WO2016198648A1 - Hair dyeing process using a titanium salt, a dye and a particular solvent - Google Patents

Hair dyeing process using a titanium salt, a dye and a particular solvent Download PDF

Info

Publication number
WO2016198648A1
WO2016198648A1 PCT/EP2016/063367 EP2016063367W WO2016198648A1 WO 2016198648 A1 WO2016198648 A1 WO 2016198648A1 EP 2016063367 W EP2016063367 W EP 2016063367W WO 2016198648 A1 WO2016198648 A1 WO 2016198648A1
Authority
WO
WIPO (PCT)
Prior art keywords
chosen
group
alkyl
acid
dyes
Prior art date
Application number
PCT/EP2016/063367
Other languages
French (fr)
Inventor
Boris Lalleman
Alain Lagrange
Original Assignee
L'oreal
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by L'oreal filed Critical L'oreal
Publication of WO2016198648A1 publication Critical patent/WO2016198648A1/en

Links

Classifications

    • 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
    • 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
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/58—Metal complex; Coordination compounds
    • 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 multi-step process for dyeing keratin fibres, in particular human keratin fibres such as the hair, in which said fibres are treated with:
  • a cosmetic composition Ci) comprising a) one or more titanium salts and b) optionally one or more particular carboxylic acids;
  • ii) at least one step of dyeing with a cosmetic dye composition Cii) comprising c) one or more dyes chosen from oxidation dyes, synthetic direct dyes and dyes of natural origin, preferably chosen from ortho-diphenols; d) at least one liquid organic compound with a Hansen solubility parameter value ⁇ of greater than 0 and less than 16 MPa 1 ⁇ 2 and optionally e) one or more chemical oxidizing agents such as hydrogen peroxide or one or more hydrogen peroxide-generating systems, iii) optionally at least one step of intermediate rinsing of said fibres,
  • 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.
  • A represents a monovalent group when n has the value zero or a polyvalent group when n is greater than or equal to 1 , saturated or unsaturated, cyclic or non-cyclic and aromatic or non-aromatic hydrocarbon-based group comprising from 1 to 50 carbon atoms which is optionally interrupted with one or more heteroatoms and/or optionally substituted, in particular with one or more hydroxyl and/or amino groups; preferably, A represents a monovalent (d-C 6 )alkyl group or a polyvalent (CrC 6 )alkylene group optionally substituted with one or more hydroxyl and/or amino groups;
  • n represents an integer between 0 and 10 inclusive; preferably, n is between 0 and 5, such as between 0 and 2; and
  • 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, sebum and light without impairing the fibres.
  • the resistance to perspiration is particularly good, as is the homogeneity of the colour between the root and the end of the fibres.
  • the dyeing process used can induce very satisfactory "build-up" and/or strength of the colouring.
  • the cosmetic composition Ci) used according to the treatment step i) of the process according to the invention comprises at least one or more titanium salts: in particular, the titanium atom of said salt(s) is of oxidation state 2, 3 or 4, denoted Ti(ll), Ti(lll) or Ti(IV), preferably Ti(IV).
  • 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 which may be of oxidation state 1 , 2, 3 or 4, preferably of oxidation state 4, denoted Ti(IV).
  • 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 C C 2 o 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) a) of the invention are chosen from those of formula (l-A) below:
  • M 1 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 (CrC 6 )alkyl or polyvalent (CrC 6 )alkylene group optionally substituted with one or more hydroxyl groups or one or more amino groups, preferably 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 a-hydroxy acids and a-amino acids; preferably, the acid is chosen from citric acid, lactic acid, malic acid, tartaric acid, glycolic acid and serine, more preferentially chosen from lactic acid and glycolic acid.
  • organic titanium salt(s) a) 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)(CrC 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 (d-C 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 (CrC 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) a) of the dyeing process are dihydroxybis(lactato)titaniumlV salts such as those having the following formula:
  • 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 titanium salt(s) a) are mineral. They are in particular chosen from titanium halides, titanium sulfates and titanium phosphates.
  • the mineral titanium salts are Ti(ll), Ti(lll) or Ti(IV) salts.
  • the mineral titanium salts are Ti(lll) or Ti(IV) salts.
  • the mineral titanium salts are Ti(IV) salts.
