy, ethoxy, propoxy and butoxy.
  • the alkyl or alkoxy radicals when they are substituted, may be substituted with at least one substituent borne by at least one carbon atom chosen from: i) a halogen atom or ii) a hydroxyl group; iii) a C C 2 alkoxy group; iv) a CrC 10 alkoxycarbonyl group; v) a (poly)hydroxy(C 2 -C 4 )alkoxy group; vi) an amino group; vii) a 5- or 6-membered heterocycloalkyl group; viii) an optionally cationic 5- or 6-membered heteroaryl group, preferably imidazolium, optionally substituted with a (d-C 4 )alkyl radical, preferably methyl; ix) an amino radical substituted with one or two identical or different CrC 6 alkyl radicals optionally bearing at least: a) one hydroxyl group, b) one amino group optionally substituted with one or two optionally substituted CrC 3 al
  • the alkyl or alkoxy radicals of formula (III) are unsubstituted.
  • the dyes of formula (III) comprise a radical R 6 representing a hydroxyl group.
  • Another particular embodiment of the invention relates to the dye(s) of formula (III) for which the radical Ri represents a hydrogen atom or a hydroxyl group.
  • the dye(s) of the invention are of formula (III) and chosen from haematoxylin, haematein, brazilin and brazilein; preferentially haematoxylin and brazilin:
  • Brazilein is a conjugated form of a chroman compound of formula (A2).
  • the tautomeric structures (Ilia) and (1Mb) illustrated above are found in the scheme below.
  • haematoxylin/haematein and brazilin/brazilein type examples that may be mentioned include haematoxylin (Natural Black 1 according to the INCI name) and brazilin (Natural Red 24 according to the INCI name), dyes of the indochroman family, which are commercially available.
  • haematoxylin Natural Black 1 according to the INCI name
  • brazilin Natural Red 24 according to the INCI name
  • dyes of the indochroman family which are commercially available.
  • the latter dyes may exist in an oxidized form and may be obtained synthetically or by extraction of plants or vegetables known to be rich in these dyes.
  • the dye(s) of natural origin of the invention may be used in the form of extracts.
  • Use may be made of the following plant extracts (genus and species): Haematoxylon campechianum, extracted from oxidized logwood (Haematoxylon campechianum) brasiletto (Haematoxylum brasiletto, rich in brazilin and protosappanin), Quebracho (Schinopsis lorentzii) Caesalpinia echinata, Caesalpinia sappan, Caesalpinia spinosa, and Caesalpina brasiliensis.
  • the extracts are obtained by extracting the various plant parts, for instance the roots, the wood, the bark or the leaves.
  • the dye(s) of natural origin are of formula (II) and are obtained from logwood, pernambuco wood, sappan wood and Brazil wood.
  • the dyes are of formula (IV), preferably those for which Rn and R 13 represent an alkyl radical, preferably methyl.
  • R 12 , Ri e, R19 and R 20 denote, independently of each other, a hydrogen atom or an alkyl radical, preferably methyl.
  • R 14 and R 17 denote, independently of each other, a hydrogen atom or an alkoxy radical, preferably methoxy.
  • R 18 and R 15 denote, independently of each other, a hydrogen atom, a hydroxyl radical or an alkoxy radical, preferably methoxy.
  • a first particularly preferred family of dyes of natural origin of the invention that are suitable for use in the present invention is that of the dyes corresponding to formula (IV) above for which R 12 , Ri 5 , Ri 6 , i 7 , R19 and R 20 each represent a hydrogen atom, R ⁇ and R 13 each represent a methyl radical and R 14 represents a methoxy radical.
  • dyes of the invention of this first family are those for which R 18 represents a methoxy radical (santalin B) or a hydroxyl radical (santalin A).
  • a second particularly preferred family of dyes that are suitable for use in the present invention is that of the dyes corresponding to formula (IV) above for which:
  • Rn and R 13 each represent a methyl radical
  • R 17 represents a methoxy radical
  • a preferred dye of this second family is that for which, in addition, R 19 represents a methyl radical, R 20 , Ri 2 , Ri 4 , Ri 8 and R 1 6 each represent a hydrogen atom and R 15 represents a hydroxyl radical (santarubin A).
  • a second preferred dye of this second family is that for which R 18 , R 20 , R12, R14 and R 1 6 represent a hydrogen atom, R 15 represents a methoxy radical and R 19 represents a methyl radical (santarubin B).
  • a third family of preferred dyes of this second family is that for which R 20 , R 12 , Ri 4 , R15,
  • Ri e and Rig represent hydrogen and R 18 represents a hydroxyl radical (santarubin C).
  • the advantageous dye(s) of this second family are that for which R 15 represents a methoxy radical, R 18 and R 14 represent a hydrogen atom and R 20 , Ri 2 , Ri 6 and R 19 represent a methyl radical (tetra-O-methylsantarubin).
  • the natural dye(s) of formula (IV) may be used in the form of extracts.
  • Use may be made of plant extracts of red woods, bringing together generally the species of red woods from Asia and West Africa of the genus Pterocarpus and of the genus Baphia.
  • These woods are, for example, Pterocarpus santalinus, Pterocarpus osun, Pterocarpus soyauxii, Pterocarpus erinaceus, Pterocarpus indicus or Baphia nitida.
  • These woods may also be called padauk, sandalwood, narra wood, camwood or bar wood.
  • extracts that may be used, comprising dyes of formula (IV), in the present invention may be obtained, for example, from red sandalwood (Pterocarpus santalinus) by aqueous basic extraction, such as the product sold under the trade name Santal Concentre SL 709C by the company COPIAA, or also by means of solvent extraction of sandalwood powder, such as the product sold under the trade name Santal Poudre SL PP by the same company COPIAA. Mention may also be made of the aqueous/alcoholic extract of powdered red sandalwood from the company Alban Muller.
  • Extracts also suitable for the present invention can be obtained from woods such as camwood (Baphia nitida) or also bar wood (Pterocarpus soyauxii, Pterocarpus erinaceus): the latter is thus split up and then ground: a conventional alcoholic extraction or one by percolation is subsequently carried out on this ground material in order to collect a pulverulent extract particularly suitable for the implementation of the present invention.
  • woods such as camwood (Baphia nitida) or also bar wood (Pterocarpus soyauxii, Pterocarpus erinaceus): the latter is thus split up and then ground: a conventional alcoholic extraction or one by percolation is subsequently carried out on this ground material in order to collect a pulverulent extract particularly suitable for the implementation of the present invention.
  • the dye(s) of formulae (III) and (IV) of the invention may be salts of acids or bases that are cosmetically acceptable.
  • the acids may be mineral or organic.
  • the acid is hydrochloric acid, which results in chlorides.
  • the bases may be mineral or organic.
  • the bases are alkali metal hydroxides such as sodium hydroxide which leads to sodium salts.
  • the dye(s) are chosen from dihydroxyflavonoids, preferably of formula (V) and also the organic or mineral acid or base salts thereof, optical, geometric and tautomeric isomers thereof, and solvates thereof such as hydrates:
  • Ft 1 , Ft 2 , Ft 3 , Ft 4 , Ft 10 , Ft 11 , Ft 12 , Ft 13 and Ft 14 represent a hydrogen or halogen atom or a group chosen from i) hydroxyl, ii) (d-C 6 )alkyl, iii) (CrC 6 )alkoxy, iv) (CrC 6 )alkylthio, v) carboxyl, vi) alkyl or alkoxycarbonyl carboxylate, vii) optionally substituted amino, viii) optionally substituted linear or branched alkenyl, ix) optionally substituted cycloalkyl, x) optionally substituted aryl, xi) a group containing one or more silicon atoms, xii) (di)((hydroxy)(Ci-C 6 )alkyl)amino, xiii) glucosyl,
  • R 5 , R 6 , R 7 , R 8 and R 9 which may be identical or different, represent a hydrogen atom or a group chosen from a hydroxyl group, a (CrC 6 )alkyl group or a group R-Z-C(X)-
  • the unit (V) constitutes a polymeric unit of a polyphenol which will be linked to the other units of said polyphenol via positions 4, 6 or 8 of the chroman ring, in which case R 1 , or R 3 and R 6 form a covalent bond with the other units of said polyphenol;
  • R 5 with R 6 and/or R 7 with R 8 form, together with the carbon atom which bears them, an oxo group
  • R 9 when is a double bond between the oxygen atom and the carbon atom in position 2, then R 9 is absent, and when is a double bond between the carbon atoms in positions 3 and 4, then R 5 and R 7 are absent;
  • the compound of formula (V) when borne by the oxygen atom is a double bond, then the compound of formula (V) is cationic and an organic or mineral anionic counterion such as halide is associated therewith.
  • At least two radicals of the compounds of formula (V) chosen from R 1 , R 2 , R 3 , R 4 , R 10 , R 11 , R 12 , R 13 and R 14 , which are contiguous, represent a hydroxyl group.
  • the group R-Z-C(X)-Y- of the compounds of formula (V) represents a 3,4,5- trihydroxyphenyl- 1-carbonyloxy (-O-gallate).
  • the radicals Ri, R 2 , R 3 , R4, R10, R11 , R12, Ri3 and Ri 4 are chosen from a hydrogen atom and hydroxyl, glycosyloxy and alkoxy groups.
  • the dye(s) of the invention are chosen from: i) the flavanols of formula (Va) which preferably comprise at least two ortho hydroxyl groups, such as catechin, extracted from pine bark, epicatechin gallate, and cocoa flavonols, especially epicatechin, flavonols, in particular flavan-3-ol from green tea, and oligomers and polymers thereof known as proanthocyanidols or fused tannins such as theaflavin, theaflavin 3'-0-gallate, theaflavin 3,3'-0-digallate, proanthocyanidins A1 , A2, B1 , B2, B3 and C1 such as profisetinidin and procyanidin, and mixtures of the preceding compounds.
  • Va the flavanols of formula (Va) which preferably comprise at least two ortho hydroxyl groups, such as catechin, extracted from pine bark, epicatechin gallate, and cocoa flavonols, especially epicatechin, fla
  • Flavan-3-ol or flavanol (Va)
  • R 7 , R 8 which may be identical or different, represent a hydrogen atom or a group chosen from hydroxyl, (d-C 6 )alkyl or a group R-Z-C(X)-Y- as defined previously, preferably O-gallate, it being understood that at least one of the two groups;
  • R 7 or R 8 represents a hydroxyl group or R-Z-C(X)-Y- as defined previously;
  • R 5 and R 6 which may be identical or different, represent a hydrogen atom or a hydroxyl group or R 6 and R 8 form a bond or the unit (Va) constitutes the polymeric unit that will be bonded to the other units via positions 4, 6 or 8, in which case R 1 , or R 3 and R 6 form a bond; the radicals R 1 , R 2 , R 3 , R 4 , R 10 , R 11 , R 12 , R 13 and R 14 being as defined previously for formula (V);
  • proanthocyanidin compounds examples that may be mentioned include profisetinidin and procyanidin, the formulae of which are represented below;
  • flavonols of formula (Vb) which comprise at least two ortho hydroxyl groups, such as quercetin, luteolin, myricetol or fisetin, and/or two meta hydroxyl groups, such as morin, heterosides thereof, methoxylated derivatives thereof such as rhamnetin (which preferably comprise at least two ortho hydroxyl groups): Flavonol:
  • formula (Vb) the radicals Ft 1 , Ft 2 , Ft 3 , Ft 4 , Ft 10 , Ft 11 , Ft 12 , Ft 13 and Ft 14 are as defined previously in formula (V);
  • the flavones of formula (Vc) which comprise at least two ortho hydroxyl groups, such as luteolin, and heterosides thereof such as luteolol 7-O-glucoside, baicalin and orientin.
  • formula (Vc) the radicals Ft 1 , Ft 2 , Ft 3 , Ft 4 , Ft 10 , Ft 11 , Ft 12 , Ft 13 and Ft 14 are as defined previously in formula (V);
  • dihydroflavonols or dihydroxyflavanonols of formula (Vd) which comprise at least two ortho hydroxyl groups, such as dihydroquercetol, and heterosides thereof such as dihydroquercetol 3-O-rhamoside:
  • Flavanone (Ve)
  • Flavan-3,4-diol (Vf) and also the organic or mineral acid or base salts thereof, the optical isomers, geometrical isomers and tautomers thereof, and the solvates thereof such as hydrates; in which formula (Vf) the radicals Ft 1 , Ft 2 , Ft 3 , Ft 4 , Ft 10 , Ft 11 , Ft 12 , Ft 13 and Ft 14 are as defined previously in formula (V);
  • anthocyanidols (or anthocyanidins) of formula (Vg) which comprise at least two ortho hydroxyl groups, such as cyanidol, delphinidin, aurantinidin, luteolinidin, heterosides thereof, such as dihydroxyanthocyans (or dihydroxyanthocyanosides, or anthocyanins on the English model), oligomers and polymers thereof such as proanthocyanins, preferably proanthocyanidols and especially from blueberry;
  • formula (Vg) which comprise at least two ortho hydroxyl groups, such as cyanidol, delphinidin, aurantinidin, luteolinidin, heterosides thereof, such as dihydroxyanthocyans (or dihydroxyanthocyanosides, or anthocyanins on the English model), oligomers and polymers thereof such as proanthocyanins, preferably proanthocyanidols and especially from blueberry;
  • the dye(s) of the invention are compounds of formula (a), or an oligomer thereof, in salified or non-salified form:
  • R represents a hydrogen atom or a hydroxyl group
  • R' represents a hydroxyl group according to ( ⁇ '):
  • R 1 ; R 2 and R 3 which may be identical or different, represent a hydrogen atom or a hydroxyl group or (CrC 6 )alkoxy such as methoxy; • R 4 represents a hydrogen atom, a hydroxyl group or -O-glycoside; or alternatively the radicals R, Y and R' form, together with the carbon atoms that bear them, a heterocyclic group fused to ring A, of formula (b), (g) or (g') below:
  • ⁇ R 5 represents a hydrogen atom or a hydroxyl or -O-glycoside group
  • R 6 to Rio which may be identical or different, represent a hydrogen atom or a hydroxyl group, preferably R 6 and R 10 represent a hydrogen atom, R 7 , R 8 and R 9 represent a hydrogen atom or a hydroxyl group;
  • the dye(s) according to the invention are compounds of formula (a), and more particularly polyphenols such as tannic acid.
  • the dye(s) according to the invention may in particular be a mixture of proanthocyanidin derivatives such as profisetinidin and procyanidin and of compounds of formula (a), and more particularly polyphenols such as tannic acid.
  • the dye(s) of the invention are derived from plant extracts. Use may also be made of mixtures of plant extracts.
  • the natural extracts of the dyes according to the invention may be in the form of powders or liquids. Preferably, the extracts are in powder form.
  • the dye(s) of the invention are chosen from catechin, quercetin, brazilin, haematein, haematoxylin, chlorogenic acid, caffeic acid, gallic acid, catechol, L-DOPA, pelargonidin, cyanidin, (-)-epicatechin, (-)-epigallocatechin, (-)-epigallocatechin 3-gallate (EGCG), (+)-catechin, isoquercetin, pomiferin, esculetin, 6,7-dihydroxy-3-(3-hydroxy-2,4- dimethoxyphenyl)coumarin, santalin AC, mangiferin, butein, maritimetin, sulfuretin, robtein, betanidin, pericampylinone A, theaflavin, proanthocyanidin A2, proanthocyanidin B2, proanthocyanidin C1 , procyanidins DP 4-8, tannic acid, purpurogallin
  • the dye(s) of the invention are chromenes or chromans and are chosen from haematein, haematoxylin, brazilein, brazilin and santalin A.
  • carboxylate means carboxylic acid salt.
  • both forms may be used in the compositions according to the invention, as may the racemates.
  • the natural dye(s) are derived from extracts of animals, bacteria, fungi, algae, plants and fruits, used in their entirety or partially.
  • the extracts are derived from fruit, including citrus fruit, from vegetables, from trees and from shrubs. Use may also be made of mixtures of these extracts, which are rich in natural dyes, especially in ortho-diphenols as defined previously.
  • the natural dye(s) of the invention are derived from extracts of plants or plant parts.
  • the extracts are obtained by extraction of various plant parts, for instance the root, the wood, the bark, the leaf, the flower, the fruit, the seed, the pod or the peel.
  • extracts of tea leaves in particular of Japanese green tea, and of rose.
  • extracts of apple of grape (in particular of grape seed) or extracts of cocoa beans and/or pods.
  • extracts of potato or of onion peel mention may be made of extracts of potato or of onion peel.
  • extracts of tree wood mention may be made of extracts of pine bark and extracts of logwood or extracts of quebracho wood.
  • the ortho-diphenol derivative(s) are natural extracts, rich in ODPs.
  • the dye(s) of the invention are solely natural extracts.
  • the dye(s) according to the invention are chosen from catechin, quercetin, haematein, haematoxylin, brazilin, brazilein, gallic acid and tannic acid, and natural extracts containing them chosen from grape marc, pine bark, green tea, onion, cocoa bean, logwood, redwood and gall nut, sorghum (Sorghum vulgare) and quebracho wood.
  • the natural extracts according to the invention may be in the form of powders or liquids.
  • the extracts of the invention are provided in the form of powders.
  • the dye(s) are chosen from direct dyes.
  • the direct dye(s) that may be used in the context of the invention are chosen from fluorescent or non-fluorescent, synthetic or natural, anionic, cationic or neutral direct dyes.
  • the dye(s) are chosen from anionic direct dyes or dyes commonly referred to as “acid” direct dyes or “acid dyes” on account of their affinity for alkaline substances.
  • anionic direct dye means any direct dye comprising in its structure at least one sulfonate S0 3 " group and/or at least one carboxylate group C(0)0 " and optionally one or more anionic groups G " with G " , which may be identical or different, representing an anionic group chosen from alkoxide O " , thiolate S “ , carboxylate and thiocarboxylate: C(Q)Q' ⁇ , with Q and Q', which may be identical or different, representing an oxygen or sulfur atom; preferably, G " represents a carboxylate, i.e. Q and Q' represents an oxygen atom.
  • the dye(s) of the invention are chosen from the direct dyes of formula (VI):
  • ⁇ Col ( ) m represents the anionic part of the anionic direct dye or "acid' dye comprising in its structure at least one sulfonate group and/or at least one carboxylate group and comprising m anionic charges:
  • ⁇ m and n which may be identical or different, represent an integer between 1 and 10 inclusive;
  • ⁇ Q + which may be identical or different, represents an organic or mineral cationic counterion preferably chosen from alkali metal or alkaline-earth metal cations such as Na + or K + .
  • the radical Col ( ) m represents the anionic part of the "acid dyes" or of the anionic direct dyes and preferentially Col ( 1 ⁇ 2 comprises in its structure:
  • At least one sulfonate group and at least one (hetero)aryl group it being understood that at least one sulfonate group is directly connected to a (hetero)aryl group, preferentially aryl such as phenyl or benzo; and
  • Col ( ) m comprises in its structure:
  • At least one (hetero)aryl group it being understood that at least one carboxylate group is directly connected to a (hetero)aryl group, preferentially aryl such as phenyl or benzo; and
  • Col ( ) m comprises in its structure:
  • At least one carboxylate group, at least one sulfonate group and at least one (hetero)aryl group it being understood that at least one sulfonate or carboxylate group is directly connected to a (hetero)aryl group, preferentially aryl such as phenyl or benzo; and
  • the dyes of formula (VI) are such that m is equal to n.
  • An advantageous variant of the invention concerns the dyes of formula (VI) for which m and n are equal to 1 , 2 or 3.
  • the preferred anionic dye(s) of formula (VI) of the invention are chosen from acidic nitro direct dyes, acidic azo dyes, acidic azine dyes, acidic triarylmethane dyes, acidic indoamine dyes, acidic anthraquinone dyes, acidic indigoids and acidic natural dyes; each of these dyes having at least one sulfonate or carboxylate group bearing a cationic counterion as defined previously; preferentially alkali metal, alkaline-earth metal or ammonium sulfonate or carboxylate.
  • dyes according to the invention mention may be made of the dyes of formulae (VII), (VII'), (VIII), (VIII'), (IX), ( ⁇ '), (X), ( ⁇ '), (XI), (XII), (XIII) and (XIV) below:
  • R 7 , R 8 , 9, R10, R'7, R's, R'9 and R'i 0 which may be identical or different, represent a hydrogen atom or a group chosen from: i) alkyl, ii) alkoxy, iii) alkylthio, iv) hydroxyl, v) mercapto, vi) nitro, vii) R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X"- with R° representing a hydrogen atom or an alkyl or aryl group; X, X' and X", which may be identical or different, represent an oxygen or sulfur atom or NR with R representing a hydrogen atom or an alkyl group; viii) (0) 2 S(0 , M + with M + as defined previously for M or represents a cationic counterion as defined previously; ix) (O)CO -, M + with M + as defined
  • W represents a sigma bond ⁇ , an oxygen or sulfur atom, or a divalent radical i) -NR- with R as defined previously, or ii) methylene -C(R a )(R b )- with R a and R b , which may be identical or different, representing a hydrogen atom or an aryl group, or alternatively R a and R b together form, with the carbon atom that bears them, a spiro cycloalkyl; preferentially, W represents a sulfur atom or R a and R b together form a cyclohexyl; it being understood that formulae (VII) and (VII') comprise at least one sulfonate (0) 2 S(0 , Q + or carboxylate (0)C(0 , Q + radical on one of the rings A, A', B, B' or C with R ! R 2 R 3 R4 as defined previously; preferentially alkali metal, alkaline-earth metal or
  • dyes of formula (VII) mention may be made of: Acid Red 1 , Acid Red 4, Acid Red 13, Acid Red 14, Acid Red 18, Acid Red 27, Acid Red 32, Acid Red 33, Acid Red 35, Acid Red 37, Acid Red 40, Acid Red 41 , Acid Red 42, Acid Red 44, Acid Red 68, Acid Red 73, Acid Red 135, Acid Red 138, Acid Red 184, Food Red 1 , Food Red 13, Acid Orange 6, Acid Orange 7, Acid Orange 10, Acid Orange 19, Acid Orange 20, Acid Orange 24, Acid Yellow 9, Acid Yellow 36, Acid Yellow 199, Food Yellow 3; Acid Violet 7, Acid Violet 14, Acid Blue 1 13, Acid Blue 1 17, Acid Black 1 , Acid Brown 4, Acid Brown 20, Acid Black 26, Acid Black 52, Food Black 1 , Food Black 2;
  • dyes of formula (VI ⁇ ) mention may be made of: Acid Red 11 1 , Acid Red 134, Acid Yellow 38;
  • R 11 ; R 12 and R 13 which may be identical or different, represent a hydrogen or halogen atom, an alkyl group or -(0) 2 S(0 ⁇ ), M + with M + as defined previously;
  • R 14 represents a hydrogen atom, an alkyl group or a group -C(0)0-, M + with M + as defined previously;
  • ⁇ Ri 5 represents a hydrogen atom
  • Ri 6 represents an oxo group, in which case R'i 6 is absent, or alternatively Ri 5 with R 16 together form a double bond; • R 17 and R 18 , which may be identical or different, represent a hydrogen atom or a group chosen from:
  • Ar-0-S(0) 2 - with Ar representing an optionally substituted aryl group, preferentially a phenyl optionally substituted with one or more alkyl groups;
  • Rig and R 20 together form either a double bond, or a benzo group D', which is optionally substituted;
  • R' 16 , R' 19 and R' 20 which may be identical or different, represent a hydrogen atom or an alkyl or hydroxyl group
  • R 2 i represents a hydrogen atom or an alkyl or alkoxy group
  • R a and R b which may be identical or different, are as defined previously, preferentially R a represents a hydrogen atom and R b represents an aryl group;
  • Y represents either a hydroxyl group or an oxo group
  • • represents a single bond when Y is an oxo group; and represents a double bond when Y represents a hydroxyl group;
  • formulae (VIII) and (VIII') comprise at least one sulfonate group (0) 2 S(0 , Q + on one of the rings D or E or formulae (VIII) and (VIII') comprise at least one carboxylate group (O)C(O )-, Q + with Q + as defined previously; preferentially comprise at least one sulfonate group (0) 2 S(0 , Q + on one of the rings D or E and more particularly sulfonate;
  • dyes of formula (VIII) mention may be made of: Acid Red 195, Acid Yellow 23, Acid Yellow 27, Acid Yellow 76, and as examples of dyes of formula (VIM'), mention may be made of Acid Yellow 17; a3c) the anthraquinone dyes of formulae (IX) and (IX'):
  • R22, R23, R24, R25, R26 and R 27 which may be identical or different, represent a hydrogen or halogen atom or a group chosen from i) alkyl, ii) hydroxyl, iii) mercapto, iv) alkoxy, v) alkylthio, vi) aryloxy or arylthio which is optionally substituted, preferentially substituted with one or more groups chosen from alkyl and (0) 2 S(0 ⁇ )-, M + with M + as defined previously, vii) aryl(alkyl)amino optionally substituted with one or more groups chosen from alkyl and (0) 2 S(0 ⁇ )-, M + with M + as defined previously, viii) (di)(alkyl)amino, ix) (di)(hydroxyalkyl)amino, x) (0) 2 S(0 , M + with M + as defined previously;
  • Z' represents a hydrogen atom or a group NR 28 R29 with R 28 and R 29 , which may be identical or different, representing a hydrogen atom or a group chosen from i) alkyl, ii) polyhydroxyalkyl such as hydroxyethyl, iii) aryl optionally substituted with one or more groups chosen from alkyl such as methyl, n-dodecyl, n-butyl; (0) 2 S(0 , M + with M + as defined previously; R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X"- with R°, X, X' and X" as defined previously, preferentially R° represents an alkyl group, iv) cycloakyl; especially cyclohexyl;
  • Z represents a group chosen from hydroxyl and NR' 28 R' 29 with R' 28 and R' 29 , which may be identical or different, representing the same atoms or groups as R 28 and R 29 as defined previously;
  • formulae (IX) and (IX') comprise at least one sulfonate group
  • dyes of formula (IX) mention may be made of: Acid Blue 25, Acid Blue 43, Acid Blue 62, Acid Blue 78, Acid Blue 129, Acid Blue 138, Acid Blue 140, Acid Blue 251 , Acid Green 25, Acid Green 41 , Acid Violet 42, Acid Violet 43, Mordant Red 3;
  • R 30 , R 3 i and R 32 which may be identical or different, represent a hydrogen or halogen atom or a group chosen from i) alkyl, ii) alkoxy optionally substituted with one or more hydroxyl groups, iii) alkylthio optionally substituted with one or more hydroxyl groups, iv) hydroxyl, mercapto, v) nitro, nitroso, vi) (poly)haloalkyl, vii) R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X"- with R°; X, X' and X" as defined previously, viii) (0) 2 S(0 , M + with M + as defined previously, ix) (O)CO -, IVTwith M + as defined previously, x) (di)(alkyl)amino, xi) (di)(hydroxyalkyl)amino
  • W is as defined previously; W particularly represents a group -NH-;
  • ALK represents a linear or branched divalent CrC 6 alkylene group; in particular, ALK represents a group -CH 2 -CH 2 -;
  • n 1 or 2;
  • J represents a nitro or nitroso group; particularly nitro
  • J represents an oxygen or sulfur atom, or a divalent radical -S(0) m - with m representing an integer 1 or 2; preferentially, J represents a radical -S0 2 -;
  • M' is as defined previously for M + ;
  • ⁇ ,i which may be present or absent, represents a benzo group optionally substituted with one or more groups R 30 as defined previously;
  • formulae (X) and ( ⁇ ') comprise at least one sulfonate group (0) 2 S(0 , Q + or carboxylate group (0)C(0 , Q + ;
  • dyes of formula (X) mention may be made of: Acid Brown 13 and Acid Orange 3; as examples of dyes of formula ( ⁇ '), mention may be made of: Acid Yellow 1 , sodium salt of 2,4-dinitro-1 -naphthol-7-sulfonic acid, 2-piperidino-5- nitrobenzenesulfonic acid, 2-(4'-N,N(2"-hydroxyethyl)amino-2'-nitro)anilineethanesulfonic acid and 4-p-hydroxyethylamino-3-nitrobenzenesulfonic acid; a3e) the triarylmethane dyes of formula (XI):
  • R33, R34, R35 and R 36 which may be identical or different, represent a hydrogen atom or a group chosen from alkyl, optionally substituted aryl and optionally substituted arylalkyl; particularly an alkyl group and benzyl optionally substituted with a group (0) m S(0 , M + with M + and m as defined previously;
  • ⁇ R37, R38, R39, R40, R41 , R42, R43 and R44 which may be identical or different, represent a hydrogen atom or a group chosen from: i) alkyl; ii) alkoxy, alkylthio; iii) (di)(alkyl)amino; iv) hydroxyl, mercapto; v) nitro, nitroso; vii) R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X"- with R° representing a hydrogen
  • R 41 with R 42 or R 42 with R 43 or R 43 with R 44 together form a fused benzo group: ⁇ ; with ⁇ optionally substituted with one or more groups chosen from i) nitro; ii) nitroso; iii) (0) 2 S(0 , M + ; iv) hydroxyl; v) mercapto; vi) (di)(alkyl)amino; vii) R°-C(X)-X'-; viii) R°-X'-C(X)- and ix) R°-X'-C(X)-X"-; with M + , R°, X, X' and X" as defined previously;
  • R 37 to R 40 represent a hydrogen atom
  • R 4 i to R 44 which may be identical or different, represent a hydroxyl group or (0) 2 S(0 ⁇ )-, M +
  • R 43 with R 44 together form a benzo group it is preferentially substituted with a group (0) 2 S(0 ;
  • At least one of the rings G, H, I or ⁇ comprises at least one sulfonate (0) 2 S(0 , Q + or carboxylate (0)C(0 , Q + group;
  • dyes of formula (XI) mention may be made of: Acid Blue 1 ; Acid Blue 3; Acid Blue 7, Acid Blue 9; Acid Violet 49 and Acid Green 50; a3f) the xanthene-based
  • R 45 , R 46 , R47 and R 48 which may be identical or different, represent a hydrogen or halogen atom
  • R49, R50, R51 and R 52 which may be identical or different, represent a hydrogen or halogen atom or a group chosen from i) alkyl; ii) alkoxy, alkylthio; iii) hydroxyl, mercapto; iv) nitro, nitroso; v) (0) 2 S(0 , M + with M + representing a hydrogen atom or a cationic counterion; vi) (O)CO -, M + with M + as defined previously;
  • R 53 , R 54 , R 55 and R 48 represent a hydrogen or halogen atom
  • ⁇ G represents an oxygen or sulfur atom or a group NR e with R e as defined previously; particularly, G represents an oxygen atom;
  • ⁇ L represents an alkoxide O " , M + ; a thioalkoxide S “ , M + or a group NR f , with R f representing a hydrogen atom or an alkyl group and M + as defined previously; M + is particularly Na + or K + ;
  • ⁇ Q and Q' which may be identical or different, represent an oxygen or sulfur atom; particularly Q and Q' represent an oxygen atom;
  • ⁇ M + is as defined previously;
  • formula (XII) comprises at least one sulfonate group (0) 2 S(0 ⁇ )-, Q + or carboxylate group (O)C(O )-, Q + with Q + as defined previously;
  • dyes of formula (XII) mention may be made of the ammonium salts derived from: Acid Yellow 73; Acid Red 51 ; Acid Red 87; Acid Red 92; Acid Red 95 and Acid Violet 9;
  • R53, R54, R55, R56, R57, R58, R59 and R 60 which may be identical or different, represent a hydrogen atom or a group chosen from: i) alkyl; ii) alkoxy, alkylthio; iii) hydroxyl, mercapto; iv) nitro, nitroso; v) R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X"- with R° representing a hydrogen atom or an alkyl or aryl group; X, X' and X", which may be identical or different, representing an oxygen or sulfur atom or NR with R representing a hydrogen atom or an alkyl group; vi) (0) 2 S(0 , M + with M + as defined previously; vii) (O)CO -, IVT with M + as defined previously;
  • G represents an oxygen or sulfur atom or a group NR e with R e as defined previously; particularly, G represents an oxygen atom;
  • R, and R h which may be identical or different, represent a hydrogen atom or an alkyl group
  • formula (XIII) comprises at least one sulfonate group (0) 2 S(0 , Q + or carboxylate group (O)C(O )-, Q + with Q + as defined previously;
  • dyes of formula (XIII) mention may be made of Acid Blue 74 and indigo carmine (or indigotine I, blue CI No. 1 ) is a blue dye (number E132) which is a natural extract of the indigo plant; a3h) the quinoline-based dyes of formula (XIV):
  • R 61 represents a hydrogen or halogen atom or an alkyl group
  • Re2, Re3 and R 64 which may be identical or different, represent a hydrogen atom or a group (0) 2 S(0 , M + with M + as defined previously;
  • R 6 i with R 62 , or R 61 with R 64 together form a benzo group optionally substituted with one or more groups (0) 2 S(0 , M + with M + representing a hydrogen atom or a cationic counterion;
  • formula (XIV) comprises at least one sulfonate group (0) 2 S(0 , Q + with Q + as defined previously.