  • the titanium salt(s) a) 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) a) are present in the cosmetic composition i) of the dyeing process according to the invention in a content ranging from 0.001% to 20% by weight relative to the total weight of said composition i) as defined previously.
  • 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.
  • one or more carboxylic acids are soluble in water in a proportion of at least 0.0001 g/l and better still at least 1 g/l.
  • the cosmetic composition Ci) used according to the treatment step i) of the process according to the invention may also comprise one or more carboxylic acids.
  • the cosmetic composition Ci) used according to the treatment step i) of the process according to the invention may also comprise b) one or more carboxylic acids of formula (I) as defined previously.
  • the carboxylic acid(s) b) are other than the carboxylic acids complexed to the Ti salts, preferably glycolic acid, lactic acid, citric acid or a salt thereof.
  • the carboxylic acid(s) b) are 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 a) is lactic acid or the carboxylate salt thereof (lactate)
  • the second acid b) is other than lactic acid or lactate, and may be, for example, glycolic acid.
  • the acid salts of formula (I) may be salts of organic or mineral bases or basifying agents e) as defined below.
  • the salts are sodium, ammonia or potassium salts or salts of organic amines such as alkanolamines.
  • composition Ci) may be present in composition Ci) in a content ranging from 0.1% to 20% by weight relative to the total weight of said composition Ci).
  • the cosmetic dye composition Cii) used in the dyeing step ii) of the process according to the invention comprises c) one or more dyes chosen from oxidation dyes, synthetic direct dyes and dyes of natural origin, preferably chosen from ortho-diphenols.
  • the total content of dyes in the dye composition Cii) is preferably between 0.001% and 20% by weight, preferably between 0.001 % and 10% by weight, preferably between 0.001% and 5% by weight, relative to the weight of composition Cii).
  • the dye composition Cii) comprises one or more 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- tolylenediamine, 2-isopropyl-para-phenylenediamine, 2- -hydroxyethyl-para- phenylenediamine, 2- -hydroxyethyloxy-para-phenylenediamine, 2,6-dimethyl-para- phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,3-dimethyl-para- phenylenediamine, N,N-bis( -hydroxyethyl)-para-phenylenediamine, 2-chloro-para- phenylenediamine, 2- -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 N,N'-bis( -hydroxyethyl)-N,N'-bis(4'-aminophenyl)-1 ,3-diaminopropanol, N,N'-bis( - hydroxyethyl)-N,N'-bis(4'-aminophenyl)ethylenediamine, N,N'-bis(4- aminophenyl)tetramethylenediamine, N,N'-bis( -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
  • 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-( -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
  • 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,
  • the heterocyclic oxidation bases of the invention are chosen from 4,5-diaminopyrazoles such as 4,5-diamino-1-( -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 especially 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.
  • the dye composition Cii) comprises one or more synthetic direct dyes.
  • the synthetic direct dye(s) that may be used in the context of the invention may be fluorescent or non-fluorescent, anionic direct dyes (also known as acid dyes), cationic direct dyes (also known as basic dyes) or neutral direct dyes.
  • direct dyes are chosen in particular from those conventionally used in direct dyeing, any commonly used aromatic and/or non-aromatic dyes such as neutral, anionic (also known as acid dyes) or cationic (also known as basic dyes) nitrobenzene direct dyes, neutral, anionic (also known as acid dyes) or cationic (also known as basic dyes) azo direct dyes, neutral, anionic (also known as acid dyes) or cationic (also known as basic dyes) quinone and in particular anthraquinone direct dyes, azine, polyarylmethane such as triarylmethane, indoamine, polymethines such as styryl, porphyrin, metalloporphyrin, phthalocyanine, methine cyanine direct dyes.
  • aromatic and/or non-aromatic dyes such as neutral, anionic (also known as acid dyes) or cationic (also known as basic dyes) nitrobenzene direct dyes, neutral, anionic
  • the synthetic direct dye(s) are preferably present in a total amount ranging from 0.001% to 20% by weight, preferably from 0.001 % to 10% by weight approximately of the total weight of the dye composition, preferably ranging from 0.005% to 5% by weight relative to the total weight of the dye composition.
  • the synthetic direct dye is preferably 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 dyes 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 anionic direct dye(s) are chosen from acidic nitro direct dyes, acidic azo dyes, acidic azine dyes, acidic triarylmethane dyes, acidic indoamine dyes, acidic anthraquinone dyes and indigoids; 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; and mixtures thereof.