  • dyes of formula (XIV) mention may be made of the ammonium salts derived from: Acid Yellow 2, Acid Yellow 3 and Acid Yellow 5.
  • dyes of formulae (VII) to (XIV) that are useful in the invention are chosen from the sal ts:
  • the anionic dyes that are most particularly preferred are the dyes designated in the Colour Index under the code C.I. 58005 (monosodium salt of 1 ,2-dihydroxy-9,10-anthraquinone-3-sulfonic acid), C.I. 60730 (monosodium salt of 2- [(9,10-dihydro-4-hydroxy-9,10-dioxo-1 -anthracenyl)amino]-5-methylbenzenesulfonic acid), C.I.
  • the dye(s) according to the invention are chosen from those of formulae (VII), (IX) and (XIII), preferably of formula (XIII).
  • the dye(s) are chosen from cationic direct dyes or dyes commonly referred to as "basic” direct dyes or “basic dyes” on account of their affinity for acidic substances.
  • the cationic dyes are preferentially chosen from hydrazono, (poly)azo, polymethine such as styryl and (poly)arylmethane dyes.
  • the cationic dye(s) of the invention are chosen from the hydrazono dyes of formulae (XVa) and (XV'a), the azo dyes (XVIa) and (XVI'a) and the diazo dyes (XVIIa) below:
  • Hef representing a cationic heteroaryl radical, preferentially bearing an endocyclic cationic charge, such as imidazolium, indolium or pyridinium, optionally substituted preferentially with one or more (CrC 8 )alkyl groups such as methyl;
  • Ar + representing an aryl radical, such as phenyl or naphthyl, bearing an exocyclic cationic charge, preferentially ammonium, particularly tri(Ci-C 8 )alkylammonium such as trimethylammonium;
  • Ar represents an aryl group, especially phenyl, which is optionally substituted, preferentially with one or more electron-donating groups such as i) optionally substituted (CrC 8 )alkyl, ii) optionally substituted (CrC 8 )alkoxy, iii) (di)(C C 8 )(alkyl)amino optionally substituted on the alkyl group(s) with a hydroxyl group, iv) aryl(Ci-C 8 )alkylamino, v) optionally substituted A/-(Ci-C 8 )alkyl-A/-aryl(Ci-C 8 )alkylamino or alternatively Ar represents a julolidine group;
  • Ar' is an optionally substituted divalent (hetero)arylene group such as phenylene, particularly para-phenylene, or naphthalene, which are optionally substituted, preferentially with one or more (CrC 8 )alkyl, hydroxyl or (d-C 8 )alkoxy groups; • Ar" is an optionally substituted (hetero)aryl group such as phenyl or pyrazolyl, which are optionally substituted, preferentially with one or more (d-C 8 )alkyl, hydroxyl, (di)(Ci-C 8 )(alkyl)amino, (CrC 8 )alkoxy or phenyl groups;
  • R a and R b which may be identical or different, represent a hydrogen atom or a (C C 8 )alkyl group, which is optionally substituted, preferentially with a hydroxyl group; or alternatively the substituent R a with a substituent of Het + and/or R b with a substituent of Ar and/or R a with R b form, together with the atoms that bear them, a (hetero)cycloalkyl; particularly, R a and R b represent a hydrogen atom or a (CrC 4 )alkyl group, which is optionally substituted with a hydroxyl group;
  • ⁇ Q " represents an anionic counterion as defined previously.
  • the cationic dyes are chosen from the polymethine dyes of formulae (XVIIIa) and (XVIII'a) below:
  • W + representing a cationic heterocyclic or heteroaryl group, particularly comprising a quaternary ammonium optionally substituted with one or more (CrC 8 )alkyl groups optionally substituted especially with one or more hydroxyl groups;
  • W' + representing a heterocyclic or heteroaryl radical as defined for W + ;
  • Ar representing a (hetero)aryl group such as phenyl or naphthyl, optionally substituted preferentially with i) one or more halogen atoms such as chlorine or fluorine; ii) one or more (CrC 8 )alkyl groups, preferably of Ci-C 4 such as methyl; iii) one or more hydroxyl groups; iv) one or more (Ci-C 8 )alkoxy groups such as methoxy; v) one or more hydroxy(CrC 8 )alkyl groups such as hydroxyethyl, vi) one or more amino groups or (di)(CrC 8 )alkylamino, preferably with the CrC 4 alkyl part optionally substituted with one or more hydroxyl groups, such as (di)hydroxyethylamino, vii) with one or more acylamino groups; viii) one or more heterocycloalkyl groups such as piperazinyl, piperidyl or
  • Ar' is a (hetero)aryl radical as defined for Ar
  • m' represents an integer between 1 and 4 inclusive, and in particular m is 1 or 2; more preferentially 1 ;
  • R c and R d which may be identical or different, represent a hydrogen atom or an optionally substituted (CrC 8 )alkyl group, preferentially of Ci-C 4 , or alternatively R c contiguous with W + or W' + and/or R d contiguous with Ar or Ar' and/or contiguous R c and R d form, with the atoms that bear them, a (hetero)cycloalkyl, particularly R c is contiguous with W + or W' + and forms a (hetero)cycloalkyl such as cyclohexyl;
  • the cationic dyes comprise an endocyclic cationic charge and particularly have the following formula:
  • - Pt 2 and R 3 which may be identical or different, represent a hydrogen atom or a (d- C 4 )alkyl group, such as methyl;
  • R 4 represents a hydrogen atom or an electron-donating group such as optionally substituted (CrC 8 )alkyl, optionally substituted (CrC 8 )alkoxy, or (di)(Ci-C 8 )(alkyl)amino optionally substituted on the alkyl group(s) with a hydroxyl group; particularly, R 4 is a hydrogen atom,
  • - Z represents a CH group or a nitrogen atom, preferentially CH
  • the dyes of the invention are chosen from those of formulae (XVIa-1 ) and
  • (XVa-1 ) is chosen from Basic Red 51 , Basic Yellow 87 and Basic Orange 31 or derivatives thereof:
  • the dye(s) are present in a total amount ranging from 0.001% to 20% by weight relative to the total weight of the dye composition, in particular ranging from 0.005% to 10% by weight relative to the total weight of the dye composition, preferentially from 0.01 % to 5% by weight relative to the total weight of the dye composition.
  • the content in the composition(s) containing them is preferably between 0.001 % and 5% by weight of each of these compositions containing them.
  • the content in the composition(s) containing the extract(s) per se is preferably between 0.1 % and 20% by weight of each of these compositions.
  • the titanium salt(s) of the invention may be one or more organic or mineral titanium salts.
  • organic titanium salt means the salts per se resulting from the action of at least one organic acid on Ti.
  • organic acid means an acid, i.e. a compound that is capable of releasing a cation or proton H + or H 3 0 + , in aqueous medium, which comprises at least one optionally unsaturated, linear or branched Ci-C 20 hydrocarbon-based chain, or a (hetero)cycloalkyl or (hetero)aryl group and at least one acid chemical function chosen in particular from carboxyl COOH, sulfuric S0 3 H, S0 2 H, and phosphoric P0 3 H 2 , P0 4 H 2 .
  • organic acid(s) for forming the organic titanium salt(s) of the invention are chosen from the carboxylic acid(s) of formula (I) as defined previously and are preferably a-hydroxy acids such as lactic acid, glycolic acid, tartaric acid or citric acid.
  • the organic titanium salt derived from the action of one or more organic acids as defined previously, preferably carboxylic acids of formula (I) as defined previously, is an optionally charged (in particular negatively charged) complex, which is complexed with one or more carboxylate groups of carboxylic acids.
  • organic titanium salt(s) of the invention are chosen from those of formula (l-A) below:
  • Mi and M 2 which may be identical or different, represent a cationic counterion chosen in particular from cations of an alkali metal such as Na or K or of an alkaline-earth metal such as Ca or an organic cation such as ammonium, preferably ammonium or a hydrogen atom;
  • the radical A of compound (l-A) as defined previously represents a monovalent (d-C 6 )alkyl or polyvalent (CrC 6 )alkylene group optionally substituted with one or more hydroxyl groups, and n representing an integer between 0 and 5, such as between 0 and 2, inclusive;
  • the carboxylic acid(s) used to form the organic titanium salt(s) of the invention are chosen from ⁇ -hydroxy acids; preferably, the acid is chosen from citric acid, lactic acid, tartaric acid and glycolic acid, better still from lactic acid and glycolic acid.
  • organic titanium salt(s) of the invention are chosen from those of formula (l-B) below:
  • L' and L which may be identical or different, represent a divalent (hetero)arylene, (CrC 6 )alkylene or (C 2 -C 6 )alkenylene group, said alkylene and arylene groups being optionally substituted with one or more atoms or groups chosen from halo, (C C 4 )alkyl, hydroxyl, thiol and (di)(Ci-C 4 )(alkyl)amino, carboxyl, and/or optionally interrupted with one or more heteroatoms such as oxygen;
  • L' and L" are identical and represent a methylene or ethylene group optionally substituted with a (CrC 4 )alkyl group;
  • X' and X which may be identical or different, represent a heteroatom such as oxygen, sulfur or amino R c -N with R c representing a hydrogen atom or a (CrC 4 )alkyl group; preferably, X' and X" are identical and represent an oxygen atom;
  • Y and Y' which may be identical or different, are as defined for X' and X"; preferably, Y and Y' are identical and represent an oxygen atom; • R a and R b , which may be identical or different, represent a hydrogen atom or a (C C 6 )alkyl, (C 2 -C 6 )alkenyl or (hetero)aryl group; particularly, R a and R b , which are identical, represent a hydrogen atom or a (d-C 4 )alkyl group, preferably hydrogen;
  • M + which may be identical or different, represents a cationic counterion such as a cation of an alkali metal (Na or K) or of an alkaline-earth metal (Ca) or an organic cation such as ammonium, preferably ammonium.
  • the organic titanium salt(s) of the dyeing process are dihydroxybis(lactato)titanium(IV) salts such as those having the following formula:
  • the dyeing process may use one or more organic acids b1 ) of formula (I) as defined previously.
  • the dyeing process also uses b1 ) one or more carboxylic acids of formula (I) as defined previously.
  • the carboxylic acid(s) b1 ) are different from the carboxylic acids complexed to the Ti salts, preferably glycolic acid, citric acid, tartaric acid, lactic acid or a salt thereof.
  • carboxylic acid(s) b) are preferably different from the carboxylic acids complexed to the Ti salts, when the Ti salt is an organic salt derived from the action of one or more carboxylic acids as defined previously.
  • the carboxylic acid complexed to the titanium salt b) is lactic acid or the carboxylate salt thereof (lactate)
  • the second acid b1 ) is other than lactic acid or lactate, and may be, for example, glycolic acid.
  • the term "mineral titanium salt" means the salts per se derived from the action of a mineral acid on Ti.
  • mineral acid means an acid which does not comprise carbon atoms, apart from carbonic acid.
  • the mineral titanium salts are preferably chosen from titanium halides, titanium sulfates and titanium phosphates.
  • the titanium salts are mineral Ti(ll), Ti(lll) or Ti(IV) salts, more particularly Ti(lll) or Ti(IV).
  • the titanium salt(s) are organic titanium salts, and better still organic Ti(IV) salts.
  • the organic Ti salt consists of a Ti(IV) atom and of 2 to 3 molar equivalents of at least one carboxylic acid of formula (I).
  • the titanium salt(s) (b) are present in the cosmetic composition(s) used in the process according to the invention in a content ranging from 0.001% to 20% by weight, relative to the total weight of the composition(s) containing them.
  • the organic titanium salt(s) and the mineral titanium salt(s) according to the invention are soluble in water in a proportion of at least 0.0001 g/l and better still at least 1 g/l.
  • the pKai of the carboxylic acid(s) b1) is less than 3.
  • composition Cii comprising one or more alkaline agents c) which comprise not more than one amine function, it being understood that when composition Cii) comprises several alkaline agents, then each of the alkaline agents comprises not more than one amine function.
  • the alkaline agent is a Bronsted, Lowry or Lewis base. It may be mineral or organic and, when it is organic, it comprises not more than one amine function NH 2 .
  • said alkaline agent is chosen from i) (bi)carbonates, ii) aqueous ammonia, iii) alkanolamines comprising only one amine function such as monoethanolamine; monopropanolamine, iv) oxyalkylenated alkanolamines comprising only one amine function and in particular oxyethylenated alkanolamines such as oxyethylenated and/or oxypropylenated ethyleneamines, v) mineral or organic hydroxides, vi) alkali metal silicates such as sodium metasilicates, vii) amino acids comprising only one amine function, preferably basic amino acids such as histidine.
  • the mineral or organic hydroxides are preferably chosen from a) hydroxides of an alkali metal, b) hydroxides of an alkaline-earth metal, for instance sodium hydroxide or potassium hydroxide, c) hydroxides of a transition metal, such as hydroxides of metals from groups III, IV, V and VI, d) hydroxides of lanthanides or actinides and quaternary ammonium hydroxides.
  • bicarbonates also known as hydrogen carbonates, of the following formulae: > R' + , HCO 3 " with R' representing a hydrogen atom, an alkali metal, an ammonium group R" 4 N + - or a phosphonium group R" 4 P + - where R", which may be identical or different, represent a hydrogen atom, an optionally substituted (d-C 6 )alkyl group such as a hydroxyethyl group and, when R' represents a hydrogen atom, the hydrogen carbonate is then known as a dihydrogen carbonate (C0 2 , H 2 0); and
  • the alkaline agent is chosen from alkali metal or alkaline-earth metal (bi)carbonates and amino acids comprising not more than one amine function such as histidine; preferentially alkali metal (bi)carbonates and amino acids comprising not more than one amine function.
  • the alkaline agent(s) c) are chosen from a mixture of two alkaline agents chosen from families i) to vii) as defined previously.
  • alkaline agent(s) c) are chosen from the following mixtures:
  • amino acids and oxyalkylenated or non-oxyalkylenated alkanolamines comprising not more than one amine function
  • the weight ratio R between 1 ) carbonates and bicarbonates or between the first alkaline agents (amino acids, alkanolamines, oxyalkylenated alkanolamines, mineral or organic hydroxides or alkali metal silicates) according to 2) to 6) and the (bi)carbonates is greater than or equal to 2, preferentially R is greater than or equal to 4, more preferentially R is greater than or equal to 6, even more preferentially R is greater than or equal to 8, better still greater than or equal to 10 and in particular R is inclusively between 2 and 16, preferentially R is inclusively between 10 and 14.
  • the alkaline agent(s) c) are chosen from i) alkali metal or alkaline-earth metal carbonates, ii) alkali metal or alkaline- earth metal bicarbonates and iii) amino acids comprising not more than one amine function such as histidine, alone or as mixtures. They are preferably together during the dyeing process.
  • Composition Cii) preferably comprises a mixture of at least one alkali metal or alkaline-earth metal carbonate i) and of at least one alkali metal or alkaline-earth metal bicarbonate ii).
  • the alkaline agent(s) c) are chosen from a mixture of carbonates and bicarbonates as defined previously with a carbonates/bicarbonates weight ratio R of greater than or equal to 2, preferentially R is greater than or equal to 4, more preferentially R is greater than or equal to 6, even more preferentially R is greater than or equal to 8, better still greater than or equal to 10 and in particular R is inclusively between 2 and 16, preferentially R is inclusively between 10 and 14.
  • carbonates and bicarbonates that are suitable for use in the present invention
  • composition Cii) comprises at least one alkaline agent chosen from alkali metal carbonate alone such as sodium carbonate alone, or a mixture of alkali metal carbonate and alkali metal bicarbonate such as the mixture of sodium carbonate and sodium bicarbonate, preferably with a carbonates/bicarbonates weight ratio R of greater than 2, preferentially R is greater than or equal to 4, more preferentially R is greater than or equal to 6, even more preferentially R is greater than or equal to 8, better still greater than or equal to 10 and in particular R is inclusively between 2 and 16, preferentially R is inclusively between 10 and 14.
  • alkali metal carbonate alone such as sodium carbonate alone
  • a mixture of alkali metal carbonate and alkali metal bicarbonate such as the mixture of sodium carbonate and sodium bicarbonate
  • each alkaline agent c) alone or as a mixture has one or more pKa values which are inclusively between 6 and 11.5, or better still between 9.5 and 11 , i.e. each pKa must preferably be between 6 and 11.5, or better still between 9.5 and 1 1.
  • the alkaline agent(s) c) as defined previously preferably represent a total amount of greater than 1% by weight in total relative to the total weight of composition Cii). More particularly, the total amount of alkaline agent(s) according to the invention is inclusively between 1 % and 15%, preferably between 2% and 10% and more preferentially between 5.1 % and 9% by weight of composition Cii).
  • chemical oxidizing agent is) According to a particular embodiment of the invention, the dyeing process also uses one or more chemical oxidizing agents.
  • chemical oxidizing agent means an oxidizing agent other than atmospheric oxygen.
  • the dyeing process uses one or more chemical oxidizing agents chosen from i) hydrogen peroxide; ii) urea peroxide; iii) polymeric complexes that can release hydrogen peroxide, such as polyvinylpyrrolidone/H 2 0 2 , provided in particular in the form of powders, and the other polymeric complexes described in US 5 008 093, US 3 376 110 and US 5 183 901 ; iv) oxidases in the presence of an appropriate substrate (for example, glucose in the case of glucose oxidase or uric acid with uricase); v) metal peroxides which generate hydrogen peroxide in water, such as calcium peroxide or magnesium peroxide; vi) perborates; and/or vii) percarbonates.
  • an appropriate substrate for example, glucose in the case of glucose oxidase or uric acid with uricase
  • metal peroxides which generate hydrogen peroxide in water, such as calcium peroxide or magnesium peroxide
  • composition Cii) comprises one or more chemical oxidizing agents chosen from i) urea peroxide; ii) polymeric complexes which can release hydrogen peroxide chosen from polyvinylpyrrolidone/H 2 0 2 ; iii) oxidases; iv) perborates and v) percarbonates.
  • composition Ci) comprises one or more chemical oxidizing agents chosen from i) urea peroxide; ii) polymeric complexes which can release hydrogen peroxide chosen from polyvinylpyrrolidone/H 2 0 2 ; iii) oxidases; iv) perborates and v) percarbonates.
  • the dyeing process uses hydrogen peroxide.
  • composition(s) comprising hydrogen peroxide or a hydrogen peroxide generating system may also include various adjuvants conventionally used in compositions for dyeing keratin fibres as defined below.
  • the chemical oxidizing agent(s) used represent from 0.001% to 12% by weight of chemical oxidizing agents (of hydrogen peroxide) relative to the total weight of the composition containing it or them, preferentially from 0.2% to 5% and more preferentially between 0.1% and 3% by weight of the composition containing it or them.
  • Water is preferably included in the process of the invention. It may originate from the moistening of the keratin fibres and/or from the composition(s) comprising compounds a) to d) as defined previously or from one or more other compositions.
  • the water comes from at least one composition comprising at least one compound chosen from a) to d) as defined previously.
  • compositions generally comprise water or a mixture of water and of one or more organic solvents or a mixture of organic solvents.
  • organic solvent means an organic substance that is capable of dissolving or dispersing another substance without chemically modifying it.
  • organic solvents means an organic substance that is capable of dissolving or dispersing another substance without chemically modifying it.
  • compositions Ci) and Cii) comprise at least one organic solvent.
  • only composition Ci) comprises at least one organic solvent.
  • organic solvents examples include Ci-C 4 lower alkanols, such as ethanol and isopropanol; polyols and polyol ethers such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, hexylene glycol, and also aromatic alcohols, such as benzyl alcohol or phenoxyethanol.
  • the dye composition i.e. comprising the dye(s), in particular the ODP(s) of the invention, comprises at least one organic solvent as defined previously and in particular an organic solvent chosen from aromatic alcohols, such as benzyl alcohol.
  • the organic solvents are present in proportions preferably of between 1 % and 40% by weight approximately and more preferably still between 5% and 30% by weight approximately, with respect to the total weight of the dyeing composition.
  • composition(s) of the dyeing process in accordance with the invention may also contain various adjuvants conventionally used in hair dye compositions, such as anionic, cationic, nonionic, amphoteric or zwitterionic surfactants or mixtures thereof, anionic, cationic, nonionic, amphoteric or zwitterionic polymers or mixtures thereof, mineral or organic thickeners, and in particular anionic, cationic, nonionic and amphoteric polymeric associative thickeners, antioxidants, penetrants, sequestrants, fragrances, buffers, dispersants, conditioning agents, for instance volatile or non-volatile, modified or unmodified silicones, film-forming agents, ceramides, preserving agents and opacifiers.
  • adjuvants conventionally used in hair dye compositions, such as anionic, cationic, nonionic, amphoteric or zwitterionic surfactants or mixtures thereof, anionic, cationic, nonionic, amphoteric or zwit
  • the dyeing process of the invention may also use, in addition to compounds a), b), c) and optionally d), at least one other particular carboxylic acid of formula (I) as defined previously. More particularly, the carboxylic acid(s) of formula (I) are such that A represents a monovalent (d-C 6 )alkyl or polyvalent (CrC 6 )alkylene group optionally substituted with one or more hydroxyl groups, and n represents an integer between 0 and 5, such as between 0 and 2, inclusive.
  • carboxylic acid(s) of the invention are chosen from the acids of formula (I) having a solubility in water of greater than or equal to 1% by weight at 25°C and at atmospheric pressure.
  • the acids of formula (I) comprise at least one hydroxyl group in their structure. Even more preferably, the acid is chosen from a-hydroxy acids.
  • the preferred acids of the invention are chosen from glycolic acid, lactic acid, tartaric acid and citric acid.
  • the salts of the acids of formula (I) may be salts of organic or mineral bases, such as sodium hydroxide, aqueous ammonia or potassium hydroxide, or salts of organic amines, such as alkanolamines.
  • the acids of formula (I) or salts thereof are present in the composition(s) containing them in a content ranging from 0.1% to 20% by weight.
  • Said adjuvants are preferably chosen from surfactants such as anionic or nonionic surfactants or mixtures thereof and mineral or organic thickeners.
  • the above adjuvants are generally present in an amount for each of them of between 0.01% and 40% by weight relative to the weight of the composition, and preferably between 0.1 % and 20% by weight relative to the weight of the composition.
  • the cosmetic composition(s) of the invention may be in various galenical forms, such as a powder, a lotion, a mousse, a cream or a gel, or in any other form that is suitable for dyeing keratin fibres. They may also be packaged in a propellant-free pump-action bottle or under pressure in an aerosol container in the presence of a propellant and form a mousse. pH of the compositions:
  • the pH of the cosmetic composition Ci) comprising at least one of the ingredients a), b) or b1 ) is acidic, i.e. less than 7.0, preferably less than 5.0, in particular at a pH of between 0 and 4 inclusive, more particularly between 0.5 and 3.5, preferentially between 1 and 3.5.
  • the pH of the cosmetic composition Cii) containing one or more alkaline agents as defined previously is alkaline, i.e. greater than 7, preferably between 8 and 12 inclusive, more particularly between 8.5 and 1 1 and preferentially between 9.5 and 10.5 inclusive.