  • anionic direct dyes means any direct dye comprising a structure at least one C0 2 R or S0 3 R substituent with R denoting a hydrogen atom or a cation originating from a metal or an amine, or an ammonium ion.
  • the anionic dyes may be chosen from acidic nitro direct dyes, acidic azo dyes, acidic azine dyes, acidic triarylmethane dyes, acidic indoamine dyes, acidic anthraquinone dyes and indigoids; and mixtures thereof.
  • the dye(s) of the invention are chosen from the direct dyes of formula (VI):
  • Col ( >m (Q + ) n (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 charge(s): ⁇ 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 dyes of formula (VI) of the invention are chosen from acidic nitro direct dyes, acidic azo dyes, acidic azine dyes, acidic triarylmethane 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), ( ⁇ '), (XI), (XII), (XIII) and (XIV) below:
  • R 7 , R 8 , R 9 , R 10 , R' 7 , R' 8 , R' 9 and R' 10 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
  • W represents a sigma bond, an oxygen or sulfur atom, or a divalent radical i) - N(R)- 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 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;
  • 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 ammonium sulfonate or carboxylate;
  • dyes of formula (II) 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 117, Acid Black 1 , Acid Brown 4, Acid Brown 20, Acid Black 26, Acid Black 52, Food Black 1 , Food Black 2;
  • dyes of formula (VII') mention may be made of: Acid Red 11 1 , Acid Red 134, Acid yellow 38;
  • Rii, Ri 2 and Ri 3 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-, IVTwith 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 Ri 6 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'i6, R'i9 and R' 2 o 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
  • 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 (0)C(0 , 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 an example of dyes of formula (VIII'), mention may be made of Acid Yellow 17; c3c) the anthraquinone dyes of formulae (IX) and (IX'):
  • R 22 , 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 29 with R 28 and R 29 , which may be identical or different, representing a hydrogen atom or a group chosen from i) alkyl, ii) polyhydroxyalkyi such as hydroxyethyl, iii) aryl optionally substituted with one or more groups, particularly 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)-, R°-X'-C(X)-
  • R° represents an alkyl group, iv) cycloakyl; especially cyclohexyl;
  • Z represents a group chosen from hydroxyl and NR' 28 R' 2 9 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 (0) 2 S(0 , Q + ;
  • 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;
  • R30, R31 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 -, IvT with M + as defined previously, x) (di)(alkyl)amino, xi) (di)(hydroxyalkyl)amino, x
  • R c and R d 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 CrC 6 alkylene group
  • ALK represents a group -CH 2 -CH 2 -;
  • n 1 or 2;
  • p represents an integer between 1 and 5 inclusively
  • q represents an integer between 1 and 4 inclusively
  • u is 0 or 1 ;
  • 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 + ; , which may be present or absent, represents a benzo group optionally substituted with one or more groups R 30 as defined previously; it being understood that 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; c3e) 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;
  • R 37 , R 38 , R 39 , R 40 , R41 , R 42 , R43 and R 44 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) 2 S(0 , M + with M + representing a hydrogen atom or a cationic counterion; ix) (
  • 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; particularly, R 37 to R 40 represent a hydrogen atom, and R 41 to R44, which may be identical or different, represent a hydroxyl group or (0) 2 S(0 , M + ; and when R 43 with R 44 together form a benzo group, it is preferentially
  • 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; c3f) the xanthene-based dyes of formula (XII):
  • 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 -, IVT 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 + ;
  • L' represents an oxygen or sulfur atom or an ammonium group: N + R f R g , with R f and R g , 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) m S(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) ses 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 (0)C(0 , 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. c3h) the quinoline-based dyes of formula (XIV):
  • R 6 i represents a hydrogen or halogen atom or an alkyl group
  • ⁇ Re2, Re3 and R 6 4 which may be identical or different, represent a hydrogen atom or a group (0) 2 S(0 , M + with M + as defined previously;
  • R 61 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 (IX) comprises at least one sulfonate group (0) 2 S(0 , Q + with Q+ as defined previously;
  • dyes of formula (IX) 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 salts:
  • 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.
  • composition used according to the invention may of course comprise a mixture of dyes of formulae (VII), (VII'), (VIII), (VIII'), (IX), ( ⁇ '), (X), ( ⁇ '), (XI), (XII), (XIII) and (XIV).