  • the pH of these compositions may be adjusted to the desired value by means of alkaline agents as defined previously in c) or by using acidifying agents usually used in the dyeing of keratin fibres, or alternatively by means of standard buffer systems.
  • acidifying agents for the compositions used in the invention examples that may be mentioned include mineral or organic acids, for instance hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids, for instance acetic acid, tartaric acid, citric acid or lactic acid, or sulfonic acids.
  • carboxylic acid means a compound comprising at least one carboxylic acid -C(0)-OH group, preferably of formula (I) as defined previously, preferably comprising between 1 and 4 carboxylic acid groups, such as 1 or 2; or chosen from: i) (CrCi 0 )alkyl- [C(0)-OH] n and ii) het-[C(0)-OH] n , with n an integer between 1 and 4 inclusive, preferably between 1 and 2, het representing a heterocylic group, such as pyrrolidone, it being possible for the alkyl or het group to be optionally substituted by one or more groups chosen in particular from OH, and (di)(CrC 6 )(alkyl)amino.
  • formula (I) as defined previously, preferably comprising between 1 and 4 carboxylic acid groups, such as 1 or 2; or chosen from: i) (CrCi 0 )alkyl- [C(0)-OH] n and i
  • the process for dyeing keratin fibres in several steps consists in applying to said fibres:
  • composition Cii a second cosmetic revealing composition comprising:
  • alkaline agent(s) c) one or more alkaline agents each comprising not more than one amine function as defined previously; preferably, the alkaline agent(s) c) are chosen from 1 ) a mixture of carbonates and bicarbonates as defined previously in particular with a carbonates/bicarbonates weight ratio R of greater than 2, preferentially R is greater than or equal to 4, more preferentially R is greater than or equal to 6, even more preferentially R is greater than or equal to 8, better still greater than or equal to 10 and in particular R is inclusively between 2 and 16, preferentially R is inclusively between 10 and 14; and
  • composition Ci is at acidic pH, i.e. less than 7, preferably less than 5, in particular at a pH of between 0 and 4 inclusive, more particularly between 0.5 and 3.5 and better still between 1 and 3.
  • At least one step of intermediate rinsing of said fibres, preferably with water, is performed in the process according to the invention.
  • the dyeing process is characterized in that the titanium salt(s) are chosen from organic or mineral titanium salts, preferably from organic titanium salts, and in which the titanium is in particular of oxidation state 2, 3 or 4, preferably of oxidation state 4.
  • the dyeing process is performed in at least two steps which comprise a first step in which the keratin fibres are treated with a cosmetic composition Ci) comprising a) one or more dyes, preferably one or more ODPs as defined previously, b) one or more organic titanium salts and optionally b1 ) one or more carboxylic acid(s) as defined previously; followed by a second step in which the keratin fibres are treated with a cosmetic composition Cii) comprising c) one or more alkaline agents as defined previously whose pH is greater than 7, preferably between 8 and 12 and in particular between 9 and 10.5, and which optionally comprises d) one or more chemical oxidizing agents as defined previously.
  • composition Ci) comprising a) + b) + optionally b1 ) is at acidic pH, i.e. less than 7, preferably less than 5, in particular at a pH of between 1 and 3 inclusive.
  • cosmetic composition Cii) applied to the keratin fibres during the second step also comprises d) one or more chemical oxidizing agents chosen especially from hydrogen peroxide and one or more hydrogen peroxide-generating systems, preferably hydrogen peroxide.
  • the dyeing process according to the invention is performed in several steps by applying to the keratin fibres, in a first stage, a cosmetic composition Ci) comprising:
  • ODPs as defined previously, especially chosen from: - haematein, brazilein, gallic acid or tannic acid, when the dyeing process does not use a chemical oxidizing agent d);
  • ingredient b) is chosen from Ti(IV) salts or complexes; b1 ) optionally one or more carboxylic acids of formula (I) as defined previously; and then
  • a cosmetic composition Cii) comprising:
  • the alkaline agent(s) c) are chosen from 1 ) a mixture of carbonates and bicarbonates as defined previously in particular with a carbonates/bicarbonates weight ratio R of greater than 2, preferentially R is greater than or equal to 4, more preferentially R is greater than or equal to 6, even more preferentially R is greater than or equal to 8, better still greater than or equal to 10 and in particular R is inclusively between 2 and 16, preferentially R is inclusively between 10 and 14, and
  • composition Ci is at acidic pH, i.e. less than 7, preferably less than 5, in particular at a pH of between 1 and 3 inclusive;
  • composition Cii) is at alkaline pH, preferably of between 8 and 12 and more particularly of between 9 and 10.5.
  • composition Ci) comprising the dye(s), especially the ODP(s) as defined previously, is generally set at between 3 and 120 minutes, preferentially between 10 and 60 minutes and more preferentially between 15 and 45 minutes.
  • the two compositions Ci) and Cii) used in the dyeing process of the invention are aqueous.
  • the leave-on time after application of Ci) for the first step is generally set at between 3 and 120 minutes, preferentially between 10 and 60 minutes and more preferentially between 15 and 45 minutes.
  • the application time of composition Cii) comprising ingredient c) during the second step is generally set at between 3 and 120 minutes, preferably between 3 and 60 minutes and more preferably between 5 and 30 minutes.
  • the process for dyeing keratin fibres is performed in two or three steps.
  • the process for dyeing keratin fibres is performed by applying to the keratin fibres, in a first step, a cosmetic composition Ci) comprising: a) one or more dyes, in particular one or more ODPs, chosen especially from:
  • b1 optionally one or more carboxylic acids of formula (I) as defined previously with A representing a monovalent (d-C 6 )alkyl or polyvalent (CrC 6 )alkylene group optionally substituted with one or more hydroxyl groups, and n representing an integer between 0 and 5, such as between 0 and 2, inclusive; more particularly, the carboxylic acid(s) of the invention are chosen from citric acid, lactic acid, glycolic acid and tartaric acid; and then, in a second step, applying to said fibres a cosmetic composition comprising: d) optionally one or more chemical oxidizing agents chosen from hydrogen peroxide or one or more hydrogen peroxide-generating systems; and then, in a third step, applying to said fibres a cosmetic composition Cii) comprising:
  • alkaline agent(s) c) one or more alkaline agents as defined previously; preferably, the alkaline agent(s) c) are chosen from 1 ) a mixture of carbonates and bicarbonates in particular with a carbonates/bicarbonates weight ratio R of greater than 2, preferentially R is greater than or equal to 4, more preferentially R is greater than or equal to 6, even more preferentially R is greater than or equal to 8, better still greater than or equal to 10 and in particular R is inclusively between 2 and 16, preferentially R is inclusively between 10 and 14,
  • composition Ci is at acidic pH, i.e. less than 7, preferably less than 5, in particular at a pH of between 1 and 3 inclusive;
  • composition Cii) comprising the alkaline agent(s) is at alkaline pH, preferably of between 8 and 12, more particularly of between 8.5 and 1 1 and better still between 9.5 and 10.5.
  • the dyeing process of the invention is performed in at least two steps: in the first step, ingredients a), b) and optionally b1 ) are applied together to the keratin fibres, in particular the hair, and then, in the second step, ingredients c) and optionally d) are applied together to said fibres.
  • the application temperature is generally between room temperature (15 to 25°C) and 220°C and more particularly between 15 and 45°C.
  • the head of hair may advantageously be subjected to a heat treatment by heating to a temperature of between 30 and 60°C.
  • this operation may be performed using a styling hood, an infrared heating hood (such as Climazon), a hairdryer, an infrared ray dispenser or other standard heating appliances.
  • Use may be made, both as means for heating and for smoothing the head of hair, of a heating iron at a temperature of between 60°C and 220°C and preferably between 120°C and 200°C.
  • the steps of intermediate mechanical wiping and drying are also known as "controlled non-rinsing" to distinguish from “standard abundant rinsing with water” and “non-rinsing".
  • the term “mechanical wiping” of the fibres means rubbing an absorbent article on the fibres and physical removal, by means of the absorbent article, of the excess ingredient(s) that have not penetrated the fibres.
  • the absorbent article may be a piece of fabric such as a towel, particularly a terry towel, a cloth or absorbent paper such as household roll towel.
  • the mechanical wiping is performed without total drying of the fibre, leaving the fibre moist.
  • drying means the action of evaporating the organic solvents and/or water present in one or more compositions used in the process of the invention, comprising or not comprising one or more ingredients a) to e) as defined previously.
  • the drying may be performed with a source of heat (convection, conduction or radiation) by sending, for example, a stream of hot gas such as air necessary to evaporate the solvent(s).
  • Sources of heat include a hairdryer, a hairstyling hood, a hair-straightening iron, an infrared ray dispenser or other standard heating appliances.
  • One particular mode of the invention relates to a dyeing process that is performed at room temperature (25°C).
  • compositions mentioned are ready-to-use compositions that may result from the extemporaneous mixing of two or more compositions and in particular of compositions present in dyeing kits.
  • dyeing device or "kit"
  • kits Another subject of the invention is a multi-compartment dyeing device or "kit".
  • this kit comprises from 2 to 5 compartments comprising from 2 to 5 compositions in which are distributed ingredients a) to d) as defined above, which may be aqueous or pulverulent, with in particular at least one of said compositions being aqueous.
  • the kit comprises five compartments, the first four compartments respectively comprising ingredients a), b) and optionally b1 ) and c), optionally in powder form, as defined previously and the fifth compartment containing an aqueous oxidizing composition, such as water comprising d) as defined previously.
  • At least one of the four compositions is aqueous and the dye(s), in particular the ODP(s), may be in powder form.
  • this kit comprises two compartments, in which the first composition contained in the first compartment comprises a), b) and optionally b1) and the second compartment comprises c) and optionally d) in powder form or in aqueous medium; preferably, the second composition is aqueous.
  • this kit comprises three compartments, in which the first composition contained in the first compartment comprises a) and b) and optionally b1 ) and the second compartment comprises d) in powder form or in aqueous medium; preferably, the second composition is aqueous and the third compartment comprises c).
  • the device according to the invention also comprises an additional composition comprising one or more treating agents.
  • compositions of the device according to the invention are packaged in separate compartments, optionally accompanied by suitable application means which may be identical or different, such as fine brushes, coarse brushes or sponges.
  • the device mentioned above may also be equipped with a means for dispensing the desired mixture on the hair, for instance the devices described in patent FR 2 586 913.
  • a subject of the invention is also the use of said cosmetic dye composition for dyeing keratin fibres.
  • a subject of the invention is also a cosmetic composition for dyeing keratin fibres, containing compounds a), b), optionally b1), c), and optionally d) as defined previously.
  • the term "build-up" of the colour on keratin fibres means the variation in colouring between locks of non-dyed white hair and locks of dyed hair.
  • compositions were prepared from the ingredients in the proportions indicated in grams per 100 g of composition according to the following tables:
  • Dye composition 1 was applied to natural Chinese hair containing 100% white hairs, and left to stand on the hair for 45 minutes at 40°C then rinsed out with tap water until the colour in the rinsing water disappeared.
  • each of the revealing compositions A to D was applied in the same amount and left to stand on the hair for 15 minutes at 40°C.
  • the colour of the locks was then evaluated in the CIE L * a * b * system using a Minolta Spectrophotometer CM3600D colorimeter.
  • the three parameters denote, respectively, the colour intensity (L * ), the green/red colour axis (a * ) and the blue/yellow colour axis (b * ).
  • L * , a * and b * represent the values measured on locks of hair after dyeing and L 0 * , a 0 * and b 0 * represent the values measured on locks of undyed virgin hair.
  • ⁇ * value the better the colour build-up.
  • Example 2 a) Preparation of the compositions and application to keratin fibres
  • compositions were prepared from the ingredients in the proportions indicated in grams per 100 g of composition according to the following tables:
  • ⁇ Dye composition 1 was prepared in the same amounts as the preceding examples.
  • Dye composition 1 was applied as defined in Example 1. Next, each of the revealing compositions E to G was then applied and left to stand on the hair for 15 minutes at 40°C. After these leave-on times, the locks were washed with Elvive multivitamin shampoo, rinsed and then dried under a hood.
  • compositions are prepared from the following ingredients in the following proportions, indicated in grams:
  • the study relates to locks of natural Caucasian hair containing 90% white hairs (90 NW).
  • the locks are pretreated separately with composition Cii) comprising the titanium salt.
  • composition Cii) is left to stand for 15 minutes on each lock at 33°C, and each lock is then rinsed.
  • the dye composition Ciii) is prepared just before use and then applied to each of the locks and left to stand for 60 minutes on each lock at 33°C. After these leave-on time the locks are rinsed and then dried under a hood.
  • the dye composition Ciii) is applied directly (without a pretreatment) to each of the locks and left to stand for 60 at 33°C (process P2) and for 120 minutes at 33°C (Process P3). After these leave-on times, the locks are rinsed and then dried under a hood.

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Abstract

The present invention relates to a process for dyeing keratin fibres, in particular human keratin fibres such as the hair, comprising at least two steps in which said fibres are treated first with a cosmetic dye composition Ci) comprising a) one or more dyes, which are preferably natural, b) one or more titanium salts and b1) optionally one or more particular carboxylic acids, and said fibres are then treated with a cosmetic revealing composition Cii) comprising c) one or more alkaline agents each comprising not more than one amine function and d) optionally one or more chemical oxidizing agents; to a cosmetic composition comprising ingredients a), b), b1), c) and d) as defined previously; and to a multi-compartment device comprising ingredients a), b), b1), c) and d).

Description

Hair dyeing process involving a dyeing step using a dye and a titanium salt, and a revealing step using an alkaline agent comprising not more than one amine function The present invention relates to a process for dyeing keratin fibres, in particular human keratin fibres such as the hair, comprising at least two steps in which said fibres are treated first with a cosmetic dye composition Ci) comprising a) one or more dyes, which are preferably natural, b) one or more titanium salts and b1 ) optionally one or more particular carboxylic acids, and said fibres are then treated with a cosmetic revealing composition Cii) comprising c) one or more alkaline agents each comprising not more than one amine function and d) optionally one or more chemical oxidizing agents; to a cosmetic composition comprising ingredients a), b), b1 ), c) and d) as defined previously; and to a multi-compartment device comprising ingredients a), b), b1 ), c) and d).
It is known practice to obtain "permanent colourings with dye compositions containing oxidation dye precursors, which are generally known as oxidation bases, such as ortho- or para-phenylenediamines, ortho- or para-aminophenols and heterocyclic compounds. These oxidation bases are colourless or weakly coloured compounds, which, when combined with oxidizing products, may give rise to coloured compounds via a process of oxidative condensation. It is also known that the shades obtained can be varied by combining these oxidation bases with couplers or colouring modifiers, the latter being chosen in particular from aromatic meta-diamines, meta-aminophenols, meta- diphenols and certain heterocyclic compounds, such as indole compounds. This oxidation dyeing process consists in applying to the keratin fibres bases or a mixture of bases and couplers with hydrogen peroxide (H202 or aqueous hydrogen peroxide solution), as oxidizing agent, in leaving it to diffuse, and then in rinsing the fibres. The colourings resulting therefrom are permanent, strong and resistant to external agents, especially to light, bad weather, washing, perspiration and rubbing.
However, it is still sought to increase the efficiency of the oxidation dyes used during this dyeing process in order to improve their build-up on keratin fibres. Indeed, such an improvement would make it possible in particular to decrease the contents of the oxidation dyes present in dyeing compositions, to reduce the leave-on time on keratin fibres and/or to use other dye families which have a weak dyeing capacity but which are capable especially of affording new shades or of producing colourings that are more persistent with respect to external agents such as light or shampoo washing, or, finally, of leading to better working qualities such as less staining of the scalp or clothing, or less colouring of the dyeing mixture (cleaner) during the application or the leave-on time.
Moreover, it is known practice to dye keratin fibres and in particular human hair with dye compositions containing direct dyes. The standard dyes that are used are, in particular, dyes of the nitrobenzene, anthraquinone, nitropyridine, azo, xanthene, acridine, azine or triarylmethane type, or natural dyes.
These dyes may be nonionic, anionic, cationic or amphoteric. These dyes are coloured or colouring molecules that have affinity for keratin fibres. These compositions containing one or more direct dyes are applied to keratin fibres for a time necessary to obtain the desired colouring, and are then rinsed out. The colourings that result therefrom are particularly chromatic colourings but are, however, only temporary or semi-permanent since the nature of the interactions that bind the direct dyes to the keratin fibre and their desorption from the surface and/or the core of the fibre are responsible for their weak dyeing power and their poor persistence with respect to light, washing or perspiration.
Progress therefore remains to be made in this field in order to afford powerful, resistant dyeing results that respect the nature of the hair using compositions containing dyes that are especially natural.
In the field of dyeing using natural extracts such as ortho-diphenols (ODPs), it is also known practice to dye keratin materials such as the hair or the skin using ODPs in the presence of a metal salt, especially of manganese (Mn) and/or zinc (Zn). In particular, patent applications FR 2 814 943, FR 2 814 945, FR 2 814 946 and FR 2 814 947 propose compositions for dyeing the skin or keratin fibres, comprising a dye precursor that contains at least one ortho-diphenol, Mn and/or Zn oxides and salts, alkaline agents of hydrogen carbonate type in a particular Mn, Zn/hydrogen carbonate ratio and optionally an enzyme. According to these documents, it is possible to obtain colourings on keratin materials with atmospheric oxygen or any oxygen-generating system.
However, the colourings obtained using ODPs are not strong enough or intense enough, and/or are not very persistent, especially in the case of hair fibres.
Moreover, it is known practice to use metals at acidic pH for dyeing keratin fibres in amounts similar to those employed for dyes using a mordanting process, which consists in preparing the fibres before performing the dyeing operation in order to obtain persistent shades (Ullmann's Encyclopaedia "Metal and Dyes", 2005 § 5.1 , page 8). However, this process generally has the drawback of not always respecting the cosmetic nature of the keratin fibre.
Other documents describe the use of ODPs in combination with Mn and Zn salts and other metal salts, including titanium salts, and a chemical oxidizing agent (FR 297 673, WO201 1/086284, WO201 1/086282 and FR 2 951 374).
Nevertheless, improvements should be further made, especially in terms of persistence of the colour with regard to shampooing and to sweat.
There is thus a real need to develop dyeing processes that make it possible to obtain more powerful and/or more persistent colourings using dyes, especially oxidation dyes, direct dyes of natural or non-natural origin, in particular ODPs, preferably using natural extracts that are rich in ODPs, less aggressive to keratin fibres, or that require smaller amounts of dyes. More particularly, there is a need to obtain colourings that satisfactorily withstand external agents (light, bad weather, shampooing or sweat), which are persistent and homogeneous, i.e. showing little dyeing selectivity between the root and the end, while at the same time remaining strong and/or chromatic. In addition, it is necessary, in order to obtain satisfactory colouring performance, for the product to be stable.
This (these) aim(s) are achieved by the present invention, one subject of which is a process for dyeing keratin fibres, in particular human keratin fibres such as the hair, in which said fibres are treated, in several steps, with:
• a cosmetic dye composition Ci) containing:
a) one or more dyes chosen in particular from direct dyes and natural dyes, preferably chosen from ortho-diphenols (ODPs);
b) one or more titanium (Ti) salts; in particular, the Ti atom of the salt is of oxidation state 2, 3 or 4, denoted Ti(ll), Ti(lll) or Ti(IV), preferably Ti(IV); and
b1 ) optionally one or more carboxylic acids of formula (I) below:
Figure imgf000004_0001
or a salt thereof, in which formula (I):
- A represents a saturated or unsaturated, cyclic or non-cyclic and aromatic or non- aromatic hydrocarbon-based group, which is monovalent when n has the value 0 or polyvalent when n is greater than or equal to 1 , comprising from 1 to 50 carbon atoms, which is optionally interrupted with one or more heteroatoms and/or optionally substituted, especially with one or more hydroxyl groups; preferably, A represents a monovalent (CrC6)alkyl group or a polyvalent (CrC6)alkylene group optionally substituted with one or more hydroxyl groups;
- n represents an integer between 0 and 10 inclusive; preferably, n is between 0 and 5, such as between 0 and 2; and then
• a cosmetic revealing composition Cii) containing:
c) one or more alkaline agents comprising not more than one amine function (-NH2); and d) optionally one or more chemical oxidizing agents such as hydrogen peroxide or one or more hydrogen peroxide-generating systems; it being understood that when composition Cii) contains several alkaline agents, then each of the alkaline agents comprises not more than one amine function, said process preferably comprising an intermediate rinsing step between the application of Ci) and Cii).
Preferably, the composition(s) used in the process of the invention are aqueous.
Another subject of the invention is a cosmetic composition, preferably an aqueous composition, for dyeing keratin fibres, containing ingredients a), b), b1 ), c) and d) as defined previously and optionally an organic solvent as defined below.
Another subject of the present invention relates to a multi-compartment device comprising ingredients a), b), c) and optionally d) distributed in several compartments.
The multi-compartment device or "kit" is suitable for performing the dyeing process according to the invention.
The process according to the invention has the advantage of dyeing human keratin fibres, with persistent dyeing results. In particular, the dyeing process according to the invention can produce colourings that are resistant to washing, perspiration and light without impairing the fibres. The resistance to perspiration is particularly good. Furthermore, the dyeing process used can induce satisfactory "build-up" and/or intensity (power) of the colouring.
Other subjects, characteristics, aspects and advantages of the present invention will emerge even more clearly on reading the description and the examples that follow. a) dve(s)
In accordance with the present invention, the process of the invention uses at least one composition Ci) comprising a) one or more dyes chosen in particular from oxidation dyes, direct dyes and dyes of natural origin, preferably chosen from ortho-diphenols or ODPs. a1 ) According to a first embodiment of the invention, the dye(s) are chosen from oxidation dyes.
The oxidation dye precursors that may be used in the present invention are generally chosen from oxidation bases, optionally combined with one or more couplers.
The oxidation bases may preferably be chosen from para-phenylenediamines, bis(phenyl)alkylenediamines, para-aminophenols, ortho-aminophenols and heterocyclic bases, and the addition salts thereof.
Preferentially, the oxidation base(s) of the invention are chosen from para- phenylenediamines and heterocyclic bases. Among the para-phenylenediamines, examples that may be mentioned include para-phenylenediamine, para-tolylenediamine, 2-chloro-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, 2,6-dimethyl- para-phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,5-dimethyl-para- phenylenediamine, Ν,Ν-dimethyl-para-phenylenediamine, N,N-diethyl-para- phenylenediamine, Ν,Ν-dipropyl-para-phenylenediamine, 4-amino-N,N-diethyl-3- methylaniline, N,N-bis(p-hydroxyethyl)-para-phenylenediamine, 4-N,N-bis(p- hydroxyethyl)amino-2-methylaniline, 4-N,N-bis(p-hydroxyethyl)amino-2-chloroaniline, 2-β- hydroxyethyl-para-phenylenediamine, 2-fluoro-para-phenylenediamine, 2-isopropyl-para- phenylenediamine, N-(p-hydroxypropyl)-para-phenylenediamine, 2-hydroxymethyl-para- phenylenediamine, 2-methoxymethyl-para-phenylenediamine, N,N-dimethyl-3-methyl- para-phenylenediamine, N-ethyl-N-(p-hydroxyethyl)-para-phenylenediamine, Ν-(β,γ- dihydroxypropyl)-para-phenylenediamine, N-(4'-aminophenyl)-para-phenylenediamine, N- phenyl-para-phenylenediamine, 2-p-hydroxyethyloxy-para-phenylenediamine, 2-β- acetylaminoethyloxy-para-phenylenediamine, N-(p-methoxyethyl)-para- phenylenediamine, 4-aminophenylpyrrolidine, 2-thienyl-para-phenylenediamine, 2-β- hydroxyethylamino-5-aminotoluene and 3-hydroxy-1 -(4'-aminophenyl)pyrrolidine, and the addition salts thereof with an acid.
Among the para-phenylenediamines mentioned above, para-phenylenediamine, para- tolylenediamine, 2-isopropyl-para-phenylenediamine, 2-p-hydroxyethyl-para- phenylenediamine, 2-p-hydroxyethyloxy-para-phenylenediamine, 2,6-dimethyl-para- phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,3-dimethyl-para- phenylenediamine, N,N-bis(p-hydroxyethyl)-para-phenylenediamine, 2-chloro-para- phenylenediamine, 2-p-acetylaminoethyloxy-para-phenylenediamine and 2- methoxymethyl-para-phenylenediamine, and the addition salts thereof with an acid, are particularly preferred.
Among the bis(phenyl)alkylenediamines, examples that may be mentioned include Ν,Ν'- bis(p-hydroxyethyl)-N,N'-bis(4'-aminophenyl)-1 ,3-diaminopropanol, N,N'-bis(p- hydroxyethyl)-N,N'-bis(4'-aminophenyl)ethylenediamine, N,N'-bis(4- aminophenyl)tetramethylenediamine, N,N'-bis(p-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 and 1 ,8-bis(2,5-diaminophenoxy)-3,6-dioxaoctane, and the addition salts thereof.
Among the para-aminophenols, examples that may be mentioned include para- aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 4-amino-3-chlorophenol, 4-amino-3-hydroxymethylphenol, 4-amino-2-methylphenol, 4-amino-2- hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol, 4-amino-2-(p-hydroxyethyl-aminomethyl)phenol and 4-amino-2-fluorophenol, and the addition salts thereof with an acid.
Among the ortho-aminophenols, examples that may be mentioned include 2- aminophenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol and 5-acetamido-2- aminophenol, and the addition salts thereof. Among the heterocyclic bases, mention may be made in particular of 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, for instance 2,5-diaminopyridine, 2- (4-methoxyphenyl)amino-3-aminopyridine and 3,4-diaminopyridine, and the addition salts thereof.
Other pyridine oxidation bases that are useful in the present invention are the 3- aminopyrazolo[1 ,5-a]pyridine oxidation bases or the addition salts thereof, described, for example, in patent application FR 2 801 308.
Examples that may be mentioned include pyrazolo[1 ,5-a]pyrid-3-ylamine, 2- acetylaminopyrazolo[1 ,5-a]pyrid-3-ylamine, 2-(morpholin-4-yl)pyrazolo[1 ,5-a]pyrid-3- ylamine, 3-aminopyrazolo[1 ,5-a]pyridine-2-carboxylic acid, 2-methoxypyrazolo[1 ,5- a]pyrid-3-ylamine, (3-aminopyrazolo[1 ,5-a]pyrid-7-yl)methanol, 2-(3-aminopyrazolo[1 ,5- a]pyrid-5-yl)ethanol, 2-(3-aminopyrazolo[1 ,5-a]pyrid-7-yl)ethanol, (3-aminopyrazolo[1 ,5- a]pyrid-2-yl)methanol, 3,6-diaminopyrazolo[1 ,5-a]pyridine, 3,4-diaminopyrazolo[1 ,5- a]pyridine, pyrazolo[1 ,5-a]pyridine-3,7-diamine, 7-(morpholin-4-yl)pyrazolo[1 ,5-a]pyrid-3- ylamine, pyrazolo[1 ,5-a]pyridine-3,5-diamine, 5-(morpholin-4-yl)pyrazolo[1 ,5-a]pyrid-3- ylamine, 2-[(3-aminopyrazolo[1 ,5-a]pyrid-5-yl)(2-hydroxyethyl)amino]ethanol, 2-[(3- aminopyrazolo[1 ,5-a]pyrid-7-yl)(2-hydroxyethyl)amino]ethanol, 3-aminopyrazolo[1 ,5- a]pyridin-5-ol, 3-aminopyrazolo[1 ,5-a]pyridin-4-ol, 3-aminopyrazolo[1 ,5-a]pyridin-6-ol, 3- aminopyrazolo[1 ,5-a]pyridin-7-ol, 2-p-hydroxyethoxy-3-aminopyrazolo[1 ,5-a]pyridine and 2-(4-dimethylpiperazinium-1 -yl)-3-aminopyrazolo[1 ,5-a]pyridine, and also the addition salts thereof.