  • the dye(s) according to the invention are chosen from those of formulae (VII), (VIII), (IX) and (XIII), and mixtures thereof, preferably chosen from those of formula (XIII).
  • the anionic direct dye(s) are chosen from the dyes of formula (XIII), and in particular carmine indigo.
  • the anionic direct dye(s) 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 + ;
  • c) is other than an azo anionic direct dye comprising a 1 ,8-dihydroxynaphthalene-3,5-disulfonate group; in particular, c) are chosen from the following anionic direct dyes:
  • R 7 , R 8 , R 9 , R 10 , R' 7 , R' 8 , R'9 and R' 10 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 -, IVT
  • formula (VII) comprises at least one sulfonate (0) 2 S(0 , Q + or carboxylate (0)C(0 , Q + radical on one of the rings A or B; preferentially alkali metal, alkaline-earth metal or ammonium sulfonate or carboxylate;
  • c) is other than an azo anionic direct dye comprising a 1 ,8-dihydroxynaphthalene-3,5-disulfonate group;
  • 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 29 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, in particular 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;
  • formula (IX) comprises at least one sulfonate group (0) 2 S(0 , Q + ;
  • R53, R54, R55, R56, R57, Res, 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 + representing a cationic counterion; vii) (O)CO -, M + 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;
  • ⁇ Ri and R h which may be identical or different, represent a hydrogen atom or an alkyl group
  • At least one of the groups R53 J R54 J R55 J R56 J R57 J R58 J R59 or R 60 represents a sulfonate group (0) 2 S(0 ⁇ )-, M + or carboxylate group (O)C(O )-, M + .
  • the synthetic direct dye(s) according to the invention are chosen from anionic direct dyes.
  • the anionic direct dye(s) are chosen from the dyes of formulae (VII), (IX) and (XIII), and mixtures thereof. They are preferably chosen from carmine indigo, Acid Blue 62, Acid Red 18 and Acid Black 1 , and mixtures thereof.
  • the total content of anionic direct dyes in the dye composition Cii) is preferably between 0.001 % and 20% by weight, preferably between 0.001 % and 10% by weight, preferably between 0.001 % and 5% by weight, relative to the weight of composition Cii).
  • the direct 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 (Va) and (V'a), the azo dyes (Via) and (Vl'a) and the diazo dyes (Vila) below:
  • Vl'a (Vila) formulae (Va), (V'a), (Via), (Vl'a) and (Vila) with:
  • Het + 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(C 1 -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 (d-C 8 )alkyl, ii) optionally substituted (C C 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-/V-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 (CrC 8 )alkyl, hydroxyl, (di)(Ci-C 8 )(alkyl)amino, (Ci-C 8 )alkoxy or phenyl groups;
  • R a and R b which may be identical or different, represent a hydrogen atom or a (CrC 8 )alkyl group, which is optionally substituted, preferentially with a hydroxyl group;
  • R a and R b represent a hydrogen atom or a (CrC 4 )alkyl group, which is optionally substituted with a hydroxyl group;
  • the cationic dyes are chosen from the polymethine dyes of formulae (Vllla)and (Vlll'a) below:
  • W + representing a cationic heterocyclic or heteroaryl group, particularly comprising a quaternary ammonium optionally substituted with one or more groups (CrC 8 )alkyl 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 (CrC 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
  • Ar' is a (hetero)aryl radical as defined for Ar
  • ⁇ m' represents an integer between 1 and 4 inclusive, and in particular m has the value 1 or 2; more preferentially 1 ;
  • R°, R d which may be identical or different, represent a hydrogen atom or an optionally substituted (CrC 8 )alkyl group, preferentially of CrC 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;
  • Q as defined previously, preferably represents a halide or a mesylate.
  • R 1 representing a (CrC 4 )alkyl group such as methyl
  • R 2 and R 3 which may be identical or different, represent a hydrogen atom or a (C
  • 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)(CrC 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 formula (llla-1 ) and (IVa- 1 ) is chosen from Basic Red 51 , Basic Yellow 87 and Basic Orange 31 or derivatives thereof:
  • the cationic synthetic direct dye(s) are present in the dye composition Cii) in a total content ranging from 0.001% to 10% by weight, preferably from 0.001 % to 5% of the total weight of composition Cii).