More particularly, the oxidation bases according to the invention are chosen from 3- aminopyrazolo[1 ,5-a]pyridines preferably substituted in position 2 with:
a) a (di)(Ci-C6)(alkyl)amino group, the alkyl groups possibly being substituted with one or more hydroxyl, amino or imidazolium groups;
b) a cationic or non-cationic 5- to 7-membered heterocycloalkyl group comprising from 1 to 3 heteroatoms, optionally substituted with one or more (CrC6)alkyl groups such as di(CrC4)alkylpiperazinium;
c) a (CrC6)alkoxy group optionally substituted with one or more hydroxyl groups, such as β-hydroxyalkoxy, and also the addition salts thereof.
Among the pyrimidine derivatives, mention may be made of the compounds described, for example, in patents DE 2359399, JP 88169571 , JP 05-63124 and EP 0 770 375 or patent application WO 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 the addition salts thereof, and the tautomeric forms thereof, when a tautomeric equilibrium exists. Among the pyrazole derivatives, mention may be made of the compounds described in patents DE 3843892 and DE 4133957 and patent applications WO 94/08969, WO 94/08970, FR-A-2 733 749 and DE 195 43 988, for instance 4,5-diamino-1 - methylpyrazole, 4,5-diamino-1 -(p-hydroxyethyl)pyrazole, 3,4-diaminopyrazole, 4,5- diamino-1 -(4'-chlorobenzyl)pyrazole, 4,5-diamino-1 ,3-dimethylpyrazole, 4,5-diamino-3- methyl-1 -phenylpyrazole, 4,5-diamino-1 -methyl-3-phenylpyrazole, 4-amino-1 ,3-dimethyl- 5-hydrazinopyrazole, 1 -benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3-tert-butyl-1 - methylpyrazole, 4,5-diamino-1 -tert-butyl-3-methylpyrazole, 4,5-diamino-1 -(β- hydroxyethyl)-3-methylpyrazole, 4,5-diamino-1 -ethyl-3-methylpyrazole, 4,5-diamino-1 - ethyl-3-(4'-methoxyphenyl)pyrazole, 4,5-diamino-1 -ethyl-3-hydroxymethylpyrazole, 4,5- diamino-3-hydroxymethyl-1 -methylpyrazole, 4,5-diamino-3-hydroxymethyl-1 - isopropylpyrazole, 4,5-diamino-3-methyl-1 -isopropylpyrazole, 4-amino-5-(2'- aminoethyl)amino-1 ,3-dimethylpyrazole, 3,4,5-triaminopyrazole, 1 -methyl-3,4,5- triaminopyrazole, 3,5-diamino-1 -methyl-4-methylaminopyrazole and 3,5-diamino-4-(p- hydroxyethyl)amino-1 -methylpyrazole, and the addition salts thereof. Preferably, the heterocyclic oxidation bases of the invention are chosen from 4,5-diaminopyrazoles such as 4,5-diamino-1 -(p-hydroxyethyl)pyrazole. Use may also be made of 4,5-diamino-1 -(p- methoxyethyl)pyrazole.
Use will preferably be made of a 4,5-diaminopyrazole and even more preferentially of 4,5-diamino-1 -(p-hydroxyethyl)pyrazole and/or a salt thereof.
Pyrazole derivatives that may also be mentioned include diamino-N,N- dihydropyrazolopyrazolones and in particular those described in patent application FR-A- 2 886 136, such as the following compounds and the addition salts thereof: 2,3-diamino- 6,7-dihydro-1 H,5H-pyrazolo[1 ,2-a]pyrazol-1 -one, 2-amino-3-ethylamino-6,7-dihydro- 1 H,5H-pyrazolo[1 ,2-a]pyrazol-1 -one, 2-amino-3-isopropylamino-6,7-dihydro-1 H,5H- pyrazolo[1 ,2-a]pyrazol-1 -one, 2-amino-3-(pyrrolidin-1 -yl)-6,7-dihydro-1 H,5H-pyrazolo[1 ,2- a]pyrazol-1 -one, 4,5-diamino-1 ,2-dimethyl-1 ,2-dihydropyrazol-3-one, 4,5-diamino-1 ,2- diethyl-1 ,2-dihydropyrazol-3-one, 4,5-diamino-1 ,2-di(2-hydroxyethyl)-1 ,2-dihydropyrazol- 3-one, 2-amino-3-(2-hydroxyethyl)amino-6,7-dihydro-1 H,5H-pyrazolo[1 ,2-a]pyrazol-1 - one, 2-amino-3-dimethylamino-6,7-dihydro-1 H,5H-pyrazolo[1 ,2-a]pyrazol-1 -one, 2,3- diamino-5,6,7,8-tetrahydro-1 H,6H-pyridazino[1 ,2-a]pyrazol-1 -one, 4-amino-1 ,2-diethyl-5- (pyrrolidin-1 -yl)-1 ,2-dihydropyrazol-3-one, 4-amino-5-(3-dimethylaminopyrrolidin-1 -yl)-1 ,2- diethyl-1 ,2-dihydropyrazol-3-one or 2,3-diamino-6-hydroxy-6,7-dihydro-1 H,5H- pyrazolo[1 ,2-a]pyrazol-1 -one.
Use will preferably be made of 2,3-diamino-6,7-dihydro-1 H,5H-pyrazolo[1 ,2-a]pyrazol-1 - one and/or a salt thereof. Heterocyclic bases that will preferentially be used include 4,5-diamino-1 -(p- hydroxyethyl)pyrazole and/or 2,3-diamino-6,7-dihydro-1 H,5H-pyrazolo[1 ,2-a]pyrazol-1 - one and/or a salt thereof.
The oxidation base(s) used in the context of the invention are generally present in an amount ranging from 0.001% to 10% by weight approximately, and preferably ranging from 0.005% to 5%, relative to the total weight of the dye composition.
The additional couplers that are conventionally used for the dyeing of keratin fibres are preferably chosen from meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalene-based couplers and heterocyclic couplers, and also the addition salts thereof.
Examples that may be mentioned include 1 ,3-dihydroxybenzene, 1 ,3-dihydroxy-2- methylbenzene, 4-chloro-1 ,3-dihydroxybenzene, 1 -hydroxy-3-aminobenzene, 2-methyl-5- aminophenol, 3-amino-2-chloro-6-methylphenol, 2-methyl-5-hydroxyethylaminophenol, 2,4-diamino-1 -(3-hydroxyethyloxy)benzene, 2-amino-4-(3-hydroxyethylamino)-1 - methoxybenzene, 1 ,3-diaminobenzene, 1 ,3-bis(2,4-diaminophenoxy)propane, 3- ureidoaniline, 3-ureido-1 -dimethylaminobenzene, sesamol, thymol, 1 -β- hydroxyethylamino-3,4-methylenedioxybenzene, a-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 -Ν-(β- hydroxyethyl)amino-3,4-methylenedioxybenzene, 2,6-bis(3-hydroxyethylamino)toluene, 6-hydroxyindoline, 2,6-dihydroxy-4-methylpyridine, 1 -H-3-methylpyrazol-5-one, 1 -phenyl- 3-methylpyrazol-5-one, 2,6-dimethylpyrazolo[1 ,5-b]-1 ,2,4-triazole, 2,6-dimethyl[3,2-c]- 1 ,2,4-triazole and 6-methylpyrazolo[1 ,5-a]benzimidazole, the addition salts thereof with an acid, and mixtures thereof.
In general, the addition salts of the oxidation bases and couplers that may be used within the context of the invention are in particular chosen from the addition salts with an acid such as the hydrochlorides, hydrobromides, sulfates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates.
In the context of the present invention, the coupler(s) are generally present in a total amount ranging from 0.001 % to 10% by weight approximately of the total weight of the dye composition, and preferably ranging from 0.005% to 5% by weight relative to the total weight of the dye composition. a2) According to one embodiment of the invention, the dye(s) are chosen from dyes of natural origin.
The dyes of natural origin may be chosen especially from spinulosin, orceins, polyphenols or ortho-diphenols (also known as ODPs in the rest of the description) and all extracts rich in ODPs, curcumin, indole derivatives such as isatin or indole-2,3-dione, indigoids including indigo, phthalocyanines and porphyrins in particular complexed to a metal, glycosyl or non-glycosyl iridoids, chromene dyes, anthraquinone and benzoquinone dyes such as lawsone or henna, juglone, spinulosin, chromene or chroman dyes, such as neoflavanols and neoflavanones, flavanols, and indigoids such as indigo; and anthocyanidols. Use may also be made of extracts or decoctions containing these natural dyes and especially plant extracts or poultices containing said dyes.
The dye(s) of natural origin according to the invention may or may not be salified. They may also be in aglycone form (without bonded sugar) or in the form of glycosylated compounds.
The term "glycosyl radical' means a radical derived from a monosaccharide or polysaccharide.
According to a particularly preferred embodiment of the invention, the dye(s) are chosen from ortho-diphenol(s): ODP(s) and polyphenols.
The term "ODP(s)" means one or more compounds comprising one or more aromatic rings, at least one of which is a benzene ring substituted with at least two hydroxyl (OH) groups borne by two adjacent carbon atoms of said benzene group which is present in the structure of the ortho-diphenol(s).
The aromatic ring is more particularly a fused aryl or fused heteroaromatic ring, i.e. optionally comprising one or more heteroatoms, such as benzene, naphthalene, tetrahydronaphthalene, indane, indene, anthracene, phenanthrene, indole, isoindole, indoline, isoindoline, benzofuran, dihydrobenzofuran, chroman, isochroman, chromene, isochromene, quinoline, tetrahydroquinoline and isoquinoline, said aromatic ring comprising at least two hydroxyl groups borne by two adjacent carbon atoms of the aromatic ring. Preferentially, the aromatic ring of the ortho-diphenol derivatives according to the invention is a benzene ring.
The term "fused ring" means that at least two saturated or unsaturated and heterocyclic or non-heterocyclic rings have a shared bond, i.e. at least one ring is placed side-by-side with another ring.
More particularly, the dye(s) of the invention represent an ODP compound of formula (II), or an oligomer, tautomer, optical isomer or geometrical isomer thereof, and also salts or solvates thereof, such as hydrat
Figure imgf000010_0001
in which formula (II): • R1 to R4, which may be identical or different, represent: i) a hydrogen atom, ii) a halogen atom, or a group chosen from iii) hydroxyl, iv) carboxyl, v) (d- C20)alkyl carboxylate or (Ci-C20)alkoxycarbonyl, vi) optionally substituted amino, vii) optionally substituted linear or branched (C C2o)alkyl, viii) optionally substituted linear or branched (C2-C20)alkenyl, ix) optionally substituted cycloalkyl, x) (CrC2o)alkoxy, xi) (C1-C2o)alkoxy(C1-C2o)alkyl, xii) (CrC20)alkoxyaryl, xiii) aryl which may optionally be substituted, xiv) aryl, xv) substituted aryl, xvi) heterocyclic aryl which is saturated or unsaturated, optionally bearing a cationic or anionic charge and which is optionally substituted and/or optionally fused with an aromatic ring, preferably a benzene ring, said aromatic ring optionally being substituted, in particular with one or more hydroxyl or glycosyloxy groups, xvii) a radical containing one or more silicon atoms;
in which two of the substituents borne by two adjacent carbon atoms R1 - R2, R2 - R3 or R3 - R4 form, together with the carbon atoms that bear them, a saturated or unsaturated, aromatic or non-aromatic ring, optionally containing one or more heteroatoms and optionally fused with one or more saturated or unsaturated rings optionally containing one or more heteroatoms. In particular, the compound of formula (II) comprises from one to four rings.
A particular embodiment of the invention relates to one or more ODPs of formula (II), two adjacent substituents R1 - R2, R2 - R3 or R3 - R4 of which cannot form, with the carbon atoms that bear them, a pyrrolyl radical. According to a variant, R2 and R3 form a pyrrolyl or pyrrolidinyl radical fused to the benzene ring bearing the two hydroxyls.
For the purposes of the present invention and unless otherwise indicated:
- the saturated or unsaturated and optionally fused rings may also be optionally substituted;
- the "alkyf radicals are saturated, linear or branched, generally Ci-C20, particularly C Cio, hydrocarbon-based radicals, preferably Ci-C6 alkyl radicals, such as methyl, ethyl, propyl, butyl, pentyl and hexyl;
- the "alkenyf radicals are unsaturated and linear or branched C2-C20 hydrocarbon- based radicals; preferably comprising at least one double bond, such as ethylene, propylene, butylene, pentylene, 2-methylpropylene and decylene;
- the "aryf radicals are monocyclic or fused or non-fused polycyclic carbon-based radicals preferentially comprising from 6 to 30 carbon atoms, at least one ring of which is aromatic; preferentially, the aryl radical is chosen from phenyl, biphenyl, naphthyl, indenyl, anthracenyl and tetrahydronaphthyl;
- the "alkoxy" radicals are alkyl-oxy radicals with alkyl as defined previously, preferably C1-C10 alkyl, such as methoxy, ethoxy, propoxy and butoxy; the " ' alkoxyalkyf radicals are (Ci-C2o)alkoxy(Ci-C2o)alkyl radicals, such as methoxymethyl, ethoxymethyl, methoxyethyl, ethoxyethyl, etc.;
the "cycloalkyl' radicals are C4-C8 cycloalkyl radicals, preferably cyclopentyl and cyclohexyl radicals; the cycloalkyl radicals may be substituted cycloalkyl radicals, in particular substituted with alkyl, alkoxy, carboxylic acid, hydroxyl, amine and ketone groups;
the "alkyl' or "alkenyl' radicals, when they are "optionally substituted', may be substituted with at least one atom or group borne by at least one carbon atom chosen from: i) halogen; ii) hydroxyl; iii) (d-C2)alkoxy; iv) (CrCi0)alkoxycarbonyl; v) (poly)hydroxy(C2-C4)alkoxy; vi) amino; vii) 5- or 6-membered heterocycloalkyl; viii) optionally cationic 5- or 6-membered heteroaryl, preferably imidazolium, optionally substituted with a (CrC4)alkyl radical, preferably methyl; ix) amino substituted with one or two identical or different CrC6 alkyl radicals optionally bearing at least: a) one hydroxyl group, b) one amino group optionally substituted with one or two optionally substituted (CrC3)alkyl radicals, it being possible for said alkyl radicals to form, with the nitrogen atom to which they are attached, a saturated or unsaturated and optionally substituted 5- to 7-membered heterocycle optionally comprising at least one other nitrogen or non-nitrogen heteroatom, c) one quaternary ammonium group - N+R'R"R"', M" for which R', R" and R"\ which may be identical or different, represent a hydrogen atom or a Ci-C4 alkyl group; and M" represents the counterion of the corresponding organic acid, mineral acid or halide, d) or one optionally cationic 5- or 6-membered heteroaryl radical, preferentially imidazolium, optionally substituted with a (d-C4)alkyl radical, preferably methyl; x) acylamino (-N(R)-C(0)-R') in which the R radical is a hydrogen atom or a (d-C4)alkyl radical optionally bearing at least one hydroxyl group and the R' radical is a d-C2 alkyl radical; a carbamoyl ((R)2N-C(0)-) radical in which the R radicals, which may be identical or different, represent a hydrogen atom or a (d-C4)alkyl radical optionally bearing at least one hydroxyl group; xi) alkylsulfonylamino (R'-S(0)2-N(R)-) in which the R radical represents a hydrogen atom or a (d-C4)alkyl radical optionally bearing at least one hydroxyl group and the R' radical represents a (d-C4)alkyl radical, a phenyl radical; xii) aminosulfonyl ((R)2N-S(0)2-) in which the R radicals, which may be identical or different, represent a hydrogen atom or a (Ci-C4)alkyl radical optionally bearing at least one group chosen from a) hydroxyl, b) carboxyl -C(0)-OH in the acid or salified form (preferably salified with an alkali metal or a substituted or unsubstituted ammonium); xiii) cyano; xiv) nitro; xv) carboxyl or glycosylcarbonyl; xvi) phenylcarbonyloxy optionally substituted with one or more hydroxyl groups; xvii) glycosyloxy; and phenyl group optionally substituted with one or more hydroxyl groups; the "aryf or "heterocyclic" radicals or the aryl or heterocyclic part of the radicals, when they are "optionally substituted", may be substituted with at least one atom or group borne by at least one carbon atom chosen from:
i) (CrC10)alkyl, preferably CrC8 alkyl, optionally substituted with one or more radicals chosen from the following radicals: hydroxyl, (C1-C2)alkoxy, (poly)hydroxy(C2-C4)alkoxy, acylamino, amino substituted with two identical or different Ci-C4 alkyl radicals optionally bearing at least one hydroxyl group or it being possible for the two radicals to form, with the nitrogen atom to which they are attached, a saturated or unsaturated and optionally substituted 5- to 7-membered, preferably 5- or 6-membered, heterocycle optionally comprising another nitrogen or non-nitrogen heteroatom; ii) halogen; iii) hydroxyl; iv) C C2 alkoxy; v) CrC10 alkoxycarbonyl; vi) (poly)hydroxy(C2-C4)alkoxy; vii) amino; viii) 5- or 6-membered heterocycloalkyl; ix) optionally cationic 5- or 6-membered heteroaryl, preferably imidazolium, optionally substituted with a (d-C4)alkyl radical, preferably methyl; x) amino substituted with one or two identical or different CrC6 alkyl radicals optionally bearing at least: a) one hydroxyl group, b) one amino group optionally substituted with one or two optionally substituted CrC3 alkyl radicals, it being possible for said alkyl radicals to form, with the nitrogen atom to which they are attached, a saturated or unsaturated and optionally substituted 5- to 7-membered heterocycle optionally comprising at least one other nitrogen or non-nitrogen heteroatom, c) one quaternary ammonium group -N+R'R"R"', M" for which R', R" and R"\ which may be identical or different, represent a hydrogen atom or a Ci-C4 alkyl group; and M" represents the counterion of the corresponding organic acid, mineral acid or halide, d) one optionally cationic 5- or 6-membered heteroaryl radical, preferably imidazolium, optionally substituted with a (Ci-C4)alkyl radical, preferentially methyl; xi) acylamino (-N(R)-C(0)-R') in which the radical R is a hydrogen atom or a Ci-C4 alkyl radical optionally bearing at least one hydroxyl group and the radical R' is a C C2 alkyl radical; xii) carbamoyl ((R)2N-C(0)-) in which the R radicals, which may be identical or different, represent a hydrogen atom or a CrC4 alkyl radical optionally bearing at least one hydroxyl group; xiii) alkylsulfonylamino (R'S(0)2-N(R)-) in which the radical R represents a hydrogen atom or a Ci-C4 alkyl radical optionally bearing at least one hydroxyl group and the radical R' represents a Ci-C4 alkyl radical, a phenyl radical; xiv) aminosulfonyl ((R)2N-S(0)2-) in which the radicals R, which may be identical or different, represent a hydrogen atom or a CrC4 alkyl radical optionally bearing at least one hydroxyl group; xv) carboxyl in the acid or salified form (preferably salified with an alkali metal or a substituted or unsubstituted ammonium); xvi) cyano; xvii) nitro; xviii) polyhaloalkyl, preferentially trifluoromethyl; xix) a glycosylcarbonyl; xx) a phenylcarbonyloxy group optionally substituted with one or more hydroxyl groups; xxi) a glycosyloxy group; and xxii) a phenyl group optionally substituted with one or more hydroxyl groups;
- for the purposes of the present invention, the term "glycosyf radical means a radical derived from a mono- or polysaccharide;
- the radicals "containing one or more silicon atoms" are preferably polydimethylsiloxane, polydiphenylsiloxane, polydimethylphenylsiloxane or stearoxy dimethicone radicals;
- the "heterocyclic" radicals are radicals comprising, in at least one ring, one or more heteroatoms chosen in particular from O, N and S, preferably O or N, optionally substituted in particular with one or more alkyl, alkoxy, carboxyl, hydroxyl, amine or ketone groups. These rings may comprise one or more oxo groups on the carbon atoms of the heterocycle; mention may in particular be made, among the heterocyclic radicals that may be used, of furyl, pyranyl, pyrrolyl, imidazolyl, pyrazolyl, pyridyl or thienyl groups; even more preferably, the heterocyclic groups are fused groups, such as benzofuryl, chromenyl, xanthenyl, indolyl, isoindolyl, quinolyl, isoquinolyl, chromanyl, isochromanyl, indolinyl, isoindolinyl, coumarinyl or isocoumarinyl groups, it being possible for these groups to be substituted, in particular with one or more OH groups.
Included among the natural dyes according to the invention are compounds that may be present in nature and that are reproduced by chemical (semi)synthesis.
The salts of the dyes of the invention may be salts of acids or of bases. The acids may be mineral or organic. Preferably, the acid is hydrochloric acid, which results in chlorides.
According to another preferred embodiment of the invention, the dye composition used in the process for dyeing keratin fibres comprises, as dye, one or more natural dyes.
More particularly, the dye(s) a) of the invention are chosen from:
- flavanols, for instance catechin and epicatechin gallate,
- flavonols, such as quercetin,
- anthocyanidins, for instance cyanidin, delphinidin and petunidin,
- anthocyanins or anthocyans, for instance myrtillin,
- ortho-hydroxybenzoates, for example gallic acid salts,
- flavones, such as luteolin,
- hydroxystilbenes, for example 3,3',4,5'-tetrahydroxystilbene, optionally oxylated (for example glucosylated),
- curcumin,
- indole derivatives, - phthalocyanines and porphyrins, in particular complexed to a metal,
- glycosyl or non-glycosyl iridoids,
- 3,4-dihydroxyphenylalanine and derivatives thereof,
- 2,3-dihydroxyphenylalanine and derivatives thereof,
- 4,5-dihydroxyphenylalanine and derivatives thereof,
- dihydroxycinnamates, such as caffeic acid and chlorogenic acid,
- ortho-polyhydroxycoumarins,
- ortho-polyhydroxyisocoumarins,
- ortho-polyhydroxycoumarones,
- ortho-polyhydroxyisocoumarones,
- ortho-polyhydroxychalcones,
- ortho-polyhydroxychromones,
- (anthra)quinones,
- hydroxyxanthones,
- 1 ,2-dihydroxybenzene and derivatives thereof,
- 1 ,2,4-trihydroxybenzene and derivatives thereof,
- 1 ,2,3-trihydroxybenzene and derivatives thereof,
- 2,4,5-trihydroxytoluene and derivatives thereof,
- proanthocyanidins and especially the proanthocyanidins A1 , A2, B1 , B2, B3 and C1 , - chroman and chromene compounds,
- proathocyanines,
- tannic acid,
- ellagic acid,
- and mixtures of these compounds.
In particular, the dye(s) a) are chosen from the following ODPs:
- flavanols, for instance catechin and epicatechin gallate,
- flavonols, such as quercetin,
- anthocyanidins, for instance cyanidin, delphinidin and petunidin,
- anthocyanins or anthocyans, for instance myrtillin,
- ortho-hydroxybenzoates, for example gallic acid salts,
- flavones, such as luteolin,
- hydroxystilbenes, for example 3,3',4,5'-tetrahydroxystilbene, optionally oxylated (for example glucosylated),
- 3,4-dihydroxyphenylalanine and derivatives thereof,
- 2,3-dihydroxyphenylalanine and derivatives thereof,
- 4,5-dihydroxyphenylalanine and derivatives thereof,
- dihydroxycinnamates, such as caffeic acid and chlorogenic acid, - ortho-polyhydroxy(iso)coumarins,
- ortho-polyhydroxy(iso)coumarones,
- ortho-polyhydroxychalcones,
- ortho-polyhydroxychromones,
- quinones,
- hydroxyxanthones,
- 1 ,2-dihydroxybenzene and derivatives thereof,
- 1 ,2,4-trihydroxybenzene and derivatives thereof,
- 1 ,2,3-trihydroxybenzene and derivatives thereof,
- 2,4,5-trihydroxytoluene and derivatives thereof,
- proanthocyanidins and especially the proanthocyanidins A1 , A2, B1 , B2, B3 and C1 ,
- chromans and chromenes,
- proanthocyanines,
- tannic acid,
- ellagic acid,
- and mixtures of the preceding compounds;
preferably, the ODP(s) are chosen from haematein, brazilein, gallic acid, tannic acid, haematoxylin and brazilin, and mixtures thereof.
According to a particular embodiment of the invention, the dye(s) of the invention are chosen from anthraquinone dyes, and preferably natural dyes, chosen from those of formulae (A1) and (A2) below:
Figure imgf000016_0001
(A1) (A2) and also the tautomeric and/or mesomeric forms thereof, the stereoisomers thereof, the addition salts thereof with a cosmetically acceptable acid or base, and the solvates thereof such as hydrates; in which formulae (A1) and (A2):
• R1 and R8, which may be identical or different, represent a hydrogen atom or a hydroxyl group or alkyl such as methyl;
• R2 represents a hydrogen atom or a hydroxyl group, carboxyl group -C(0)OH or carboxylate group -C(0)0", CTwith Q+ representing an alkali metal or alkaline-earth metal such as potassium or calcium;
• R3 represents i) a hydrogen atom, ii) a hydroxyl group or iii) an optionally substituted aryl group, preferably a phenyl group optionally substituted with one or more groups chosen from a) hydroxyl, b) amino, c) (d-C6)alkyl optionally substituted with one or more groups chosen from hydroxyl, carboxyl and (CrC4)alkylcarbonylamino;
• R4 represents a hydrogen atom or a hydroxyl group;
• R5 represents a hydrogen atom, or a hydroxyl, carboxyl or carboxylate group -C(0)0", CTwith Q+ as defined previously;
• R6 represents a hydrogen atom, a hydroxyl group, -O", Q+ with Q+ as defined previously, carboxyl or carboxylate group -C(0)0", CTwith Q+ as defined previously;
• R7 represents a hydrogen atom or a glycosyl radical, preferably glucose;
• M represents a metal, preferably from column IIIA of the Periodic Table of the Elements, such as aluminium; and
• G represents a hydroxyl group, a water molecule or a ligand such as alkoxy or (di)(alkyl)amino.
Preferentially, the dyes of the invention are of formula (A1) and in particular, taken together or separately:
■ R1 represents a hydroxyl or (CrC4)alkyl group;
■ R2, R4 and R8, which may be identical or different, represent a hydrogen atom or a hydroxyl group;
■ R3 represents a hydrogen atom, a hydroxyl group or a phenyl group optionally substituted with one or more groups chosen from hydroxyl, carboxyl and (C C4)alkylcarbonylamino such as:
Figure imgf000017_0001
molecule.
• R5 and R6, which may be identical or different, represent a hydrogen atom or a hydroxyl group, carboxyl group -C(0)OH or carboxylate group -C(0)0", Q+ with Q+ representing an alkali metal or alkaline-earth metal such as potassium or calcium; and
• R7 represents a hydrogen atom. According to one embodiment, the dye(s) of the invention are of formula (A2) and in particular, taken together or separately:
■ R1 represents a (CrC4)alkyl group;
■ R2 represents a carboxyl or carboxylate group -C(0)0", Q+ with Q+ representing an alkali metal or alkaline-earth metal such as potassium or calcium;
■ R3 and R8 represent a hydroxyl group;
■ R4 represents a hydrogen atom or a hydroxyl group, preferably hydrogen;
■ R6 represents a hydroxyl group or -O", Q+ with Q+ as defined previously; and
• R7 represents a glycosyl radical such as glucose.
More preferentially, the dye(s) of the invention are chosen from the following anthraquinones and extracts containing them:
• Garance (Rubia tinctorum or Rubia cordifolia);
• 1 ,3-dihydroxyanthraquinone (purpuroxanthine);
· 1 ,4-dihydroxyanthraquinone (quinizarine);
• 1 ,2,4-trihydroxyanthraquinone (purpurin, veratin, Smoke Brown G, C.I. 1037, C.I.