  • the synthetic direct dye(s) are present in the dye composition Cii) in a total content ranging from 0.001% to 10% by weight, preferably from 0.001% to 5% of the total weight of composition Cii).
  • the dye composition Cii) comprises one or more dyes of natural origin.
  • the dyes of natural origin may be chosen especially from lawsone, juglone, indigo, isatin, curcumin, spinulosin, apigenidin, orceins, polyphenols or ortho-diphenols (also known as ODPs in the remainder of the description) and any extract rich in ODPs. Use may also be made of extracts or decoctions comprising these natural dyes and especially henna-based and/or indigo-based extracts or poultices.
  • At least one dye of natural origin is chosen from lawsone (or henna), and/or from indigo.
  • the dye(s) are chosen from ortho-diphenol(s) (also known as ODP(s)).
  • the invention relates to one or more ODPs or mixtures of 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 being 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 ODP(s) 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 ODP(s) a) represent a compound of formula (II), or an oligomer, tautomer, optical isomer or geometrical isomer thereof, and also salts or solvates thereof, such as hydrates:
  • 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) (Ci-C 20 )alkyl carboxylate or (CrC 2 o)alkoxycarbonyl, vi) optionally substituted amino, vii) optionally substituted linear or branched (CrC 20 )alkyl, viii) optionally substituted linear or branched (C 2 -C 20 )alkenyl, ix) optionally substituted cycloalkyl, x) (CrC 20 )alkoxy, xi) (Ci-C 2 o)alkoxy(Ci-C 2 o)alkyl, xii) (Ci-C 20 )alkoxyaryl, xiii) aryl which may optionally be substituted, xiv) aryl, xi
  • R 1 - R 2 , R 2 - R 3 or R 3 - R 4 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.
  • 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 d-
  • 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
  • CrC 10 alkyl such as methoxy, ethoxy, propoxy and butoxy
  • alkoxyalkyf radicals are (C 1 -C 2 o)alkoxy(C 1 -C 2 o)alkyl radicals, such as methoxymethyl, ethoxymethyl, methoxyethyl, ethoxyethyl, etc.;
  • cycloalkyr 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;
  • alkyf or "alkenyf 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 )alkyl
  • 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:
  • 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 ODP(s) that are useful in the process of the invention may be natural or synthetic.
  • the natural ODPs are compounds that may be present in nature and that are reproduced by chemical (semi)synthesis.
  • the salts of the ODPs 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 composition comprises, as ingredient c), one or more synthetic ortho-diphenols.
  • the dye composition used in the process for dyeing keratin fibres comprises, as dye, one or more natural ODPs. More particularly, the ODP(s) that may be used in the process of the invention according to a) are in particular:
  • 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 ,
  • chromene or chroman ODP compounds means ODPs which comprise in their structure at least one bicycle of formula (A) below:
  • ODPs of the invention are of formula (A) and are preferably chosen from the dyes of the following formulae: > formula (III), comprising, in its structure, the bicycle of formula (A2):
  • ⁇ 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;
  • R 11 ; R 12 , Ri3, Ri6, Rig and R 20 which may be identical or different, represent a hydrogen atom or a CrC 4 alkyl radical, and
  • Ri4, Ri5, Ri7 and Ri 8 which may be identical or different, represent a hydrogen atom, a hydroxyl radical or a Ci-C 4 alkoxy radical.
  • 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 1 0 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 CrC 2 alkoxy group; iv) a C 1 -C 1 0 alkoxycarbonyl group; v) a (poly)hydroxy(C 2 -C 4 )alkoxy group; vi) an amino group; vii) a 5- or 6-membered heterocycloalkyi 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,
  • glycosyl radical means a radical derived from a monosaccharide or polysaccharide.
  • 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 ODPs of formula (III) for which the radical Ri represents a hydrogen atom or a hydroxyl group.
  • composition according to the invention may comprise one or more ODPs of formula (III) chosen from haematox lin, haematein, brazilin and brazilein.
  • 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 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 ODPs of formula (III) may be used in the form of extracts. Use may be made of the following plant extracts (genus and species): Haematoxylon campechianum, Haematoxylon brasiletto, Caesalpinia echinata, Caesalpinia sappan, Caesalpinia spinosa and Caesalpinia brasiliensis.