58205, C.I. 75410, C.I. Natural Red 16, C.I. Natural Red 8) ;
• 1 ,2-dihydroxyanthraquinone (alizarin);
• carmine (Crimson lake, cochineal, natural red 4, C.I. 75470 or E120), the aluminium salt of carminic acid;
• laccaic acid A, B, C or D; and
• anthragallol or 1 ,2,3-trihydroxyanthraquinone.
According to another particular mode of the invention, the dye(s) are chosen from benzoquinones and naphthoquinones, in particular juglone and lawsone. In particular those derived from leaves of shrubs of the genus Lawsonia from the family of Lythraceae, which is based on the principle of dyeing with the active agent lawsone: 2-hydroxy-1 ,4- naphthoquinone from henna. Lawsone [83-72-7] (CI Natural Orange 6; CI 75420), also known as isojuglone, may be found in henna shrubs (Lawsonia alba, Lawsonia inermis). Preferably, henna is in powder form. The henna powder may be screened to obtain particles with upper limit sizes corresponding to the orifices or mesh sizes of the screen particularly between 35 and 80 mesh (US). According to one particular mode of the invention, the size of the henna powder particles is fine. According to the invention, a particle size of less than or equal to 500 mm is more particularly intended. Preferentially, the powder is constituted of fine particles with a size inclusively between 50 and 300 mm and more particularly between 10 and 200 mm. It is understood that said henna particles preferentially have a moisture content of between 0 to 10% by weight, relative to the total weight of the powders. According to another particular embodiment, the dye(s) are chosen from indole derivatives such as isatin or indole-2,3-dione and indigo, preferably isatin. In particular, the dye(s) are derived from the plants Isatis tinctoria, Calanthe discolor or Couroupita guianensis.
According to a preferred embodiment of the invention, at least one cosmetic composition comprises at least one natural dye c) chosen from naphtoquinone dyes, such as lawsone or henna, juglone, spinulosin, preferably lawsone or henna, and/or from indole derivatives such as isatin or indole-2,3-dione, indigoids including indigo, preferably indigo.
According to another preferred embodiment of the invention, at least one cosmetic composition comprises at least two natural dyes c), wherein preferably at least one dye is chosen from naphtoquinone dyes, such as lawsone or henna, juglone, spinulosin, preferably lawsone or henna, and/or from indole derivatives such as isatin or indole-2,3- dione, indigoids including indigo, preferably indigo ; or mixture thereof, better still said at least two natural dyes c) are chosen from naphtoquinone dyes such as lawsone or henna, juglone, spinulosin, preferably lawsone or henna, and indole derivatives such as isatin or indole-2,3-dione, indigoids including indigo, preferably indigo.
According to a particular embodiment, the dye(s) are curcumine or curcumin. This is a compound that is naturally present in curry, which is a polyphenol whose chemical name is (1 £,6£)-1 ,7-bis(4-hydroxy-3-methoxyphenyl)-1 ,6-heptadiene-3,5-dione, and also the tautomeric forms thereof.
According to a particular embodiment, the dye(s) of the invention are chosen from natural porphyrins and phthalocyanines, in particular those complexed with a metal, especially chlorophyllin and in particular that complexed with copper or magnesium, preferably copper chlorophyllin.
According to one embodiment, the dye(s) are chosen from glycosyl or non-glycosyl iridoids. In particular, the dye(s) of the invention are chosen from (seco)iridoid glycoside or non-glycosyl (seco)iridoid (also known as aglycone), extracted from plants such as Rubiaceae, Euphorbiaceae, Valerianaceae, Cornaceae, Gentianaceae, Caprifoliaceae, Oleaceae, Ericaceae, Loganiaceae, etc., preferably Rubiaceae. More particularly, the dye(s) of the invention are derived from extracts of the following plants: Veronica persica; Genipa americana; Apodytes dimidiata; Randia canthioides; Tarenna attenuata and preferably Genipa americana. According to a particularly preferred embodiment of the invention, the dye(s) a) are chosen from chromene or chroman dyes. According to the invention, the term "chromene or chroman dyes" means dyes which comprise in their structure at least one bicycle of formula (B) below:
Figure imgf000020_0001
(B)
the endocyclic bond representing a carbon-carbon single bond or else a carbon- carbon double bond, as illustrated by formula (B1) below, denoting the chromene family, and formula (B2) below, denoting the chroman family:
Figure imgf000020_0002
(B1) (B2)
More particularly, the dye(s) a) of the invention are of formula (B) and are preferentially chosen from neoflavonols and neoflavanones, particularly chosen from the dyes of the following formulae:
> formula (III), comprising, in its structure, the bicycle of formula (B2),
Figure imgf000020_0003
and also the tautomeric and/or mesomeric forms thereof, the stereoisomers thereof, the addition salts thereof with a cosmetically acceptable acid or base, and the solvates thereof such as hydrates;
in which formula (III):
• zz ^ represents a carbon-carbon single bond or a carbon-carbon double bond, the sequence of these bonds denoting two carbon-carbon single bonds and two carbon-carbon double bonds, said bonds being conjugated,
· X represents a group: // /
HO-C or 0=C
\ \
• R1 , R2, R3, R4, R5 and R6, which may be identical or different, represent a hydrogen atom, a hydroxyl group, an optionally substituted alkyl group, an optionally substituted alkoxy group or an optionally substituted acyloxy group; and
> formula (IV), comprising, in its structure, the bicycle of formula (B1):
Figure imgf000021_0001
and also the tautomeric and/or mesomeric forms thereof, the stereoisomers thereof, the addition salts thereof with a cosmetically acceptable acid or base, and the hydrates thereof;
in which formula (IV):
• Rn , Ri2, Ri3, Ri 6, ig and R20, which may be identical or different, represent a hydrogen atom or a CrC4 alkyl radical, and
• Ri4, Ri5, Ri7 and R18, which may be identical or different, represent a hydrogen atom, a hydroxyl radical or a Ci-C4 alkoxy radical.
As regards the dyes of formula (III) as defined previously, they may be found in two tautomeric forms denoted (Ilia) and (1Mb):
Figure imgf000021_0002
The alkyl radicals mentioned in the preceding definitions of the substituents are saturated and linear or branched hydrocarbon-based radicals, generally C C-20, particularly CrC10, preferably CrC6, hydrocarbon-based radicals, such as methyl, ethyl, propyl, butyl, pentyl and hexyl. The alkoxy radicals are alkyl-oxy radicals with the alkyl radicals as defined above and preferably the alkoxy radicals are C1-C10 alkoxy radicals, such as methoxy, ethoxy, propoxy and butoxy.
The alkyl or alkoxy radicals, when they are substituted, may be substituted with at least one substituent borne by at least one carbon atom chosen from: i) a halogen atom or ii) a hydroxyl group; iii) a C C2 alkoxy group; iv) a CrC10 alkoxycarbonyl group; v) a (poly)hydroxy(C2-C4)alkoxy group; vi) an amino group; vii) a 5- or 6-membered heterocycloalkyl group; viii) an optionally cationic 5- or 6-membered heteroaryl group, preferably imidazolium, optionally substituted with a (d-C4)alkyl radical, preferably methyl; ix) an amino radical substituted with one or two identical or different CrC6 alkyl radicals optionally bearing at least: a) one hydroxyl group, b) one amino group optionally substituted with one or two optionally substituted CrC3 alkyl radicals, it being possible for said alkyl radicals to form, with the nitrogen atom to which they are attached, a saturated or unsaturated and optionally substituted 5- to 7-membered heterocycle optionally comprising at least one other nitrogen or non-nitrogen heteroatom, c) one quaternary ammonium group -N+R'R"R"', M" for which R', R" and R"\ which may be identical or different, represent a hydrogen atom or a CrC4 alkyl group and M" represents the counterion of the corresponding organic acid, mineral acid or halide, d) or one optionally cationic 5- or 6-membered heteroaryl radical, preferably imidazolium, optionally substituted with a (Ci-C4)alkyl radical, preferably methyl; x) an acylamino (-N(R)-C(0)-R') radical in which the R radical is a hydrogen atom or a Ci-C4 alkyl radical optionally bearing at least one hydroxyl group and the R' radical is a C C2 alkyl radical; xi) a carbamoyl ((R)2N-C(0)-) radical in which the R radicals, which may be identical or different, represent a hydrogen atom or a CrC4 alkyl radical optionally bearing at least one hydroxyl group; xii) an alkylsulfonylamino (R'-S(0)2-N(R)-) radical in which the R radical represents a hydrogen atom or a Ci-C4 alkyl radical optionally bearing at least one hydroxyl group and the R' radical represents a Ci-C4 alkyl radical, a phenyl radical; xiii) an aminosulfonyl ((R)2N-S02-) radical in which the R radicals, which may be identical or different, represent a hydrogen atom or a CrC4 alkyl radical optionally bearing at least one hydroxyl group; xiv) a carboxyl radical in the acid or salified form (preferably salified with an alkali metal or a substituted or unsubstituted ammonium); xv) a cyano group; xvi) a nitro group; xvii) a carboxyl or glycosylcarbonyl group; xviii) a phenylcarbonyloxy group optionally substituted with one or more hydroxyl groups; xix) a glycosyloxy group; and xx) a phenyl group optionally substituted with one or more hydroxyl groups.
Preferably, the alkyl or alkoxy radicals of formula (III) are unsubstituted.
According to a particular embodiment of the invention, the dyes of formula (III) comprise a radical R6 representing a hydroxyl group. Another particular embodiment of the invention relates to the dye(s) of formula (III) for which the radical Ri represents a hydrogen atom or a hydroxyl group.
More particularly, the dye(s) of the invention are of formula (III) and chosen from haematoxylin, haematein, brazilin and brazilein; preferentially haematoxylin and brazilin:
Figure imgf000023_0001
Haematoxylin (Natural Black 1 Brazilin (Natural Red 24 - CAS 517-28-2) CAS 474-07-7)
Brazilein is a conjugated form of a chroman compound of formula (A2). The tautomeric structures (Ilia) and (1Mb) illustrated above are found in the scheme below.
Figure imgf000023_0002
Brazilein
Among the dyes of the invention of haematoxylin/haematein and brazilin/brazilein type, examples that may be mentioned include haematoxylin (Natural Black 1 according to the INCI name) and brazilin (Natural Red 24 according to the INCI name), dyes of the indochroman family, which are commercially available. The latter dyes may exist in an oxidized form and may be obtained synthetically or by extraction of plants or vegetables known to be rich in these dyes.
The dye(s) of natural origin of the invention may be used in the form of extracts. Use may be made of the following plant extracts (genus and species): Haematoxylon campechianum, extracted from oxidized logwood (Haematoxylon campechianum) brasiletto (Haematoxylum brasiletto, rich in brazilin and protosappanin), Quebracho (Schinopsis lorentzii) Caesalpinia echinata, Caesalpinia sappan, Caesalpinia spinosa, and Caesalpina brasiliensis. The extracts are obtained by extracting the various plant parts, for instance the roots, the wood, the bark or the leaves.
According to a particular embodiment of the invention, the dye(s) of natural origin are of formula (II) and are obtained from logwood, pernambuco wood, sappan wood and Brazil wood.
According to a particular embodiment of the invention, the dyes are of formula (IV), preferably those for which Rn and R13 represent an alkyl radical, preferably methyl.
Preferably, R12, Ri e, R19 and R20 denote, independently of each other, a hydrogen atom or an alkyl radical, preferably methyl.
Preferably, R14 and R17 denote, independently of each other, a hydrogen atom or an alkoxy radical, preferably methoxy.
Preferably, R18 and R15 denote, independently of each other, a hydrogen atom, a hydroxyl radical or an alkoxy radical, preferably methoxy.
A first particularly preferred family of dyes of natural origin of the invention that are suitable for use in the present invention is that of the dyes corresponding to formula (IV) above for which R12, Ri5, Ri 6, i7, R19 and R20 each represent a hydrogen atom, R^ and R13 each represent a methyl radical and R14 represents a methoxy radical.
Among the preferred dyes of the invention of this first family are those for which R18 represents a methoxy radical (santalin B) or a hydroxyl radical (santalin A).
A second particularly preferred family of dyes that are suitable for use in the present invention is that of the dyes corresponding to formula (IV) above for which:
- Rn and R13 each represent a methyl radical,
- R17 represents a methoxy radical.
A preferred dye of this second family is that for which, in addition, R19 represents a methyl radical, R20, Ri2, Ri4, Ri8 and R1 6 each represent a hydrogen atom and R15 represents a hydroxyl radical (santarubin A).
A second preferred dye of this second family is that for which R18, R20, R12, R14 and R1 6 represent a hydrogen atom, R15 represents a methoxy radical and R19 represents a methyl radical (santarubin B).
A third family of preferred dyes of this second family is that for which R20, R12, Ri4, R15,
Ri e and Rig represent hydrogen and R18 represents a hydroxyl radical (santarubin C). The advantageous dye(s) of this second family are that for which R15 represents a methoxy radical, R18 and R14 represent a hydrogen atom and R20, Ri2, Ri 6 and R19 represent a methyl radical (tetra-O-methylsantarubin).
The natural dye(s) of formula (IV) may be used in the form of extracts. Use may be made of plant extracts of red woods, bringing together generally the species of red woods from Asia and West Africa of the genus Pterocarpus and of the genus Baphia. These woods are, for example, Pterocarpus santalinus, Pterocarpus osun, Pterocarpus soyauxii, Pterocarpus erinaceus, Pterocarpus indicus or Baphia nitida. These woods may also be called padauk, sandalwood, narra wood, camwood or bar wood.
Thus, extracts that may be used, comprising dyes of formula (IV), in the present invention may be obtained, for example, from red sandalwood (Pterocarpus santalinus) by aqueous basic extraction, such as the product sold under the trade name Santal Concentre SL 709C by the company COPIAA, or also by means of solvent extraction of sandalwood powder, such as the product sold under the trade name Santal Poudre SL PP by the same company COPIAA. Mention may also be made of the aqueous/alcoholic extract of powdered red sandalwood from the company Alban Muller.
Extracts also suitable for the present invention can be obtained from woods such as camwood (Baphia nitida) or also bar wood (Pterocarpus soyauxii, Pterocarpus erinaceus): the latter is thus split up and then ground: a conventional alcoholic extraction or one by percolation is subsequently carried out on this ground material in order to collect a pulverulent extract particularly suitable for the implementation of the present invention.
The dye(s) of formulae (III) and (IV) of the invention may be salts of acids or bases that are cosmetically acceptable.
The acids may be mineral or organic. Preferably, the acid is hydrochloric acid, which results in chlorides.
The bases may be mineral or organic. In particular, the bases are alkali metal hydroxides such as sodium hydroxide which leads to sodium salts.
According to a particular embodiment of the invention, the dye(s) are chosen from dihydroxyflavonoids, preferably of formula (V) and also the organic or mineral acid or base salts thereof, optical, geometric and tautomeric isomers thereof, and solvates thereof such as hydrates:
Figure imgf000025_0001
in which formula (V):
represents a single bond or a double bond;
Ft1, Ft2, Ft3, Ft4, Ft10, Ft11, Ft12, Ft13 and Ft14, which may be identical or different, represent a hydrogen or halogen atom or a group chosen from i) hydroxyl, ii) (d-C6)alkyl, iii) (CrC6)alkoxy, iv) (CrC6)alkylthio, v) carboxyl, vi) alkyl or alkoxycarbonyl carboxylate, vii) optionally substituted amino, viii) optionally substituted linear or branched alkenyl, ix) optionally substituted cycloalkyl, x) optionally substituted aryl, xi) a group containing one or more silicon atoms, xii) (di)((hydroxy)(Ci-C6)alkyl)amino, xiii) glucosyl, xiv) R-Z-C(X)- Y- with R representing a hydrogen atom or a (d-C6)alkyl or aryl group that is optionally substituted, especially with at least one hydroxyl group, such as 3,4,5-trihydroxyphenyl; Y and Z, which may be identical or different, represent a bond or an oxygen or sulfur atom or a group -N(R with R' representing a hydrogen atom or a (CrC6)alkyl group, Y also possibly representing a (CrC6)alkylene group; X representing an oxygen or sulfur atom or N-R" with R" representing a hydrogen atom or a (CrC6)alkyl group;
• R5, R6, R7, R8 and R9, which may be identical or different, represent a hydrogen atom or a group chosen from a hydroxyl group, a (CrC6)alkyl group or a group R-Z-C(X)-
Y- as defined previously;
• or alternatively the unit (V) constitutes a polymeric unit of a polyphenol which will be linked to the other units of said polyphenol via positions 4, 6 or 8 of the chroman ring, in which case R1, or R3 and R6 form a covalent bond with the other units of said polyphenol;
• or else R5 with R6 and/or R7 with R8 form, together with the carbon atom which bears them, an oxo group;
• or else R8 and R9 together form a bond;
it being understood that:
- when R5with R6 and/or R7 with R8 together form an oxo group, or R8 with R9 together form a bond, then represent a single bond;
- when is a double bond between the oxygen atom and the carbon atom in position 2, then R9 is absent, and when is a double bond between the carbon atoms in positions 3 and 4, then R5 and R7 are absent;
- when borne by the oxygen atom is a double bond, then the compound of formula (V) is cationic and an organic or mineral anionic counterion such as halide is associated therewith.
Preferably, at least two radicals of the compounds of formula (V) chosen from R1, R2, R3, R4, R10, R11, R12, R13 and R14, which are contiguous, represent a hydroxyl group.
Preferably, the group R-Z-C(X)-Y- of the compounds of formula (V) represents a 3,4,5- trihydroxyphenyl- 1-carbonyloxy (-O-gallate). Preferably, the radicals Ri, R2, R3, R4, R10, R11 , R12, Ri3 and Ri4 are chosen from a hydrogen atom and hydroxyl, glycosyloxy and alkoxy groups.
According to a particular embodiment, the dye(s) of the invention are chosen from: i) the flavanols of formula (Va) which preferably comprise at least two ortho hydroxyl groups, such as catechin, extracted from pine bark, epicatechin gallate, and cocoa flavonols, especially epicatechin, flavonols, in particular flavan-3-ol from green tea, and oligomers and polymers thereof known as proanthocyanidols or fused tannins such as theaflavin, theaflavin 3'-0-gallate, theaflavin 3,3'-0-digallate, proanthocyanidins A1 , A2, B1 , B2, B3 and C1 such as profisetinidin and procyanidin, and mixtures of the preceding compounds.
Flavan-3-ol or flavanol:
Figure imgf000027_0001
(Va)
and also the organic or mineral acid or base salts thereof, the optical isomers, geometrical isomers and tautomers thereof, and the solvates thereof such as hydrates; in which formula (Va):
• R7, R8, which may be identical or different, represent a hydrogen atom or a group chosen from hydroxyl, (d-C6)alkyl or a group R-Z-C(X)-Y- as defined previously, preferably O-gallate, it being understood that at least one of the two groups;
• R7 or R8 represents a hydroxyl group or R-Z-C(X)-Y- as defined previously;
• R5 and R6, which may be identical or different, represent a hydrogen atom or a hydroxyl group or R6 and R8 form a bond or the unit (Va) constitutes the polymeric unit that will be bonded to the other units via positions 4, 6 or 8, in which case R1, or R3 and R6 form a bond; the radicals R1, R2, R3, R4, R10, R11, R12, R13 and R14 being as defined previously for formula (V);
Among the proanthocyanidin compounds, examples that may be mentioned include profisetinidin and procyanidin, the formulae of which are represented below;
- ii) flavonols of formula (Vb) which comprise at least two ortho hydroxyl groups, such as quercetin, luteolin, myricetol or fisetin, and/or two meta hydroxyl groups, such as morin, heterosides thereof, methoxylated derivatives thereof such as rhamnetin (which preferably comprise at least two ortho hydroxyl groups): Flavonol:
Figure imgf000028_0001
3-hydroxy-2-phenylchromen-4-one
and also the organic or mineral acid or base salts thereof, the optical, geometrical and tautomeric isomers thereof, and the solvates thereof such as hydrates;
in which formula (Vb) the radicals Ft1, Ft2, Ft3, Ft4, Ft10, Ft11, Ft12, Ft13 and Ft14 are as defined previously in formula (V);
- iii) the flavones of formula (Vc) which comprise at least two ortho hydroxyl groups, such as luteolin, and heterosides thereof such as luteolol 7-O-glucoside, baicalin and orientin.
Figure imgf000028_0002
2-phenylchromen-4-one
and also the organic or mineral acid or base salts thereof, the optical, geometrical and tautomeric isomers thereof, and the solvates thereof such as hydrates;
in which formula (Vc) the radicals Ft1, Ft2, Ft3, Ft4, Ft10, Ft11, Ft12, Ft13 and Ft14 are as defined previously in formula (V);
- iv) the dihydroflavonols or dihydroxyflavanonols of formula (Vd) which comprise at least two ortho hydroxyl groups, such as dihydroquercetol, and heterosides thereof such as dihydroquercetol 3-O-rhamoside:
Dihydroflavonol or Flavanonol:
Figure imgf000029_0001
3-hydroxy-2,3-dihydro-2-phenylchromen-4-one
and also the organic or mineral acid or base salts thereof, the optical, geometrical and tautomeric isomers thereof, and the solvates thereof such as hydrates;
in which formula (Vd) the radicals Ft1, Ft2, Ft3, Ft4, Ft10, Ft11, Ft12, Ft13 and Ft14 are as defined previously in formula (V);
- v) the flavanones of formula (Ve) which comprise at least two ortho hydroxyl groups, such as eriodictyol;
Flavanone:
Figure imgf000029_0002
(Ve)
2,3-dihydro-2-phenylchromen-4-one
and also the organic or mineral acid or base salts thereof, the optical, geometrical and tautomeric isomers thereof, and the solvates thereof such as hydrates;
in which formula (lie) the radicals Ft1, Ft2, Ft3, Ft4, Ft10, Ft11, Ft12, Ft13 and Ft14 are as defined previously in formula (V);
- vi) the flavan-3,4-diols or leucoanthocyanidins of formula (Vf) which comprise at least two ortho hydroxyl groups, such as le
Flavan-3,4-diol:
Figure imgf000029_0003
(Vf) and also the organic or mineral acid or base salts thereof, the optical isomers, geometrical isomers and tautomers thereof, and the solvates thereof such as hydrates; in which formula (Vf) the radicals Ft1, Ft2, Ft3, Ft4, Ft10, Ft11, Ft12, Ft13 and Ft14 are as defined previously in formula (V);
- vii) anthocyanidols (or anthocyanidins) of formula (Vg) which comprise at least two ortho hydroxyl groups, such as cyanidol, delphinidin, aurantinidin, luteolinidin, heterosides thereof, such as dihydroxyanthocyans (or dihydroxyanthocyanosides, or anthocyanins on the English model), oligomers and polymers thereof such as proanthocyanins, preferably proanthocyanidols and especially from blueberry;
Anthocyanidol:
Figure imgf000030_0001
(Vg)
Flavylium cation
According to another advantageous embodiment of the invention, the dye(s) of the invention are compounds of formula (a), or an oligomer thereof, in salified or non-salified form:
Figure imgf000030_0002
in which formula (a):
• R represents a hydrogen atom or a hydroxyl group;
• R' represents a hydroxyl group according to (α'):
Figure imgf000030_0003
• Y represents a divalent, trivalent or tetravalent group chosen from (d-C6)alkylene such as methylene; carbonyl -C(O)-, -CH=, >C<;
• R1 ; R2 and R3, which may be identical or different, represent a hydrogen atom or a hydroxyl group or (CrC6)alkoxy such as methoxy; • R4 represents a hydrogen atom, a hydroxyl group or -O-glycoside; or alternatively the radicals R, Y and R' form, together with the carbon atoms that bear them, a heterocyclic group fused to ring A, of formula (b), (g) or (g') below:
Figure imgf000031_0001
(b) (g) (g')
· R5 represents a hydrogen atom or a hydroxyl or -O-glycoside group;
• R6 to Rio, which may be identical or different, represent a hydrogen atom or a hydroxyl group, preferably R6 and R10 represent a hydrogen atom, R7, R8 and R9 represent a hydrogen atom or a hydroxyl group;
• Z
Figure imgf000031_0002
it being understood that the compound of formula (a) bears at least two hydroxyl groups ortho to a phenyl radical.
In a preferred variant, the dye(s) according to the invention are compounds of formula (a), and more particularly polyphenols such as tannic acid.
The dye(s) according to the invention may in particular be a mixture of proanthocyanidin derivatives such as profisetinidin and procyanidin and of compounds of formula (a), and more particularly polyphenols such as tannic acid.
Preferably, the dye(s) of the invention are derived from plant extracts. Use may also be made of mixtures of plant extracts. The natural extracts of the dyes according to the invention may be in the form of powders or liquids. Preferably, the extracts are in powder form.
In particular, the dye(s) of the invention are chosen from catechin, quercetin, brazilin, haematein, haematoxylin, chlorogenic acid, caffeic acid, gallic acid, catechol, L-DOPA, pelargonidin, cyanidin, (-)-epicatechin, (-)-epigallocatechin, (-)-epigallocatechin 3-gallate (EGCG), (+)-catechin, isoquercetin, pomiferin, esculetin, 6,7-dihydroxy-3-(3-hydroxy-2,4- dimethoxyphenyl)coumarin, santalin AC, mangiferin, butein, maritimetin, sulfuretin, robtein, betanidin, pericampylinone A, theaflavin, proanthocyanidin A2, proanthocyanidin B2, proanthocyanidin C1 , procyanidins DP 4-8, tannic acid, purpurogallin, 5,6-dihydroxy- 2-methyl-1 ,4-naphthoquinone, alizarin, wedelolactone, variegatic acid, gomphidic acid, xerocomic acid and carnosol, and natural extracts containing them.
Preferably, the dye(s) of the invention are chromenes or chromans and are chosen from haematein, haematoxylin, brazilein, brazilin and santalin A.
The term " carboxylate" means carboxylic acid salt.
When the dye precursors have D and L forms, both forms may be used in the compositions according to the invention, as may the racemates.
According to one embodiment, the natural dye(s) are derived from extracts of animals, bacteria, fungi, algae, plants and fruits, used in their entirety or partially. In particular regarding plants, the extracts are derived from fruit, including citrus fruit, from vegetables, from trees and from shrubs. Use may also be made of mixtures of these extracts, which are rich in natural dyes, especially in ortho-diphenols as defined previously.
Preferably, the natural dye(s) of the invention are derived from extracts of plants or plant parts.
For the purposes of the invention, these extracts will be placed in the same category as ingredient c).
The extracts are obtained by extraction of various plant parts, for instance the root, the wood, the bark, the leaf, the flower, the fruit, the seed, the pod or the peel.
Among the plant extracts, mention may be made of extracts of tea leaves, in particular of Japanese green tea, and of rose.
Among the fruit extracts, mention may be made of extracts of apple, of grape (in particular of grape seed) or extracts of cocoa beans and/or pods.
Among the vegetable extracts, mention may be made of extracts of potato or of onion peel.
Among the extracts of tree wood, mention may be made of extracts of pine bark and extracts of logwood or extracts of quebracho wood.
Use may also be made of mixtures of plant extracts.
According to a particular embodiment of the invention, the ortho-diphenol derivative(s) are natural extracts, rich in ODPs. According to a preferred embodiment, the dye(s) of the invention are solely natural extracts.
Preferentially, the dye(s) according to the invention are chosen from catechin, quercetin, haematein, haematoxylin, brazilin, brazilein, gallic acid and tannic acid, and natural extracts containing them chosen from grape marc, pine bark, green tea, onion, cocoa bean, logwood, redwood and gall nut, sorghum (Sorghum vulgare) and quebracho wood.
The natural extracts according to the invention may be in the form of powders or liquids. Preferably, the extracts of the invention are provided in the form of powders. a3) According to another embodiment of the invention, the dye(s) are chosen from direct dyes.
The direct dye(s) that may be used in the context of the invention are chosen from fluorescent or non-fluorescent, synthetic or natural, anionic, cationic or neutral direct dyes.
According to a particular embodiment of the invention, the dye(s) are chosen from anionic direct dyes or dyes commonly referred to as "acid" direct dyes or "acid dyes" on account of their affinity for alkaline substances.