  • the extracts are obtained by extracting the various plant parts, for instance the roots, the wood, the bark or the leaves.
  • the natural ODP(s) are of formula (I) and are obtained from logwood, pernambuco wood, sappan wood and Brazil wood.
  • the ODPs are of formula (IV), preferably those for which Rn and R 13 represent an alkyl radical, preferably methyl.
  • R 12 , Rie, 19 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 ODPs that are suitable for use in the present invention is that of the dyes corresponding to formula (II) above for which R 12 , Ri 5 , Ri 6 , R 17 , Rig and R 20 each represent a hydrogen atom.
  • R ⁇ and R 13 each represent a methyl radical and R 14 represents a methoxy radical.
  • the preferred ODPs of this first family include those for which R 18 represents a methoxy radical (santalin B) or a hydroxyl radical (santalin A).
  • a second particularly preferred family of ODPs that are suitable for use in the present invention is that of the dyes corresponding to the 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 2 o, R12, R14, Ris 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 1 8 , R 20 , R12, Ri 4 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 preferred family of ODPs of this second family is that for which R 2 o, R12, R14, Ris, R16 and R 19 represent hydrogen and R 18 represents a hydroxyl radical (santarubin C).
  • the preferred ODP(s) of this second family is 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 ODP(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 ODPs of formula (II), 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.
  • ODP salts 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 ODP(s) of formulae (III) and (IV) included in the composition according to the invention are derived from plant extracts. Use may also be made of mixtures of plant extracts.
  • the natural extracts of ODPs according to the invention may be in the form of powders or liquids. Preferably, the extracts are in powder form.
  • the ODPs of the invention are included among 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 ODPs of the invention are chromenes or chromans and are chosen from haematein, haematoxylin, brazilein, brazilin and santalin A.
  • carboxylate is understood to mean carboxylic acid salt.
  • both forms may be used in the compositions according to the invention, as may the racemates.
  • the natural ODPs 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 ODPs as defined above.
  • the natural ODP(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 and of rose mention may be made of extracts of tea leaves and of rose.
  • extracts of apple, of grape (in particular of grape seed) or extracts of cocoa beans and/or pods mention may be made of 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.
  • 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.
  • ODP(s) of the invention are chosen from:
  • 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) of natural origin are present in the dye composition Cii) in a total content ranging from 0.001% to 10% by weight, preferably from 0.001% to 5% of the total weight of composition Cii).
  • the content in the dye composition(s) containing them is preferably between 0.001 % and 5% by weight of each of the compositions containing them.
  • the content in the composition(s) (preferably the dye composition Cii)) containing the extracts per se is preferably between 0.1 % and 20% by weight of each of these compositions, and better still between 0.5% and 10% by weight of the compositions containing them.
  • the synthetic direct dye(s), and/or the dyes of natural origin, and/or the natural extract(s) used, present in the dye composition Cii), preferably represent from 0.001% to 20% by weight relative to the total weight of the composition(s) containing them.
  • the dye composition Cii) used in the process according to the invention comprises at least one liquid organic compound with a Hansen solubility parameter ⁇ of greater than 0 and less than 16 MPa 1/2 .
  • such a compound is also known as a hydrotropic compound.
  • hydrotropic compound means a compound that is capable of increasing the solubility of hydrophobic compounds in aqueous phases. Said liquid compounds more preferentially have a Hansen solubility parameter ⁇ of between 5 and 15.8 MPa 1/2 , even more preferentially between 8 and 15.8 MPa 1/2 and better still between 8 and and 15 MPa 1/2 .
  • These compounds are liquid at a temperature of 25°C and at atmospheric pressure (760 mmHg; i.e. 1.013 ⁇ 10 5 Pa).
  • the compound(s) with a Hansen solubility parameter value ⁇ as defined previously are, for example, described in the reference publication "Hansen Solubility Parameters: A User's Handbook” by Charles M. Hansen, CRC Press, 2000, pages 167 to 185, or in the publication "Handbook of Solubility Parameters and Other Cohesion Parameters", CRC Press, pages 95 to 121 and pages 177 to 185.
  • This solubility parameter value ⁇ is associated with the formation of hydrogen bonds. It may be recalled that there are three major types of interaction in organic compounds: non-polar interactions, permanent dipole-dipole interactions and interactions of hydrogen bonding type, the latter forming the subject of the parameter defining the hydrotropic compound present in the composition used in accordance with the invention.