The term "anionic direct dye" means any direct dye comprising in its structure at least one sulfonate S03 " group and/or at least one carboxylate group C(0)0" and optionally one or more anionic groups G" with G", which may be identical or different, representing an anionic group chosen from alkoxide O", thiolate S", carboxylate and thiocarboxylate: C(Q)Q'~, with Q and Q', which may be identical or different, representing an oxygen or sulfur atom; preferably, G" represents a carboxylate, i.e. Q and Q' represents an oxygen atom.
More particularly, the dye(s) of the invention are chosen from the direct dyes of formula (VI):
CoK->m (Q+)n (VI)
in which formula (VI):
■ Col( ) m represents the anionic part of the anionic direct dye or "acid' dye comprising in its structure at least one sulfonate group and/or at least one carboxylate group and comprising m anionic charges:
■ m and n, which may be identical or different, represent an integer between 1 and 10 inclusive;
■ Q+, which may be identical or different, represents an organic or mineral cationic counterion preferably chosen from alkali metal or alkaline-earth metal cations such as Na+ or K+. In formula (VI) of the invention, the radical Col( )m represents the anionic part of the "acid dyes" or of the anionic direct dyes and preferentially Col(½ comprises in its structure:
o at least one sulfonate group and at least one (hetero)aryl group, it being understood that at least one sulfonate group is directly connected to a (hetero)aryl group, preferentially aryl such as phenyl or benzo; and
o optionally one or more anionic groups G" as defined previously.
According to another preferred embodiment of the invention, Col( )m comprises in its structure:
o at least one carboxylate group and
o at least one (hetero)aryl group, it being understood that at least one carboxylate group is directly connected to a (hetero)aryl group, preferentially aryl such as phenyl or benzo; and
o optionally one or more anionic groups G" as defined previously.
According to yet another preferred embodiment of the invention, Col( )m comprises in its structure:
o at least one carboxylate group, at least one sulfonate group and at least one (hetero)aryl group, it being understood that at least one sulfonate or carboxylate group is directly connected to a (hetero)aryl group, preferentially aryl such as phenyl or benzo; and
o optionally one or more anionic groups G" as defined previously.
According to a particular embodiment of the invention, the dyes of formula (VI) are such that m is equal to n.
An advantageous variant of the invention concerns the dyes of formula (VI) for which m and n are equal to 1 , 2 or 3.
The preferred anionic dye(s) of formula (VI) of the invention are chosen from acidic nitro direct dyes, acidic azo dyes, acidic azine dyes, acidic triarylmethane dyes, acidic indoamine dyes, acidic anthraquinone dyes, acidic indigoids and acidic natural dyes; each of these dyes having at least one sulfonate or carboxylate group bearing a cationic counterion as defined previously; preferentially alkali metal, alkaline-earth metal or ammonium sulfonate or carboxylate.
As dyes according to the invention, mention may be made of the dyes of formulae (VII), (VII'), (VIII), (VIII'), (IX), (ΙΧ'), (X), (Χ'), (XI), (XII), (XIII) and (XIV) below:
a3a) the anionic diaryl azo dyes of formula (VII) or (VII'):
Figure imgf000035_0001
in which formulae (VII) and (VII'):
• R7, R8, 9, R10, R'7, R's, R'9 and R'i0, which may be identical or different, represent a hydrogen atom or a group chosen from: i) alkyl, ii) alkoxy, iii) alkylthio, iv) hydroxyl, v) mercapto, vi) nitro, vii) R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X"- with R° representing a hydrogen atom or an alkyl or aryl group; X, X' and X", which may be identical or different, represent an oxygen or sulfur atom or NR with R representing a hydrogen atom or an alkyl group; viii) (0)2S(0 , M+ with M+ as defined previously for M or represents a cationic counterion as defined previously; ix) (O)CO -, M+ with M+ as defined previously; x) R"-S(0)2-, with R" representing a hydrogen atom, an alkyl group, an aryl, (di)(alkyl)amino or aryl(alkyl)amino group; preferentially a phenylamino or phenyl group; xi) R'"-S(0)2-X'- with R'" representing an optionally substituted alkyl or aryl group, X' as defined previously; xii) (di)(alkyl)amino; xiii) aryl(alkyl)amino optionally substituted with one or more groups chosen from nitro; nitroso; (0)2S(0 , M+ and alkoxy with M+ as defined previously; xiv) optionally substituted heteroaryl; preferentially a benzo thiazolyl group; xv) cycloalkyl; especially cyclohexyl, xvi) Ar- N=N- with Ar representing an optionally substituted aryl group; preferentially a phenyl optionally substituted with one or more alkyl groups, (0)2S(0~)-, M+ or phenylamino; · or alternatively two contiguous groups R7 with R8 or R8 with R9 or R9 with R10 together form a fused benzo group A'; and R'7 with R'8 or R'8 with R'9 or R'9 with R'10 together form a fused benzo group B'; with A' and B' optionally substituted with one or more groups chosen from i) nitro; ii) nitroso; iii) (0)2S(0 , M+; iv) hydroxyl; v) mercapto; vi) (di)(alkyl)amino; vii) R°-C(X)-X'-; viii) R°-X'-C(X)-; ix) R°-X'-C(X)-X"-; x) Ar-N=N- and xi) optionally substituted aryl(alkyl)amino; with M+, R°, X, X', X" and Ar as defined previously;
• W represents a sigma bond σ, an oxygen or sulfur atom, or a divalent radical i) -NR- with R as defined previously, or ii) methylene -C(Ra)(Rb)- with Ra and Rb, which may be identical or different, representing a hydrogen atom or an aryl group, or alternatively Ra and Rb together form, with the carbon atom that bears them, a spiro cycloalkyl; preferentially, W represents a sulfur atom or Ra and Rb together form a cyclohexyl; it being understood that formulae (VII) and (VII') comprise at least one sulfonate (0)2S(0 , Q+ or carboxylate (0)C(0 , Q+ radical on one of the rings A, A', B, B' or C with R! R2R3R4 as defined previously; preferentially alkali metal, alkaline-earth metal or ammonium sulfonate or carboxylate;
As examples of dyes of formula (VII), mention may be made of: Acid Red 1 , Acid Red 4, Acid Red 13, Acid Red 14, Acid Red 18, Acid Red 27, Acid Red 32, Acid Red 33, Acid Red 35, Acid Red 37, Acid Red 40, Acid Red 41 , Acid Red 42, Acid Red 44, Acid Red 68, Acid Red 73, Acid Red 135, Acid Red 138, Acid Red 184, Food Red 1 , Food Red 13, Acid Orange 6, Acid Orange 7, Acid Orange 10, Acid Orange 19, Acid Orange 20, Acid Orange 24, Acid Yellow 9, Acid Yellow 36, Acid Yellow 199, Food Yellow 3; Acid Violet 7, Acid Violet 14, Acid Blue 1 13, Acid Blue 1 17, Acid Black 1 , Acid Brown 4, Acid Brown 20, Acid Black 26, Acid Black 52, Food Black 1 , Food Black 2;
and as examples of dyes of formula (VI Γ), mention may be made of: Acid Red 11 1 , Acid Red 134, Acid Yellow 38;
a3b) the pyrazolone anionic azo dyes of formulae (VIII) and (VIII'):
Figure imgf000036_0001
in which formulae (VIII) and (VIII'):
• R11 ; R12 and R13, which may be identical or different, represent a hydrogen or halogen atom, an alkyl group or -(0)2S(0~), M+ with M+ as defined previously;
• R14 represents a hydrogen atom, an alkyl group or a group -C(0)0-, M+ with M+ as defined previously;
· Ri5 represents a hydrogen atom;
• Ri6 represents an oxo group, in which case R'i6 is absent, or alternatively Ri5 with R16 together form a double bond; • R17 and R18, which may be identical or different, represent a hydrogen atom or a group chosen from:
- (0)2S(0 , M+ with M+ as defined previously;
- Ar-0-S(0)2- with Ar representing an optionally substituted aryl group, preferentially a phenyl optionally substituted with one or more alkyl groups;
• Rig and R20 together form either a double bond, or a benzo group D', which is optionally substituted;
• R'16, R'19 and R'20, which may be identical or different, represent a hydrogen atom or an alkyl or hydroxyl group;
· R2i represents a hydrogen atom or an alkyl or alkoxy group;
• Ra and Rb, which may be identical or different, are as defined previously, preferentially Ra represents a hydrogen atom and Rb represents an aryl group;
• Y represents either a hydroxyl group or an oxo group;
• represents a single bond when Y is an oxo group; and represents a double bond when Y represents a hydroxyl group;
it being understood that formulae (VIII) and (VIII') comprise at least one sulfonate group (0)2S(0 , Q+ on one of the rings D or E or formulae (VIII) and (VIII') comprise at least one carboxylate group (O)C(O )-, Q+ with Q+ as defined previously; preferentially comprise at least one sulfonate group (0)2S(0 , Q+ on one of the rings D or E and more particularly sulfonate;
As examples of dyes of formula (VIII), mention may be made of: Acid Red 195, Acid Yellow 23, Acid Yellow 27, Acid Yellow 76, and as examples of dyes of formula (VIM'), mention may be made of Acid Yellow 17; a3c) the anthraquinone dyes of formulae (IX) and (IX'):
Figure imgf000037_0001
in which formulae (IX) and (IX'):
• R22, R23, R24, R25, R26 and R27, which may be identical or different, represent a hydrogen or halogen atom or a group chosen from i) alkyl, ii) hydroxyl, iii) mercapto, iv) alkoxy, v) alkylthio, vi) aryloxy or arylthio which is optionally substituted, preferentially substituted with one or more groups chosen from alkyl and (0)2S(0~)-, M+ with M+ as defined previously, vii) aryl(alkyl)amino optionally substituted with one or more groups chosen from alkyl and (0)2S(0~)-, M+ with M+ as defined previously, viii) (di)(alkyl)amino, ix) (di)(hydroxyalkyl)amino, x) (0)2S(0 , M+ with M+ as defined previously;
• Z' represents a hydrogen atom or a group NR28R29 with R28 and R29, which may be identical or different, representing a hydrogen atom or a group chosen from i) alkyl, ii) polyhydroxyalkyl such as hydroxyethyl, iii) aryl optionally substituted with one or more groups chosen from alkyl such as methyl, n-dodecyl, n-butyl; (0)2S(0 , M+ with M+ as defined previously; R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X"- with R°, X, X' and X" as defined previously, preferentially R° represents an alkyl group, iv) cycloakyl; especially cyclohexyl;
• Z represents a group chosen from hydroxyl and NR'28R'29 with R'28 and R'29, which may be identical or different, representing the same atoms or groups as R28 and R29 as defined previously;
it being understood that formulae (IX) and (IX') comprise at least one sulfonate group
(0)2S(0 , Q+;
As examples of dyes of formula (IX), mention may be made of: Acid Blue 25, Acid Blue 43, Acid Blue 62, Acid Blue 78, Acid Blue 129, Acid Blue 138, Acid Blue 140, Acid Blue 251 , Acid Green 25, Acid Green 41 , Acid Violet 42, Acid Violet 43, Mordant Red 3;
and as examples of dyes of formula (IX'), mention may be made of Acid Black 48; a3d) the nitro dyes of formulae (X) and (Χ'):
Figure imgf000038_0001
(X) (Χ')
in which formulae (X) and (Χ'):
• R30, R3i and R32, which may be identical or different, represent a hydrogen or halogen atom or a group chosen from i) alkyl, ii) alkoxy optionally substituted with one or more hydroxyl groups, iii) alkylthio optionally substituted with one or more hydroxyl groups, iv) hydroxyl, mercapto, v) nitro, nitroso, vi) (poly)haloalkyl, vii) R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X"- with R°; X, X' and X" as defined previously, viii) (0)2S(0 , M+ with M+ as defined previously, ix) (O)CO -, IVTwith M+ as defined previously, x) (di)(alkyl)amino, xi) (di)(hydroxyalkyl)amino, xii) heterocycloalkyl such as piperidino, piperazino or morpholino; in particular, R30, R3i and R32 represent a hydrogen atom; • Rc and Rd, which may be identical or different, represent a hydrogen atom or an alkyl group;
• W is as defined previously; W particularly represents a group -NH-;
• ALK represents a linear or branched divalent CrC6 alkylene group; in particular, ALK represents a group -CH2-CH2-;
• n is 1 or 2;
• p represents an integer between 1 and 5 inclusive;
• q represents an integer between 1 and 4 inclusive;
• u is 0 or 1 ;
· when n is 1 , J represents a nitro or nitroso group; particularly nitro;
• when n is 2, J represents an oxygen or sulfur atom, or a divalent radical -S(0)m- with m representing an integer 1 or 2; preferentially, J represents a radical -S02-;
• M' is as defined previously for M+; ■ ,i which may be present or absent, represents a benzo group optionally substituted with one or more groups R30 as defined previously;
it being understood that formulae (X) and (Χ') comprise at least one sulfonate group (0)2S(0 , Q+ or carboxylate group (0)C(0 , Q+;
As examples of dyes of formula (X), mention may be made of: Acid Brown 13 and Acid Orange 3; as examples of dyes of formula (Χ'), mention may be made of: Acid Yellow 1 , sodium salt of 2,4-dinitro-1 -naphthol-7-sulfonic acid, 2-piperidino-5- nitrobenzenesulfonic acid, 2-(4'-N,N(2"-hydroxyethyl)amino-2'-nitro)anilineethanesulfonic acid and 4-p-hydroxyethylamino-3-nitrobenzenesulfonic acid; a3e) the triarylmethane dyes of formula (XI):
Figure imgf000039_0001
in which formula (XI):
■ R33, R34, R35 and R36, which may be identical or different, represent a hydrogen atom or a group chosen from alkyl, optionally substituted aryl and optionally substituted arylalkyl; particularly an alkyl group and benzyl optionally substituted with a group (0)mS(0 , M+ with M+ and m as defined previously; ■ R37, R38, R39, R40, R41 , R42, R43 and R44, which may be identical or different, represent a hydrogen atom or a group chosen from: i) alkyl; ii) alkoxy, alkylthio; iii) (di)(alkyl)amino; iv) hydroxyl, mercapto; v) nitro, nitroso; vii) R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X"- with R° representing a hydrogen atom or an alkyl or aryl group; X, X' and X", which may be identical or different, representing an oxygen or sulfur atom or NR with R representing a hydrogen atom or an alkyl group; viii) (0)2S(0 , M+ with M+ representing a hydrogen atom or a cationic counterion; ix) (O)CO -, M+ with M+ as defined previously;
■ or alternatively two contiguous groups R41 with R42 or R42 with R43 or R43 with R44 together form a fused benzo group: Γ; with Γ optionally substituted with one or more groups chosen from i) nitro; ii) nitroso; iii) (0)2S(0 , M+; iv) hydroxyl; v) mercapto; vi) (di)(alkyl)amino; vii) R°-C(X)-X'-; viii) R°-X'-C(X)- and ix) R°-X'-C(X)-X"-; with M+, R°, X, X' and X" as defined previously;
particularly, R37 to R40 represent a hydrogen atom, and R4i to R44, which may be identical or different, represent a hydroxyl group or (0)2S(0~)-, M+; and when R43 with R44 together form a benzo group, it is preferentially substituted with a group (0)2S(0 ;
it being understood that at least one of the rings G, H, I or Γ comprises at least one sulfonate (0)2S(0 , Q+ or carboxylate (0)C(0 , Q+ group;
As examples of dyes of formula (XI), mention may be made of: Acid Blue 1 ; Acid Blue 3; Acid Blue 7, Acid Blue 9; Acid Violet 49 and Acid Green 50; a3f) the xanthene-based
Figure imgf000040_0001
in which formula (XII):
■ R45, R46, R47 and R48, which may be identical or different, represent a hydrogen or halogen atom;
■ R49, R50, R51 and R52, which may be identical or different, represent a hydrogen or halogen atom or a group chosen from i) alkyl; ii) alkoxy, alkylthio; iii) hydroxyl, mercapto; iv) nitro, nitroso; v) (0)2S(0 , M+ with M+ representing a hydrogen atom or a cationic counterion; vi) (O)CO -, M+ with M+ as defined previously;
particularly, R53, R54, R55 and R48 represent a hydrogen or halogen atom; ■ G represents an oxygen or sulfur atom or a group NRe with Re as defined previously; particularly, G represents an oxygen atom;
■ L represents an alkoxide O", M+; a thioalkoxide S", M+ or a group NRf, with Rf representing a hydrogen atom or an alkyl group and M+ as defined previously; M+ is particularly Na+ or K+;
■ U represents an oxygen or sulfur atom or an ammonium group: N+R,Rg, with R, and Rg, which may be identical or different, representing a hydrogen atom, an alkyl group or optionally substituted aryl; L' represents particularly an oxygen atom or a phenylamino group optionally substituted with one or more alkyl or (0)mS(0~)-, M+ groups with m and M+ as defined previously;
■ Q and Q', which may be identical or different, represent an oxygen or sulfur atom; particularly Q and Q' represent an oxygen atom;
■ M+ is as defined previously;
it being understood that formula (XII) comprises at least one sulfonate group (0)2S(0~)-, Q+ or carboxylate group (O)C(O )-, Q+ with Q+ as defined previously;
As examples of dyes of formula (XII), mention may be made of the ammonium salts derived from: Acid Yellow 73; Acid Red 51 ; Acid Red 87; Acid Red 92; Acid Red 95 and Acid Violet 9;
a3g) the indigoid dyes of formula (XIII):
Figure imgf000041_0001
in which formula (XIII):
■ R53, R54, R55, R56, R57, R58, R59 and R60, which may be identical or different, represent a hydrogen atom or a group chosen from: i) alkyl; ii) alkoxy, alkylthio; iii) hydroxyl, mercapto; iv) nitro, nitroso; v) R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X"- with R° representing a hydrogen atom or an alkyl or aryl group; X, X' and X", which may be identical or different, representing an oxygen or sulfur atom or NR with R representing a hydrogen atom or an alkyl group; vi) (0)2S(0 , M+ with M+ as defined previously; vii) (O)CO -, IVT with M+ as defined previously;
■ G represents an oxygen or sulfur atom or a group NRe with Re as defined previously; particularly, G represents an oxygen atom;
■ R, and Rh, which may be identical or different, represent a hydrogen atom or an alkyl group;
it being understood that formula (XIII) comprises at least one sulfonate group (0)2S(0 , Q+ or carboxylate group (O)C(O )-, Q+ with Q+ as defined previously; As examples of dyes of formula (XIII), mention may be made of Acid Blue 74 and indigo carmine (or indigotine I, blue CI No. 1 ) is a blue dye (number E132) which is a natural extract of the indigo plant; a3h) the quinoline-based dyes of formula (XIV):
Figure imgf000042_0001
■ R61 represents a hydrogen or halogen atom or an alkyl group;
■ Re2, Re3 and R64, which may be identical or different, represent a hydrogen atom or a group (0)2S(0 , M+ with M+ as defined previously;
■ or alternatively R6i with R62, or R61 with R64, together form a benzo group optionally substituted with one or more groups (0)2S(0 , M+ with M+ representing a hydrogen atom or a cationic counterion;
it being understood that formula (XIV) comprises at least one sulfonate group (0)2S(0 , Q+ with Q+ as defined previously.
As examples of dyes of formula (XIV), mention may be made of the ammonium salts derived from: Acid Yellow 2, Acid Yellow 3 and Acid Yellow 5.
More particularly, the dyes of formulae (VII) to (XIV) that are useful in the invention are chosen from the sal ts:
(C.I. 45380) Acid Red 87 (XIV)
(C.I. 10316) ammonium salts of 2,4-dinitro-1 -naphthol-7-sulfonic acid (Χ')
(C.I. 10383) Acid Orange 3 (XII)
(C.I. 13015) Acid Yellow 9 / Food Yellow 2 (VII)
(C.I. 14780) / Direct Red 45 / Food Red 13 (VII)
(C.I. 13711 ) Acid Black 52 (VII)
(C.I. 13065) Acid Yellow 36 (VII)
(C.I. 14700) ammonium salt of 1 -hydroxy-2-(2',4'-xylyl-5- sulfonatoazo)naphthalene-4-sulfonic acid / Food Red 1 (VII)
(C.I. 14720) Acid Red 14 / Food Red 3 / Mordant Blue 79 (VII)
(C. I. 14805) ammonium salt of 4-hydroxy-3-[(2-methoxy-5-nitrophenyl)diaza]- 6-(phenylamino)naphthalene-2-sulfonic acid / Acid Brown 4 (VII)
(C.I. 15510) Acid Orange 7 / Pigment Orange 17 / Solvent Orange 49 (VII)
(C.I. 15985) Food Yellow 3 / Pigment Yellow 104 (VII)
(C.I. 16185) Acid Red 27 / Food Red 9 (VII)
(C.I. 16230) Acid Orange 10 / Food Orange 4 (VII)
(C.I. 16250) Acid Red 44 (VII)
(C.I. 17200) Acid Red 33 / Food Red 12 (VII)
(C.I. 15685) Acid Red 184 (VII)
(C.I. 19125) Acid Violet 3 (VII)
(C.I. 18055) ammonium salt of 1 -hydroxy-2-(4'-acetamidophenylazo)-8-
Figure imgf000043_0001
Most of these dyes are described in particular in the Colour Index published by The
Society of Dyers and Colourists, P.O. Box 244, Perkin House, 82 Grattan Road, Bradford, Yorkshire, BD12 JBN England. The anionic dyes that are most particularly preferred are the dyes designated in the Colour Index under the code C.I. 58005 (monosodium salt of 1 ,2-dihydroxy-9,10-anthraquinone-3-sulfonic acid), C.I. 60730 (monosodium salt of 2- [(9,10-dihydro-4-hydroxy-9,10-dioxo-1 -anthracenyl)amino]-5-methylbenzenesulfonic acid), C.I. 15510 (monosodium salt of 4-[(2-hydroxy-1 -naphthalenyl)azo]benzenesulfonic acid), C.I. 15985 (disodium salt of 6-hydroxy-5-[(4-sulfophenyl)azo]-2- naphthalenesulfonic acid), C.I. 17200 (disodium salt of 5-amino-4-hydroxy-3-(phenylazo)- 2,7-naphthalenedisulfonic acid), C.I. 20470 (disodium salt of 1 -amino-2-(4'- nitrophenylazo)-7-phenylazo-8-hydroxy-3,6-naphthalenedisulfonic acid), C.I. 42090 (disodium salt of N-ethyl-N-[4-[[4-[ethyl[3-sulfophenyl)methyl]amino]phenyl](2- sulfophenyl)methylene]-2,5-cyclohexadien-1 -ylidene]-3-sulfobenzenemethanaminium hydroxide, inner salt), C.I. 61570 (disodium salt of 2,2'-[(9,10-dihydro-9,10-dioxo-1 ,4- anthracenediyl)diimino]bis[5-methyl]benzenesulfonic acid).
It is also possible to use compounds corresponding to the mesomeric or tautomeric forms of structures (VII) to (XIV).
More particularly, the dye(s) according to the invention are chosen from those of formulae (VII), (IX) and (XIII), preferably of formula (XIII). a4) According to another particular embodiment of the invention, the dye(s) are chosen from cationic direct dyes or dyes commonly referred to as "basic" direct dyes or "basic dyes" on account of their affinity for acidic substances. The cationic dyes are preferentially chosen from hydrazono, (poly)azo, polymethine such as styryl and (poly)arylmethane dyes. More preferentially, the cationic dye(s) of the invention are chosen from the hydrazono dyes of formulae (XVa) and (XV'a), the azo dyes (XVIa) and (XVI'a) and the diazo dyes (XVIIa) below:
Het+-C(Ra)=N-N(Rb)-Ar, Cf Het+-N(Ra)-N=C(Rb)-Ar, Cf Het+-N=N-Ar,Q"
(XVa) (XV'a) (XVIa)
Ar+-N=N-Ar", Cf and Het+-N=N-Ar'-N=N-Ar, Q"
(XVI'a) (XVIIa)
formulae (XVa), (XV'a), (XVIa), (XVI'a) and (XVIIa) with:
• Hef representing a cationic heteroaryl radical, preferentially bearing an endocyclic cationic charge, such as imidazolium, indolium or pyridinium, optionally substituted preferentially with one or more (CrC8)alkyl groups such as methyl;
• Ar+ representing an aryl radical, such as phenyl or naphthyl, bearing an exocyclic cationic charge, preferentially ammonium, particularly tri(Ci-C8)alkylammonium such as trimethylammonium;
• Ar represents an aryl group, especially phenyl, which is optionally substituted, preferentially with one or more electron-donating groups such as i) optionally substituted (CrC8)alkyl, ii) optionally substituted (CrC8)alkoxy, iii) (di)(C C8)(alkyl)amino optionally substituted on the alkyl group(s) with a hydroxyl group, iv) aryl(Ci-C8)alkylamino, v) optionally substituted A/-(Ci-C8)alkyl-A/-aryl(Ci-C8)alkylamino or alternatively Ar represents a julolidine group;
» Ar' is an optionally substituted divalent (hetero)arylene group such as phenylene, particularly para-phenylene, or naphthalene, which are optionally substituted, preferentially with one or more (CrC8)alkyl, hydroxyl or (d-C8)alkoxy groups; • Ar" is an optionally substituted (hetero)aryl group such as phenyl or pyrazolyl, which are optionally substituted, preferentially with one or more (d-C8)alkyl, hydroxyl, (di)(Ci-C8)(alkyl)amino, (CrC8)alkoxy or phenyl groups;
• Ra and Rb, which may be identical or different, represent a hydrogen atom or a (C C8)alkyl group, which is optionally substituted, preferentially with a hydroxyl group; or alternatively the substituent Ra with a substituent of Het+ and/or Rb with a substituent of Ar and/or Ra with Rb form, together with the atoms that bear them, a (hetero)cycloalkyl; particularly, Ra and Rb represent a hydrogen atom or a (CrC4)alkyl group, which is optionally substituted with a hydroxyl group;
· Q" represents an anionic counterion as defined previously.
According to a preferred variant of the invention, the cationic dyes are chosen from the polymethine dyes of formulae (XVIIIa) and (XVIII'a) below:
W+-[C(Rc)=C(Rd)]m-Ar', Q" Ar-[C(Rd)=C(Rc)]m-W'+, Q"
(XVIIIa) (Vill a) formula (XVIIIa) or (XVIII'a) with:
• W+ representing a cationic heterocyclic or heteroaryl group, particularly comprising a quaternary ammonium optionally substituted with one or more (CrC8)alkyl groups optionally substituted especially with one or more hydroxyl groups;
• W'+ representing a heterocyclic or heteroaryl radical as defined for W+;
• Ar representing a (hetero)aryl group such as phenyl or naphthyl, optionally substituted preferentially with i) one or more halogen atoms such as chlorine or fluorine; ii) one or more (CrC8)alkyl groups, preferably of Ci-C4 such as methyl; iii) one or more hydroxyl groups; iv) one or more (Ci-C8)alkoxy groups such as methoxy; v) one or more hydroxy(CrC8)alkyl groups such as hydroxyethyl, vi) one or more amino groups or (di)(CrC8)alkylamino, preferably with the CrC4 alkyl part optionally substituted with one or more hydroxyl groups, such as (di)hydroxyethylamino, vii) with one or more acylamino groups; viii) one or more heterocycloalkyl groups such as piperazinyl, piperidyl or 5- or 6-membered heteroaryl such as pyrrolidinyl, pyridyl and imidazolinyl;
• Ar' is a (hetero)aryl radical as defined for Ar;
• m' represents an integer between 1 and 4 inclusive, and in particular m is 1 or 2; more preferentially 1 ;
· Rc and Rd, which may be identical or different, represent a hydrogen atom or an optionally substituted (CrC8)alkyl group, preferentially of Ci-C4, or alternatively Rc contiguous with W+ or W'+ and/or Rd contiguous with Ar or Ar' and/or contiguous Rc and Rd form, with the atoms that bear them, a (hetero)cycloalkyl, particularly Rc is contiguous with W+ or W'+ and forms a (hetero)cycloalkyl such as cyclohexyl;
· Q" as defined previously, preferably represents a halide or a mesylate. Mention may be made more particularly of the azo and hydrazono dyes bearing an endocyclic cationic charge of formulae (XVa), (XV'a), (XVIa) and (XVI'a) as defined previously. More particularly those of formulae (XVa), (XV'a) and (XVIa) derived from the dyes described in patent applications WO 95/15144, WO 95/01772 and EP-714954. Preferentially, the cationic dyes comprise an endocyclic cationic charge and particularly have the following formula:
Figure imgf000046_0001
(XVa-1) (XVIa-1)
formulae (XVa-1) and (XVIa-1) with:
- Pt1 representing a (CrC4)alkyl group such as methyl;
- Pt2 and R3, which may be identical or different, represent a hydrogen atom or a (d- C4)alkyl group, such as methyl; and
- R4 represents a hydrogen atom or an electron-donating group such as optionally substituted (CrC8)alkyl, optionally substituted (CrC8)alkoxy, or (di)(Ci-C8)(alkyl)amino optionally substituted on the alkyl group(s) with a hydroxyl group; particularly, R4 is a hydrogen atom,
- Z represents a CH group or a nitrogen atom, preferentially CH,
- Q" as defined previously, preferably represents a halide or a mesylate.
Particularly, the dyes of the invention are chosen from those of formulae (XVIa-1 ) and
(XVa-1 ) is chosen from Basic Red 51 , Basic Yellow 87 and Basic Orange 31 or derivatives thereof:
Figure imgf000046_0002
Basic Red 51 Basic Orange 31 Basic Yellow 87 with Q" as defined previously, preferably represents a halide or a mesylate.
In the context of the present invention, the dye(s) are present in a total amount ranging from 0.001% to 20% by weight relative to the total weight of the dye composition, in particular ranging from 0.005% to 10% by weight relative to the total weight of the dye composition, preferentially from 0.01 % to 5% by weight relative to the total weight of the dye composition.
As regards the pure natural dyes, especially the pure ODPs, the content in the composition(s) containing them is preferably between 0.001 % and 5% by weight of each of these compositions containing them.
As regards the extracts, the content in the composition(s) containing the extract(s) per se is preferably between 0.1 % and 20% by weight of each of these compositions. b) titanium salt(s):
The titanium salt(s) of the invention may be one or more organic or mineral titanium salts.
For the purposes of the present invention, the term "organic titanium salt means the salts per se resulting from the action of at least one organic acid on Ti.
The term "organic acid' means an acid, i.e. a compound that is capable of releasing a cation or proton H+ or H30+, in aqueous medium, which comprises at least one optionally unsaturated, linear or branched Ci-C20 hydrocarbon-based chain, or a (hetero)cycloalkyl or (hetero)aryl group and at least one acid chemical function chosen in particular from carboxyl COOH, sulfuric S03H, S02H, and phosphoric P03H2, P04H2. In particular, the organic acid(s) for forming the organic titanium salt(s) of the invention are chosen from the carboxylic acid(s) of formula (I) as defined previously and are preferably a-hydroxy acids such as lactic acid, glycolic acid, tartaric acid or citric acid.
Preferentially, the organic titanium salt derived from the action of one or more organic acids as defined previously, preferably carboxylic acids of formula (I) as defined previously, is an optionally charged (in particular negatively charged) complex, which is complexed with one or more carboxylate groups of carboxylic acids.
Preferentially, the organic titanium salt(s) of the invention are chosen from those of formula (l-A) below:
Figure imgf000047_0001
(l-A)
in which formula (l-A):
• A is identical to that of formula (I)
• n, n' and n", which may be identical or different, are equal to 1 , 2, 3 or 4 and n' + n" = 6;
• Mi and M2, which may be identical or different, represent a cationic counterion chosen in particular from cations of an alkali metal such as Na or K or of an alkaline-earth metal such as Ca or an organic cation such as ammonium, preferably ammonium or a hydrogen atom;
• TiYn- denoting Ti(OH)n-, or Ti(0)n /2, or Ti(OH)m1(0)m2with m!+m2 = n".
Preferentially, the radical A of compound (l-A) as defined previously represents a monovalent (d-C6)alkyl or polyvalent (CrC6)alkylene group optionally substituted with one or more hydroxyl groups, and n representing an integer between 0 and 5, such as between 0 and 2, inclusive; in particular, the carboxylic acid(s) used to form the organic titanium salt(s) of the invention are chosen from α-hydroxy acids; preferably, the acid is chosen from citric acid, lactic acid, tartaric acid and glycolic acid, better still from lactic acid and glycolic acid.
Preferentially, the organic titanium salt(s) of the invention are chosen from those of formula (l-B) below:
Figure imgf000048_0001
(l-B)
in which formula (l-B):
• L' and L", which may be identical or different, represent a divalent (hetero)arylene, (CrC6)alkylene or (C2-C6)alkenylene group, said alkylene and arylene groups being optionally substituted with one or more atoms or groups chosen from halo, (C C4)alkyl, hydroxyl, thiol and (di)(Ci-C4)(alkyl)amino, carboxyl, and/or optionally interrupted with one or more heteroatoms such as oxygen;
preferably, L' and L" are identical and represent a methylene or ethylene group optionally substituted with a (CrC4)alkyl group;
• X' and X", which may be identical or different, represent a heteroatom such as oxygen, sulfur or amino Rc-N with Rc representing a hydrogen atom or a (CrC4)alkyl group; preferably, X' and X" are identical and represent an oxygen atom;
• Y and Y', which may be identical or different, are as defined for X' and X"; preferably, Y and Y' are identical and represent an oxygen atom; • Ra and Rb, which may be identical or different, represent a hydrogen atom or a (C C6)alkyl, (C2-C6)alkenyl or (hetero)aryl group; particularly, Ra and Rb, which are identical, represent a hydrogen atom or a (d-C4)alkyl group, preferably hydrogen;
• M+, which may be identical or different, represents a cationic counterion such as a cation of an alkali metal (Na or K) or of an alkaline-earth metal (Ca) or an organic cation such as ammonium, preferably ammonium.
Preferably, the organic titanium salt(s) of the dyeing process are dihydroxybis(lactato)titanium(IV) salts such as those having the following formula:
Figure imgf000049_0001
The dyeing process may use one or more organic acids b1 ) of formula (I) as defined previously.
According to an advantageous variant, the dyeing process also uses b1 ) one or more carboxylic acids of formula (I) as defined previously.
More preferentially, the carboxylic acid(s) b1 ) are different from the carboxylic acids complexed to the Ti salts, preferably glycolic acid, citric acid, tartaric acid, lactic acid or a salt thereof.
In particular, the carboxylic acid(s) b) are preferably different from the carboxylic acids complexed to the Ti salts, when the Ti salt is an organic salt derived from the action of one or more carboxylic acids as defined previously.
For example, if the carboxylic acid complexed to the titanium salt b) is lactic acid or the carboxylate salt thereof (lactate), the second acid b1 ) is other than lactic acid or lactate, and may be, for example, glycolic acid.
For the purposes of the present invention, the term "mineral titanium salt means the salts per se derived from the action of a mineral acid on Ti.
The term "mineral acid' means an acid which does not comprise carbon atoms, apart from carbonic acid.
The mineral titanium salts are preferably chosen from titanium halides, titanium sulfates and titanium phosphates. Preferably, the titanium salts are mineral Ti(ll), Ti(lll) or Ti(IV) salts, more particularly Ti(lll) or Ti(IV).
Preferably, the titanium salt(s) are organic titanium salts, and better still organic Ti(IV) salts. According to an advantageous embodiment of the invention, the organic Ti salt consists of a Ti(IV) atom and of 2 to 3 molar equivalents of at least one carboxylic acid of formula (I).
The titanium salt(s) (b) are present in the cosmetic composition(s) used in the process according to the invention in a content ranging from 0.001% to 20% by weight, relative to the total weight of the composition(s) containing them.
Particularly, the organic titanium salt(s) and the mineral titanium salt(s) according to the invention are soluble in water in a proportion of at least 0.0001 g/l and better still at least 1 g/l.
According to a particular embodiment, the pKai of the carboxylic acid(s) b1) is less than 3. c) alkaline agent(s)
The dyeing process of the invention uses a revealing composition Cii) comprising one or more alkaline agents c) which comprise not more than one amine function, it being understood that when composition Cii) comprises several alkaline agents, then each of the alkaline agents comprises not more than one amine function. These are compounds that can increase the pH of the composition(s) containing them. The alkaline agent is a Bronsted, Lowry or Lewis base. It may be mineral or organic and, when it is organic, it comprises not more than one amine function NH2.
In particular, said alkaline agent is chosen from i) (bi)carbonates, ii) aqueous ammonia, iii) alkanolamines comprising only one amine function such as monoethanolamine; monopropanolamine, iv) oxyalkylenated alkanolamines comprising only one amine function and in particular oxyethylenated alkanolamines such as oxyethylenated and/or oxypropylenated ethyleneamines, v) mineral or organic hydroxides, vi) alkali metal silicates such as sodium metasilicates, vii) amino acids comprising only one amine function, preferably basic amino acids such as histidine.
The mineral or organic hydroxides are preferably chosen from a) hydroxides of an alkali metal, b) hydroxides of an alkaline-earth metal, for instance sodium hydroxide or potassium hydroxide, c) hydroxides of a transition metal, such as hydroxides of metals from groups III, IV, V and VI, d) hydroxides of lanthanides or actinides and quaternary ammonium hydroxides.
The term "(bi)carbonates i)" is understood to mean:
a) carbonates of alkali metals (Met2+, C03 2~), of alkaline-earth metals (Met'2+, C03 2~) of ammonium ((R"4N+)2,C03 2~) or of phosphonium ((R"4P+)2,C03 2" with Met' representing an alkaline-earth metal and Met representing an alkali metal, and R", which may be identical or different, represent a hydrogen atom or an optionally substituted (CrC6)alkyl group such as hydroxyethyl), and
b) bicarbonates, also known as hydrogen carbonates, of the following formulae: > R'+, HCO3 " with R' representing a hydrogen atom, an alkali metal, an ammonium group R"4N+- or a phosphonium group R"4P+- where R", which may be identical or different, represent a hydrogen atom, an optionally substituted (d-C6)alkyl group such as a hydroxyethyl group and, when R' represents a hydrogen atom, the hydrogen carbonate is then known as a dihydrogen carbonate (C02, H20); and
> Met'2+ (HC03 ")2 with Met' representing an alkaline-earth metal.
More particularly, the alkaline agent is chosen from alkali metal or alkaline-earth metal (bi)carbonates and amino acids comprising not more than one amine function such as histidine; preferentially alkali metal (bi)carbonates and amino acids comprising not more than one amine function.
According to a particular embodiment of the invention, the alkaline agent(s) c) are chosen from a mixture of two alkaline agents chosen from families i) to vii) as defined previously.
In particular, the alkaline agent(s) c) are chosen from the following mixtures:
1 ) carbonates + bicarbonates;
2) amino acids + (bi)carbonates;
3) alkanolamines + (bi)carbonates;
4) oxyalkylenated alkanolamines + (bi)carbonates;
5) mineral or organic hydroxides + (bi)carbonates;
6) alkali metal silicates + (bi)carbonates;
the amino acids and oxyalkylenated or non-oxyalkylenated alkanolamines comprising not more than one amine function;
more particularly, the weight ratio R between 1 ) carbonates and bicarbonates or between the first alkaline agents (amino acids, alkanolamines, oxyalkylenated alkanolamines, mineral or organic hydroxides or alkali metal silicates) according to 2) to 6) and the (bi)carbonates is greater than or equal to 2, preferentially R is greater than or equal to 4, more preferentially R is greater than or equal to 6, even more preferentially R is greater than or equal to 8, better still greater than or equal to 10 and in particular R is inclusively between 2 and 16, preferentially R is inclusively between 10 and 14.
According to a particularly advantageous embodiment, the alkaline agent(s) c) are chosen from i) alkali metal or alkaline-earth metal carbonates, ii) alkali metal or alkaline- earth metal bicarbonates and iii) amino acids comprising not more than one amine function such as histidine, alone or as mixtures. They are preferably together during the dyeing process. Composition Cii) preferably comprises a mixture of at least one alkali metal or alkaline-earth metal carbonate i) and of at least one alkali metal or alkaline-earth metal bicarbonate ii). According to a preferred embodiment of the invention, the alkaline agent(s) c) are chosen from a mixture of carbonates and bicarbonates as defined previously with a carbonates/bicarbonates weight ratio R of greater than or equal to 2, preferentially R is greater than or equal to 4, more preferentially R is greater than or equal to 6, even more preferentially R is greater than or equal to 8, better still greater than or equal to 10 and in particular R is inclusively between 2 and 16, preferentially R is inclusively between 10 and 14.
Among the carbonates and bicarbonates that are suitable for use in the present invention, mention may be made of the carbonates and bicarbonates (also known as hydrogen carbonates) of Na, K, Mg and Ca, and mixtures thereof, and in particular Na carbonate and bicarbonate. These bicarbonates may originate from a natural water, for example spring water from the Vichy basin or from La Roche Posay or Badoit water (cf. for example, patent FR 2 814 943). Mention may in particular be made of sodium carbonate [497-19-8] = Na2C03, sodium hydrogen carbonate or sodium bicarbonate [144- 55-8] = NaHC03, and sodium dihydrogen carbonate = Na(HC03)2-
According to a particularly advantageous embodiment of the invention, composition Cii) comprises at least one alkaline agent chosen from alkali metal carbonate alone such as sodium carbonate alone, or a mixture of alkali metal carbonate and alkali metal bicarbonate such as the mixture of sodium carbonate and sodium bicarbonate, preferably with a carbonates/bicarbonates weight ratio R of greater than 2, preferentially R is greater than or equal to 4, more preferentially R is greater than or equal to 6, even more preferentially R is greater than or equal to 8, better still greater than or equal to 10 and in particular R is inclusively between 2 and 16, preferentially R is inclusively between 10 and 14.
Preferentially, the pKa value(s) of each alkaline agent are inclusively between 6 and 11.5, more particularly between 9.5 and 11 , at room temperature, said alkaline agent possibly having several pKa values when it comprises several basic functions. Mention may be made, for example, of sodium bicarbonate, which has two pKa values (pKal = 6.33 and pKa2 = 10.33). Thus, preferably, each alkaline agent c) alone or as a mixture has one or more pKa values which are inclusively between 6 and 11.5, or better still between 9.5 and 11 , i.e. each pKa must preferably be between 6 and 11.5, or better still between 9.5 and 1 1.
The alkaline agent(s) c) as defined previously preferably represent a total amount of greater than 1% by weight in total relative to the total weight of composition Cii). More particularly, the total amount of alkaline agent(s) according to the invention is inclusively between 1 % and 15%, preferably between 2% and 10% and more preferentially between 5.1 % and 9% by weight of composition Cii). d) chemical oxidizing agent is) According to a particular embodiment of the invention, the dyeing process also uses one or more chemical oxidizing agents. The term "chemical oxidizing agent" means an oxidizing agent other than atmospheric oxygen. More particularly, the dyeing process uses one or more chemical oxidizing agents chosen from i) hydrogen peroxide; ii) urea peroxide; iii) polymeric complexes that can release hydrogen peroxide, such as polyvinylpyrrolidone/H202, provided in particular in the form of powders, and the other polymeric complexes described in US 5 008 093, US 3 376 110 and US 5 183 901 ; iv) oxidases in the presence of an appropriate substrate (for example, glucose in the case of glucose oxidase or uric acid with uricase); v) metal peroxides which generate hydrogen peroxide in water, such as calcium peroxide or magnesium peroxide; vi) perborates; and/or vii) percarbonates.
According to a preferred embodiment of the invention, composition Cii) comprises one or more chemical oxidizing agents chosen from i) urea peroxide; ii) polymeric complexes which can release hydrogen peroxide chosen from polyvinylpyrrolidone/H202; iii) oxidases; iv) perborates and v) percarbonates.
According to another particular embodiment of the invention, composition Ci) comprises one or more chemical oxidizing agents chosen from i) urea peroxide; ii) polymeric complexes which can release hydrogen peroxide chosen from polyvinylpyrrolidone/H202; iii) oxidases; iv) perborates and v) percarbonates. In particular, the dyeing process uses hydrogen peroxide.
Moreover, the composition(s) comprising hydrogen peroxide or a hydrogen peroxide generating system may also include various adjuvants conventionally used in compositions for dyeing keratin fibres as defined below.
According to a particular embodiment of the invention, the chemical oxidizing agent(s) used represent from 0.001% to 12% by weight of chemical oxidizing agents (of hydrogen peroxide) relative to the total weight of the composition containing it or them, preferentially from 0.2% to 5% and more preferentially between 0.1% and 3% by weight of the composition containing it or them.
Water: According to one embodiment of the invention, water is preferably included in the process of the invention. It may originate from the moistening of the keratin fibres and/or from the composition(s) comprising compounds a) to d) as defined previously or from one or more other compositions.
Preferably, the water comes from at least one composition comprising at least one compound chosen from a) to d) as defined previously.
The compositions: The compositions according to the invention generally comprise water or a mixture of water and of one or more organic solvents or a mixture of organic solvents.
The term "organic solvent" means an organic substance that is capable of dissolving or dispersing another substance without chemically modifying it. The organic solvents:
According to a particular embodiment, at least one of the cosmetic compositions of the invention also comprises an organic solvent. According to one variant, compositions Ci) and Cii) comprise at least one organic solvent. According to an advantageous variant, only composition Ci) comprises at least one organic solvent.
Examples of organic solvents that may be mentioned include Ci-C4 lower alkanols, such as ethanol and isopropanol; polyols and polyol ethers such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, hexylene glycol, and also aromatic alcohols, such as benzyl alcohol or phenoxyethanol. Preferably, the dye composition, i.e. comprising the dye(s), in particular the ODP(s) of the invention, comprises at least one organic solvent as defined previously and in particular an organic solvent chosen from aromatic alcohols, such as benzyl alcohol.
The organic solvents are present in proportions preferably of between 1 % and 40% by weight approximately and more preferably still between 5% and 30% by weight approximately, with respect to the total weight of the dyeing composition.
The adjuvants: The composition(s) of the dyeing process in accordance with the invention may also contain various adjuvants conventionally used in hair dye compositions, such as anionic, cationic, nonionic, amphoteric or zwitterionic surfactants or mixtures thereof, anionic, cationic, nonionic, amphoteric or zwitterionic polymers or mixtures thereof, mineral or organic thickeners, and in particular anionic, cationic, nonionic and amphoteric polymeric associative thickeners, antioxidants, penetrants, sequestrants, fragrances, buffers, dispersants, conditioning agents, for instance volatile or non-volatile, modified or unmodified silicones, film-forming agents, ceramides, preserving agents and opacifiers.
The dyeing process of the invention may also use, in addition to compounds a), b), c) and optionally d), at least one other particular carboxylic acid of formula (I) as defined previously. More particularly, the carboxylic acid(s) of formula (I) are such that A represents a monovalent (d-C6)alkyl or polyvalent (CrC6)alkylene group optionally substituted with one or more hydroxyl groups, and n represents an integer between 0 and 5, such as between 0 and 2, inclusive.
More particularly, the carboxylic acid(s) of the invention are chosen from the acids of formula (I) having a solubility in water of greater than or equal to 1% by weight at 25°C and at atmospheric pressure.
Preferably, the acids of formula (I) comprise at least one hydroxyl group in their structure. Even more preferably, the acid is chosen from a-hydroxy acids. The preferred acids of the invention are chosen from glycolic acid, lactic acid, tartaric acid and citric acid.
The salts of the acids of formula (I) may be salts of organic or mineral bases, such as sodium hydroxide, aqueous ammonia or potassium hydroxide, or salts of organic amines, such as alkanolamines. The acids of formula (I) or salts thereof are present in the composition(s) containing them in a content ranging from 0.1% to 20% by weight.
Said adjuvants are preferably chosen from surfactants such as anionic or nonionic surfactants or mixtures thereof and mineral or organic thickeners.
The above adjuvants are generally present in an amount for each of them of between 0.01% and 40% by weight relative to the weight of the composition, and preferably between 0.1 % and 20% by weight relative to the weight of the composition.
Needless to say, a person skilled in the art will take care to select this or these additional compound(s) such that the advantageous properties intrinsically associated with the composition(s) that are useful in the dyeing process in accordance with the invention are not, or are not substantially, adversely affected by the envisaged addition(s).
The cosmetic composition(s) of the invention may be in various galenical forms, such as a powder, a lotion, a mousse, a cream or a gel, or in any other form that is suitable for dyeing keratin fibres. They may also be packaged in a propellant-free pump-action bottle or under pressure in an aerosol container in the presence of a propellant and form a mousse. pH of the compositions:
According to a preferred embodiment of the invention, the pH of the cosmetic composition Ci) comprising at least one of the ingredients a), b) or b1 ) is acidic, i.e. less than 7.0, preferably less than 5.0, in particular at a pH of between 0 and 4 inclusive, more particularly between 0.5 and 3.5, preferentially between 1 and 3.5.
According to one embodiment, the pH of the cosmetic composition Cii) containing one or more alkaline agents as defined previously is alkaline, i.e. greater than 7, preferably between 8 and 12 inclusive, more particularly between 8.5 and 1 1 and preferentially between 9.5 and 10.5 inclusive.
The pH of these compositions may be adjusted to the desired value by means of alkaline agents as defined previously in c) or by using acidifying agents usually used in the dyeing of keratin fibres, or alternatively by means of standard buffer systems. Among the acidifying agents for the compositions used in the invention, examples that may be mentioned include mineral or organic acids, for instance hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids, for instance acetic acid, tartaric acid, citric acid or lactic acid, or sulfonic acids.
The term "carboxylic acid" means a compound comprising at least one carboxylic acid -C(0)-OH group, preferably of formula (I) as defined previously, preferably comprising between 1 and 4 carboxylic acid groups, such as 1 or 2; or chosen from: i) (CrCi0)alkyl- [C(0)-OH]n and ii) het-[C(0)-OH]n, with n an integer between 1 and 4 inclusive, preferably between 1 and 2, het representing a heterocylic group, such as pyrrolidone, it being possible for the alkyl or het group to be optionally substituted by one or more groups chosen in particular from OH, and (di)(CrC6)(alkyl)amino.
Multi-step dyeing process
According to a particular embodiment, the process for dyeing keratin fibres in several steps consists in applying to said fibres:
- a first cosmetic dye composition Ci) comprising:
a) one or more dyes as defined previously, preferably ODPs as defined previously; b) one or more titanium salts; optionally b1 ) one or more carboxylic acids of formula (I) as defined previously;
and then
- a second cosmetic revealing composition Cii) comprising:
c) one or more alkaline agents each comprising not more than one amine function as defined previously; preferably, the alkaline agent(s) c) are chosen from 1 ) a mixture of carbonates and bicarbonates as defined previously in particular with a carbonates/bicarbonates weight ratio R of greater than 2, preferentially R is greater than or equal to 4, more preferentially R is greater than or equal to 6, even more preferentially R is greater than or equal to 8, better still greater than or equal to 10 and in particular R is inclusively between 2 and 16, preferentially R is inclusively between 10 and 14; and
d) optionally one or more chemical oxidizing agents chosen especially from hydrogen peroxide or one or more hydrogen peroxide-generating systems as defined previously;
preferably, composition Ci) is at acidic pH, i.e. less than 7, preferably less than 5, in particular at a pH of between 0 and 4 inclusive, more particularly between 0.5 and 3.5 and better still between 1 and 3.
According to a particularly advantageous embodiment of the invention, between the step of applying composition Ci) and Cii), at least one step of intermediate rinsing of said fibres, preferably with water, is performed in the process according to the invention.
According to a particular embodiment of the invention, the dyeing process is characterized in that the titanium salt(s) are chosen from organic or mineral titanium salts, preferably from organic titanium salts, and in which the titanium is in particular of oxidation state 2, 3 or 4, preferably of oxidation state 4.
According to a particular embodiment of the invention, the dyeing process is performed in at least two steps which comprise a first step in which the keratin fibres are treated with a cosmetic composition Ci) comprising a) one or more dyes, preferably one or more ODPs as defined previously, b) one or more organic titanium salts and optionally b1 ) one or more carboxylic acid(s) as defined previously; followed by a second step in which the keratin fibres are treated with a cosmetic composition Cii) comprising c) one or more alkaline agents as defined previously whose pH is greater than 7, preferably between 8 and 12 and in particular between 9 and 10.5, and which optionally comprises d) one or more chemical oxidizing agents as defined previously.
Preferentially, composition Ci) comprising a) + b) + optionally b1 ) is at acidic pH, i.e. less than 7, preferably less than 5, in particular at a pH of between 1 and 3 inclusive.
Preferentially, cosmetic composition Cii) applied to the keratin fibres during the second step also comprises d) one or more chemical oxidizing agents chosen especially from hydrogen peroxide and one or more hydrogen peroxide-generating systems, preferably hydrogen peroxide.
According to a particular embodiment, the dyeing process according to the invention is performed in several steps by applying to the keratin fibres, in a first stage, a cosmetic composition Ci) comprising:
a) one or more ODPs as defined previously, especially chosen from: - haematein, brazilein, gallic acid or tannic acid, when the dyeing process does not use a chemical oxidizing agent d);
or else
- haematoxylin or brazilin, when the dyeing process uses a chemical oxidizing agent d); b) one or more organic titanium salts as defined previously; advantageously, ingredient b) is chosen from Ti(IV) salts or complexes; b1 ) optionally one or more carboxylic acids of formula (I) as defined previously; and then
in a second stage, a cosmetic composition Cii) comprising:
c) one or more alkaline agents as defined previously;
preferably, the alkaline agent(s) c) are chosen from 1 ) a mixture of carbonates and bicarbonates as defined previously in particular with a carbonates/bicarbonates weight ratio R of greater than 2, preferentially R is greater than or equal to 4, more preferentially R is greater than or equal to 6, even more preferentially R is greater than or equal to 8, better still greater than or equal to 10 and in particular R is inclusively between 2 and 16, preferentially R is inclusively between 10 and 14, and
d) optionally one or more chemical oxidizing agents chosen from hydrogen peroxide or one or more hydrogen peroxide-generating systems as defined previously;
it being understood that:
- preferentially, composition Ci) is at acidic pH, i.e. less than 7, preferably less than 5, in particular at a pH of between 1 and 3 inclusive; and
- composition Cii) is at alkaline pH, preferably of between 8 and 12 and more particularly of between 9 and 10.5.
The leave-on time after applying composition Ci) comprising the dye(s), especially the ODP(s) as defined previously, is generally set at between 3 and 120 minutes, preferentially between 10 and 60 minutes and more preferentially between 15 and 45 minutes.
Preferably, the two compositions Ci) and Cii) used in the dyeing process of the invention are aqueous.
For this dyeing process, the leave-on time after application of Ci) for the first step is generally set at between 3 and 120 minutes, preferentially between 10 and 60 minutes and more preferentially between 15 and 45 minutes. The application time of composition Cii) comprising ingredient c) during the second step is generally set at between 3 and 120 minutes, preferably between 3 and 60 minutes and more preferably between 5 and 30 minutes.
According to another embodiment, the process for dyeing keratin fibres is performed in two or three steps.
According to this embodiment, the process for dyeing keratin fibres is performed by applying to the keratin fibres, in a first step, a cosmetic composition Ci) comprising: a) one or more dyes, in particular one or more ODPs, chosen especially from:
- haematein, brazilein, gallic acid or tannic acid, when the dyeing process does not use a chemical oxidizing agent d);
or else
- haematoxylin or brazilin, when the dyeing process uses a chemical oxidizing agent d); b) one or more titanium salts as defined previously, and
b1 ) optionally one or more carboxylic acids of formula (I) as defined previously with A representing a monovalent (d-C6)alkyl or polyvalent (CrC6)alkylene group optionally substituted with one or more hydroxyl groups, and n representing an integer between 0 and 5, such as between 0 and 2, inclusive; more particularly, the carboxylic acid(s) of the invention are chosen from citric acid, lactic acid, glycolic acid and tartaric acid; and then, in a second step, applying to said fibres a cosmetic composition comprising: d) optionally one or more chemical oxidizing agents chosen from hydrogen peroxide or one or more hydrogen peroxide-generating systems; and then, in a third step, applying to said fibres a cosmetic composition Cii) comprising:
c) one or more alkaline agents as defined previously; preferably, the alkaline agent(s) c) are chosen from 1 ) a mixture of carbonates and bicarbonates in particular with a carbonates/bicarbonates weight ratio R of greater than 2, preferentially R is greater than or equal to 4, more preferentially R is greater than or equal to 6, even more preferentially R is greater than or equal to 8, better still greater than or equal to 10 and in particular R is inclusively between 2 and 16, preferentially R is inclusively between 10 and 14,
it being understood that:
- preferentially, composition Ci) is at acidic pH, i.e. less than 7, preferably less than 5, in particular at a pH of between 1 and 3 inclusive; and
- composition Cii) comprising the alkaline agent(s) is at alkaline pH, preferably of between 8 and 12, more particularly of between 8.5 and 1 1 and better still between 9.5 and 10.5.
In particular, the dyeing process of the invention is performed in at least two steps: in the first step, ingredients a), b) and optionally b1 ) are applied together to the keratin fibres, in particular the hair, and then, in the second step, ingredients c) and optionally d) are applied together to said fibres.
Irrespective of the application method, the application temperature is generally between room temperature (15 to 25°C) and 220°C and more particularly between 15 and 45°C.
Thus, after application of composition Ci) and/or Cii) according to the invention, the head of hair may advantageously be subjected to a heat treatment by heating to a temperature of between 30 and 60°C. In practice, this operation may be performed using a styling hood, an infrared heating hood (such as Climazon), a hairdryer, an infrared ray dispenser or other standard heating appliances. Use may be made, both as means for heating and for smoothing the head of hair, of a heating iron at a temperature of between 60°C and 220°C and preferably between 120°C and 200°C.
Irrespective of the application method, it is possible to perform rinsing or mechanical wiping and/or drying of the keratin fibres between each step, in particular before performing the final step comprising the application of composition Cii) containing ingredient c).
The steps of intermediate mechanical wiping and drying are also known as "controlled non-rinsing" to distinguish from "standard abundant rinsing with water" and "non-rinsing". The term "mechanical wiping" of the fibres means rubbing an absorbent article on the fibres and physical removal, by means of the absorbent article, of the excess ingredient(s) that have not penetrated the fibres. The absorbent article may be a piece of fabric such as a towel, particularly a terry towel, a cloth or absorbent paper such as household roll towel.
According to one particularly advantageous process of the invention, the mechanical wiping is performed without total drying of the fibre, leaving the fibre moist.
The term "drying" means the action of evaporating the organic solvents and/or water present in one or more compositions used in the process of the invention, comprising or not comprising one or more ingredients a) to e) as defined previously. The drying may be performed with a source of heat (convection, conduction or radiation) by sending, for example, a stream of hot gas such as air necessary to evaporate the solvent(s). Sources of heat that may be mentioned include a hairdryer, a hairstyling hood, a hair-straightening iron, an infrared ray dispenser or other standard heating appliances.
One particular mode of the invention relates to a dyeing process that is performed at room temperature (25°C).
In all the particular forms and variants of the processes previously described, the compositions mentioned are ready-to-use compositions that may result from the extemporaneous mixing of two or more compositions and in particular of compositions present in dyeing kits. dyeing device or "kit"
Another subject of the invention is a multi-compartment dyeing device or "kit". Advantageously, this kit comprises from 2 to 5 compartments comprising from 2 to 5 compositions in which are distributed ingredients a) to d) as defined above, which may be aqueous or pulverulent, with in particular at least one of said compositions being aqueous.
According to a first variant, the kit comprises five compartments, the first four compartments respectively comprising ingredients a), b) and optionally b1 ) and c), optionally in powder form, as defined previously and the fifth compartment containing an aqueous oxidizing composition, such as water comprising d) as defined previously.
In this embodiment, at least one of the four compositions is aqueous and the dye(s), in particular the ODP(s), may be in powder form.
In another kit variant, this kit comprises two compartments, in which the first composition contained in the first compartment comprises a), b) and optionally b1) and the second compartment comprises c) and optionally d) in powder form or in aqueous medium; preferably, the second composition is aqueous.
In another kit variant, this kit comprises three compartments, in which the first composition contained in the first compartment comprises a) and b) and optionally b1 ) and the second compartment comprises d) in powder form or in aqueous medium; preferably, the second composition is aqueous and the third compartment comprises c). According to one variant, the device according to the invention also comprises an additional composition comprising one or more treating agents.
The compositions of the device according to the invention are packaged in separate compartments, optionally accompanied by suitable application means which may be identical or different, such as fine brushes, coarse brushes or sponges.
The device mentioned above may also be equipped with a means for dispensing the desired mixture on the hair, for instance the devices described in patent FR 2 586 913.
A subject of the invention is also the use of said cosmetic dye composition for dyeing keratin fibres.
A subject of the invention is also a cosmetic composition for dyeing keratin fibres, containing compounds a), b), optionally b1), c), and optionally d) as defined previously.
For the purposes of the present invention, the term "build-up" of the colour on keratin fibres means the variation in colouring between locks of non-dyed white hair and locks of dyed hair.
The examples that follow serve to illustrate the invention without, however, being limiting in nature. EXAMPLES:
Example 1 :
a) Preparation of the compositions and application to keratin fibres
The following compositions were prepared from the ingredients in the proportions indicated in grams per 100 g of composition according to the following tables:
Figure imgf000062_0002
Figure imgf000062_0001
Dye composition 1 was applied to natural Chinese hair containing 100% white hairs, and left to stand on the hair for 45 minutes at 40°C then rinsed out with tap water until the colour in the rinsing water disappeared.
Next, each of the revealing compositions A to D was applied in the same amount and left to stand on the hair for 15 minutes at 40°C.
After these leave-on times, the locks are washed with Elvive multivitamin shampoo, rinsed and then dried under a hood. b) Visual and colorimetric evaluations
It was found that the locks treated via the process of the invention are very intensely coloured, which was corroborated by the colorimetric measurements below. In addition, it is seen that the colouring was visually homogeneous and persistent with respect to successive shampoo washing.
The colour of the locks was then evaluated in the CIE L* a* b* system using a Minolta Spectrophotometer CM3600D colorimeter. In this L* a* b* system, the three parameters denote, respectively, the colour intensity (L*), the green/red colour axis (a*) and the blue/yellow colour axis (b*).
Colour build-up:
The variation in colouring between the locks of permanent-waved Chinese hair containing 90% white hairs, before and after treatment or dyeing, is defined by (ΔΕ*) according to the following equation:
ΔΕ* = (L*-Lo*)2 + (a*-ao *)2 + (b* -bD *)2
In this equation, L*, a* and b* represent the values measured on locks of hair after dyeing and L0 *, a0 * and b0 * represent the values measured on locks of undyed virgin hair. The higher the ΔΕ* value, the better the colour build-up.
The results L, a, b of colour build-up are collated in the table below:
Figure imgf000063_0001
It is seen that the process according to the invention which used the revealing composition A made it possible to obtain significantly more intense colouring, with significantly greater build-up than when the dyeing process used a comparative revealing composition containing an alkaline agent comprising two amine functions such as arginine (comparative compositions B to D).
Example 2: a) Preparation of the compositions and application to keratin fibres
The following compositions were prepared from the ingredients in the proportions indicated in grams per 100 g of composition according to the following tables:
■ Dye composition 1 : was prepared in the same amounts as the preceding examples.
Figure imgf000064_0001
Dye composition 1 was applied as defined in Example 1. Next, each of the revealing compositions E to G was then applied and left to stand on the hair for 15 minutes at 40°C. After these leave-on times, the locks were washed with Elvive multivitamin shampoo, rinsed and then dried under a hood.
High-performance colourings were visually observed (intensity, colour homogeneity), irrespective of the revealing composition E to G applied.
After the keratin fibres had been treated with composition 1 and the revealing compositions E to G, the locks obtained were a very strong and intense black.
This is confirmed by the spectrocolorimetric measurements with low L* values and high build-up ΔΕ values:
Processes according to the invention L* a* b* ΔΕ*
Composition 1 + Composition E 20.71 -0.02 -0.5 62.7
Composition 1 + Composition F 21 0.03 -0.13 62.28
Composition 1 + Composition G 21.43 -0.13 -0.31 61.96 Example 3:
The following compositions are prepared from the following ingredients in the following proportions, indicated in grams:
■ Pretreatment composition Cii) :
Figure imgf000065_0001
Protocol
The study relates to locks of natural Caucasian hair containing 90% white hairs (90 NW). According to a first treatment process P1 according to the invention, the locks are pretreated separately with composition Cii) comprising the titanium salt. During this pretreatment step, composition Cii) is left to stand for 15 minutes on each lock at 33°C, and each lock is then rinsed. The dye composition Ciii) is prepared just before use and then applied to each of the locks and left to stand for 60 minutes on each lock at 33°C. After these leave-on time the locks are rinsed and then dried under a hood.
In parallel, according to a second and a third comparative treatment processes P2 and P3 outside of the invention, the locks of natural Caucasian hair containing 90% white hairs (90 NW) are not pretreated with composition Cii).
The dye composition Ciii) is applied directly (without a pretreatment) to each of the locks and left to stand for 60 at 33°C (process P2) and for 120 minutes at 33°C (Process P3). After these leave-on times, the locks are rinsed and then dried under a hood.
Dyeing results
According to the process of the invention P1 , i.e. with pretreatment with the titanium salts, very intensely coloured locks were obtained, whereas those which did not receive the pretreatment with titanium salts are less intensely dyed, even with a leave on time of 120 minutes. This is confirmed by the colorimetric measurements below.
Table 4
Figure imgf000066_0001
It is clearly seen that the locks treated according to the process of the invention P1 with a pretreatment with composition Cii) and then dyed with composition Ciii) are much more intensely dyed and with significantly greater colour build-up than the locks treated with the comparative processes P2 and P3, /'e with the dye composition Ciii), with a leave-on time of 60 mn or even 120 mn, without pretreatment with the composition Cii) comprising the titanium salt, since the value of L* decreases greatly with the process according to the invention and the value of the colour build-up ΔΕ is higher according to the invention.

Claims

1. Process for dyeing keratin fibres, in particular human keratin fibres such as the hair, in which said fibres are treated, in several steps:
· with a cosmetic dye composition Ci) containing:
a) one or more dyes chosen in particular from direct dyes and natural dyes, preferably chosen from ortho-diphenols (ODPs);
b) one or more titanium (Ti) salts; in particular, the Ti atom of the salt is of oxidation state 2, 3 or 4, denoted Ti(ll), Ti(lll) or Ti(IV), preferably Ti(IV); and
b1 ) optionally one or more carboxylic acids of formula (I) below:
Figure imgf000067_0001
or a salt thereof, in which formula (I):
- A represents a saturated or unsaturated, cyclic or non-cyclic and aromatic or non- aromatic hydrocarbon-based group, which is monovalent when n has the value 0 or polyvalent when n is greater than or equal to 1 , comprising from 1 to 50 carbon atoms, which is optionally interrupted with one or more heteroatoms and/or optionally substituted, especially with one or more hydroxyl groups; preferably, A represents a monovalent (CrC6)alkyl group or a polyvalent (CrC6)alkylene group optionally substituted with one or more hydroxyl groups;
- n represents an integer between 0 and 10 inclusive; preferably, n is between 0 and 5, such as between 0 and 2; and then
with a cosmetic revealing composition Cii) containing:
c) one or more alkaline agents comprising not more than one amine function; and d) optionally one or more chemical oxidizing agents chosen from hydrogen peroxide or one or more hydrogen peroxide-generating systems;
it being understood that when composition Cii) contains several alkaline agents, then each of the alkaline agents comprises not more than one amine function;
said process preferably comprising an intermediate rinsing step between the application of Ci) and Cii).
2. Dyeing process according to Claim 1 , in which composition Ci) is at acidic pH, i.e. less than 7.0, preferably less than 5.0, particularly at a pH between 0 and 4 inclusive, more particularly between 0.5 and 3.5, preferentially between 1 and 3.5; and/or the pH of composition Cii) containing one or more alkaline agents is alkaline, i.e. greater than 7, preferably between 8 and 12 inclusive, more particularly between 8.5 and 1 1 , preferentially between 9.5 and 10.5 inclusive.
3. Process according to either of the preceding claims, in which the dye(s) of the dye composition Ci) are chosen from dyes of natural origin; especially chosen from spinulosin, orceins, polyphenols or ODPs and all extracts rich in ODPs, curcumin, indole derivatives such as isatin or indole-2,3-dione, indigoids including indigo, phthalocyanines and porphyrins in particular complexed to a metal, glycosyl or non-glycosyl iridoids, chromene dyes, anthraquinone and benzoquinone dyes such as lawsone or henna, juglone, spinulosin, chromene or chroman dyes, such as neoflavanols and neoflavanones, flavanols, indigoids such as indigo; and anthocyanidols.
4. Dyeing process according to any one of the preceding claims, in which the dye(s) a) of the dye composition Ci) are chosen from the ODPs of formula (II) below, or an oligomer, tautomer, optical isomer or geometrical isomer thereof, and also salts or solvates thereof, such as hydrates:
Figure imgf000068_0001
in which formula (II):
• R1 to R4, which may be identical or different, represent: i) a hydrogen atom, ii) a halogen atom, or a group chosen from iii) hydroxyl, iv) carboxyl, v) (d-C2o)alkyl carboxylate or (Ci-C20)alkoxycarbonyl, vi) optionally substituted amino, vii) optionally substituted linear or branched (Ci-C20)alkyl, viii) optionally substituted linear or branched (C2-C2o)alkenyl, ix) optionally substituted cycloalkyl, x) (CrC20)alkoxy, xi) (C1-C20)alkoxy(C1-C20)alkyl, xii) (CrC20)alkoxyaryl, xiii) aryl which may optionally be substituted, xiv) aryl, xv) substituted aryl, xvi) heterocyclic aryl which is saturated or unsaturated, optionally bearing a cationic or anionic charge and which is optionally substituted and/or optionally fused with an aromatic ring, preferably a benzene ring, said aromatic ring optionally being substituted, in particular with one or more hydroxyl or glycosyloxy groups, xvii) a radical containing one or more silicon atoms;
or two of the substituents borne by two adjacent carbon atoms R1 - R2, R2 - R3 or R3 - R4 form, together with the carbon atoms bearing them, a saturated or unsaturated and aromatic or non-aromatic ring optionally containing one or more heteroatoms and optionally fused with one or more saturated or unsaturated rings optionally containing one or more heteroatoms; in particular, R1 to R4 together form from one to four rings; more particularly, R2 and R3 form a pyrrolyl or pyrrolidinyl radical fused to the benzene ring bearing the two hydroxyls;
in particular, the ODPs are chosen from:
- flavanols, such as catechin and epicatechin gallate,
- flavonols, for instance quercetin,
- anthocyanidins, for instance cyanidin, delphinidin and petunidin,
- anthocyanins or anthocyans, for instance myrtillin,
- ortho-hydroxybenzoates, for example gallic acid salts,
- flavones, for instance luteolin,
- hydroxystilbenes, for example 3,3',4,5'-tetrahydroxystilbene, optionally oxylated (for example glucosylated),
- 3,4-dihydroxyphenylalanine and derivatives thereof,
- 2,3-dihydroxyphenylalanine and derivatives thereof,
- 4,5-dihydroxyphenylalanine and derivatives thereof,
- dihydroxycinnamates, such as caffeic acid and chlorogenic acid,
- ortho-polyhydroxycoumarins,
- ortho-polyhydroxyisocoumarins,
- ortho-polyhydroxycoumarones,
- ortho-polyhydroxyisocoumarones,
- ortho-polyhydroxychalcones,
- ortho-polyhydroxychromones,
- quinones,
- hydroxyxanthones,
- 1 ,2-dihydroxybenzene and derivatives thereof,
- 1 ,2,4-trihydroxybenzene and derivatives thereof,
- 1 ,2,3-trihydroxybenzene and derivatives thereof,
- 2,4,5-trihydroxytoluene and derivatives thereof,
- proanthocyanidins and especially the proanthocyanidins A1 , A2, B1 , B2, B3 and C1 ,
- chromans and chromenes,
- proanthocyanins,
- tannic acid,
- ellagic acid,
- and mixtures of the preceding compounds;
preferably, the ortho-diphenol(s) are chosen from haematein, brazilein, gallic acid, tannic acid, haematoxylin and brazilin, and mixtures thereof.
5. Dyeing process according to any one of the preceding claims, in which the dye(s) of the dye composition Ci) are chosen from chromene or chroman ODP dyes and particularly chosen from neoflavanols and neoflavanones, more particularly chosen from the dyes having the following formulae:
> formula (III), comprising, in its structure, the bicycle of formula (B2),
Figure imgf000070_0001
and also the tautomeric and/or mesomeric forms thereof, the stereoisomers thereof, the addition salts thereof with a cosmetically acceptable acid or base, and the solvates thereof such as hydrates;
in which formula (III):
• represents a carbon-carbon single bond or a carbon-carbon double bond, the sequence of these bonds denoting two carbon-carbon single bonds and two carbon-carbon double bonds, said bonds being conjugated,
• X represents a group:
// /
HO-C or 0=C
\ \
• R1, R2, R3, R4, R5 and R6, which may be identical or different, represent a hydrogen atom, a hydroxyl group, an optionally substituted alkyl group, an optionally substituted alkoxy group or an optionally substituted acyloxy group; and
> formula (IV), comprising, in its structure, the bicycle of formula (B1):
Figure imgf000070_0002
and also the tautomeric and/or mesomeric forms thereof, the stereoisomers thereof, the addition salts thereof with a cosmetically acceptable acid or base, and the hydrates thereof;
in which formula (IV): • Rn , R12, Ri3, Ri6, Rig and R20, which may be identical or different, represent a hydrogen atom or a Ci-C4 alkyl radical, and
• Ri4, Ri5, Ri7 and R18, which may be identical or different, represent a hydrogen atom, a hydroxyl radical or a CrC4 alkoxy radical;
in particular, the dye(s) a) are of formula (III) and more particularly chosen from haematoxylin, haematein, brazilin and brazilein; preferentially haematoxylin and brazilin:
Figure imgf000071_0001
Haematein Brazilein
Figure imgf000071_0002
Hematoxylin Brazilin
6. Dyeing process according to any one of the preceding claims, in which the dye(s) a) of the dye composition Ci) are chosen from natural dyes and are chosen from extracts of animals, of bacteria, of fungi, of algae, of plants and of fruits.
7. Dyeing process according to any one of the preceding claims, in which the acid(s) b1 ) of the dye composition Ci) are of formula (I) with A representing a monovalent (d- C6)alkyl or polyvalent (CrC6)alkylene group optionally substituted with one or more hydroxyl groups, and n representing an integer between 0 and 5 inclusive, such as 0, 1 or 2; in particular, the carboxylic acid or acids of the invention are chosen from a-hydroxy acids; preferentially, the acid is chosen from citric acid, lactic acid, tartaric acid and glycolic acid; more preferentially, the acid(s) b1 ) of formula (I) or salts thereof are present in a content ranging from 0.1% to 20% by weight relative to the total weight of composition Ci).
8. Dyeing process according to any one of the preceding claims, in which the titanium salt(s) b) of the dye composition Ci) are chosen from organic or mineral titanium salts, preferably from organic titanium salts, and in which the titanium is in particular of oxidation state 2, 3 or 4, preferably of oxidation state 4.
9. Dyeing process according to the preceding claim, in which the organic titanium salt(s) b) of the dye composition Ci) are derived from the reaction of organic acid(s) with titanium, in which the organic acid(s) are chosen from organic acids comprising:
a) at least one optionally unsaturated, linear or branched C C2o hydrocarbon-based chain, or a (hetero)cycloalkyl or (hetero)aryl group, and
b) at least one acid chemical function chosen in particular from carboxyl COOH, sulfuric S03H, S02H, and phosphoric P03H2, P04H2;
preferably, the organic acid(s) are chosen from the carboxylic acids of formula (I) as defined in Claim 1 or 7, better still from citric acid, lactic acid, tartaric acid and glycolic acid and more particularly lactic acid and glycolic acid.
10. Dyeing process according to any one of the preceding claims, in which the acid(s) b1 ) of the dye composition Ci) are of formula (I) as defined in Claim 1 or 7 and these acids are different from the organic acid(s) of the titanium salt as defined in Claim 8 or 9.
11. Dyeing process according to any one of the preceding claims, in which the organic titanium salt(s) b) of the dye composition Ci) are chosen from those of formula (l-A) below:
Figure imgf000072_0001
in which formula (l-A):
• A is as defined in Claim 1 or 7;
• n, n' and n", which may be identical or different, are equal to 1 , 2, 3 or 4 and n' + n" =
6;
• M! and M2, which may be identical or different, represent a cationic counterion such as a cation of an alkali metal such as Na or K or of an alkaline-earth metal such as Ca or an organic cation such as ammonium, preferably ammonium or a hydrogen atom;
• TiYn" represents Ti(OH)n-, or Ti(0)n /2, or Ti(OH)m1(0)m2with m!+m2 = n";
preferably, the organic titanium salt(s) of the dyeing process are dihydroxybis(lactato)titanium(IV) salts such as those having the following formula:
Figure imgf000072_0002
12. Dyeing process according to any one of the preceding claims, in which the alkaline agent(s) c) of the revealing composition Cii) are chosen from i) (bi)carbonates, ii) ammonia, iii) alkanolamines comprising only one amine function such as monoethanolamine; monopropanolamine, iv) oxyalkylenated alkanolamines comprising only one amine function and in particular oxyethylenated alkanolamines such as oxyethylenated and/or oxypropylenated ethyleneamines, v) mineral or organic hydroxides, vi) alkali metal silicates such as sodium metasilicates, vii) amino acids comprising only one amine function, preferably basic amino acids such as histidine ; particularly the alkaline agent is chosen from alkali metal or alkaline-earth metal (bi)carbonates and amino acids comprising only one amine function such as histidine; preferentially, the alkaline agent(s) c) of the revealing composition Cii) are chosen from alkali metal (bi)carbonates and amino acids comprising only one amine function; it being understood that when composition Cii) contains several alkaline agents, then each of the alkaline agents comprises not more than one amine function.
13. Dyeing process according to any one of the preceding claims, in which the alkaline agent(s) c) of the revealing composition Cii) are chosen from a mixture of two alkaline agents i) to vii) as defined in the preceding claim; in particular, the alkaline agent(s) c) are chosen from the following mixtures:
1 ) carbonates + bicarbonates;
2) amino acids + (bi)carbonates;
3) alkanolamines + (bi)carbonates;
4) oxyalkylenated alkanolamines + (bi)carbonates;
5) mineral or organic hydroxides + (bi)carbonates;
6) alkali metal silicates + (bi)carbonates;
the amino acids and oxyalkylenated or non-oxyalkylenated alkanolamines comprising not more than one amine function;
more particularly, the weight ratio R between carbonates and bicarbonates according to 1 ) or between the first alkaline agents: amino acids, alkanolamines, oxyalkylenated alkanolamines, mineral or organic hydroxides or alkali metal silicates, and the (bi)carbonates according to 2) to 6) is greater than or equal to 2, preferentially R is greater than or equal to 4, more preferentially R is greater than or equal to 6, even more preferentially R is greater than or equal to 8, better still greater than or equal to 10 and in particular R is inclusively between 2 and 16, preferentially R is inclusively between 10 and 14.
14. Dyeing process according to the preceding claim, in which the alkaline agent(s) c) of the revealing composition Cii) are chosen from a mixture of carbonates and bicarbonates with a carbonates/bicarbonates weight ratio R of greater than 2, preferentially R is greater than or equal to 4, more preferentially R is greater than or equal to 6, even more preferentially R is greater than or equal to 8, better still greater than or equal to 10 and in particular R is inclusively between 2 and 16, preferentially R is inclusively between 10 and 14;
advantageously, composition Cii) comprises at least one alkaline agent chosen from alkali metal carbonate such as sodium carbonate alone or a mixture of alkali metal carbonate and alkali metal bicarbonate such as the mixture of sodium carbonate and sodium bicarbonate, preferably with a carbonates/bicarbonates weight ratio R of greater than 2, preferentially R is greater than or equal to 4, more preferentially R is greater than or equal to 6, even more preferentially R is greater than or equal to 8, better still greater than or equal to 10 and in particular R is inclusively between 2 and 16, preferentially R is inclusively between 10 and 14.
15. Dyeing process according to any one of the preceding claims, in which the alkaline agent(s) c) of composition Cii) have one or more pKa values between 6 and 1 1.5 inclusive, more particularly between 9.5 and 1 1 , at room temperature.
16. Dyeing process according to any one of the preceding claims, in which the carboxylic acid(s) b1 ) have a pKai value of less than 3.
17. Dyeing process according to any one of the preceding claims, in which the alkaline agent(s) c) of composition Cii) represent a total amount of greater than 1% by weight in total relative to the total weight of composition Cii), particularly between 1% and 15% inclusive, more particularly between 2% and 10%, preferentially between 5.1 % and 9% by weight of composition Cii).
18 Dyeing process according to any one of the preceding claims, in which composition Cii) comprises one or more chemical oxidizing agents d) chosen from hydrogen peroxide or one or more hydrogen peroxide generating systems, in particular chosen from hydrogen peroxide or urea peroxide, preferably hydrogen peroxide.
19. Dyeing process according to any one of the preceding claims, in which composition Ci) and/or composition Cii), preferably composition Ci), comprise one or more organic solvents, especially chosen from lower Ci-C4 alkanols, such as ethanol and isopropanol; polyols and polyol ethers, such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, hexylene glycol; and also aromatic alcohols, such as benzyl alcohol or phenoxyethanol, preferably aromatic alcohols, such as benzyl alcohol.
20. Dyeing process according to any one of the preceding claims, which comprises, in a first stage, the application to keratin fibres of a cosmetic composition Ci) comprising: a) one or more ODPs as defined in any one of Claims 3 to 6, chosen especially from:
- haematein, brazilein, gallic acid or tannic acid, when the dyeing process does not use a chemical oxidizing agent d) as defined in Claim 1 or 18;
or else
- haematoxylin or brazilin, when the dyeing process uses a chemical oxidizing agent d) as defined in Claim 1 or 18;
b) one or more organic titanium salts as defined in any one of Claims 1 and 8 to 1 1 ; b1 ) optionally one or more carboxylic acids of formula (I) as defined in any one of Claims 1 , 7 and 16; and then
in a second stage, the application of a cosmetic composition Cii) comprising:
c) one or more alkaline agent(s) as defined in any one of Claims 1 , 13 to 15 and 17; and d) optionally one or more chemical oxidizing agents chosen from hydrogen peroxide or one or more hydrogen peroxide-generating systems as defined previously;
it being understood that:
- composition Ci) is at acidic pH, i.e. less than 7, preferably less than 5, in particular at a pH of between 1 and 3 inclusive; and
- composition Cii) is at alkaline pH, preferably of between 8 and 12 and more particularly of between 9 and 10.5.
21. Cosmetic composition comprising ingredients a), b), optionally b1 ), c) and optionally d) as defined according to any one of Claims 1 to 18 and optionally an organic solvent as defined in Claim 19.
22. Multi-compartment device comprising from 2 to 5 compartments containing from 2 to 5 compositions, in which are distributed ingredients a), b), optionally b1 ), c) and optionally d) as defined according to any one of Claims 1 to 18, said compositions being aqueous or pulverulent, with at least one of these compositions being aqueous.
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CN110573135A (en) * 2018-02-20 2019-12-13 株式会社Ｎｉｌ Wool dyeing agent
JP6624628B1 (en) * 2018-02-20 2019-12-25 株式会社Ｎｉｌ Hair dye
CN110573135B (en) * 2018-02-20 2022-07-22 株式会社Nil Wool dyeing agent

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