  • solubility parameter value ⁇ is usually given for a temperature of 25°C and at atmospheric pressure (760 mmHg, i.e. 1.013 ⁇ 10 5 Pa).
  • liquid organic compounds with a Hansen solubility parameter value ⁇ of greater than 0 and less than 16 MPa 1/2 are nonionic compounds.
  • Said liquid organic compound(s) with a Hansen solubility parameter value ⁇ of greater than 0 and less than 16 MPa 1/2 may be chosen from:
  • alcohol ethers in particular CrC 4 ethers of C 5 -C 30 alcohols, which are preferably saturated, linear or branched, optionally interrupted with one or more non- adjacent ether functions;
  • alkanols bearing an aryl substituent preferably for which the aryl part is C 6 -C 10 , advantageously C 6 , and the alkyl part of the alkanol is C C 4 , this alkyl part possibly ending or being interrupted with a heteroatom, advantageously oxygen or a hydroxyl group, preferably such as benzyl alcohol;
  • R' represents a hydrogen, a linear or branched CrC 8 alkyl, a linear or branched CrC 4 hydroxyalkyi, n being equal to 1 , 2 or 3, and preferably R' represents a hydrogen, a linear or branched CrC 6 alkyl or a linear or branched CrC 2 hydroxyalkyi.
  • lactones that may be mentioned is ⁇ - butyrolactone.
  • said liquid organic compound(s) with a Hansen solubility parameter value ⁇ of greater than 0 and less than 16 MPa 1/2 are chosen from alcohol ethers, aliphatic esters, aromatic ethers and alkanols bearing aryl substituents, and mixtures thereof.
  • said liquid organic compound(s) according to the invention are chosen from dipropylene glycol monomethyl ether acetate, dipropylene glycol methyl ether, dipropylene glycol mono-n-butyl ether (the INCI name of which is PPG-2 Butyl Ether), tripropylene glycol methyl ether, propylene glycol n-butyl ether, propylene glycol n-propyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether and monoethyl ether, 3-phenyl-1 -propanol, 2-phenyl-1 -propanol, benzyl alcohol, benzyloxyethanol and phenoxyethanol, and mixtures of these compounds.
  • liquid organic compound(s) with a Hansen solubility parameter value ⁇ of greater than 0 and less than 16 MPa 1/2 are even more preferentially chosen from alkanols bearing aryl substituents and even more preferentially benzyl alcohol.
  • the liquid organic compound(s) with a Hansen solubility parameter value ⁇ of greater than 0 and less than 16 MPa 1/2 represent a total content ranging from 0.5% to 35% by weight, preferably from 0.5% to 20% by weight and better still from 0.5% to 10% by weight relative to the total weight of the dye composition Cii).
  • composition Ci) also comprises one or more liquid organic compounds with a Hansen solubility parameter value ⁇ of greater than 0 and less than 16 MPa 1/2 .
  • liquid organic compound(s) with a Hansen solubility parameter value ⁇ of greater than 0 and less than 16 MPa 1/2 are preferably chosen from alcohol ethers, aliphatic esters, aromatic ethers and alkanols bearing aryl substituents, and mixtures thereof.
  • liquid organic compound(s) with a Hansen solubility parameter value ⁇ of greater than 0 and less than 16 MPa 1/2 represent a total content ranging from 0.5% to 10% by weight relative to the total weight of composition Ci).
  • the dyeing process also uses one or more chemical oxidizing agents.
  • This embodiment is particularly preferred in the case where the dye composition Cii) used in the process according to the invention comprises at least one oxidation dye.
  • the term "chemical oxidizing agent” means an oxidizing agent other than atmospheric oxygen. More particularly, the dyeing process uses 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 1 10 and US 5 183 901 ; iv) oxidases in the presence of a suitable substrate (for example glucose in the case of glucose oxidase or uric acid with uricase); v) metal peroxides which generate hydrogen peroxide in water, for instance calcium peroxide or magnesium peroxide; vi) perborates; and/or vii) percarbonates.
  • a suitable substrate for example glucose in the case of glucose oxidase or uric acid with uricase
  • metal peroxides which generate hydrogen peroxide in water
  • the composition 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 preferably represent from 0.01% to 12% by weight of chemical oxidizing agents (preferably of hydrogen peroxide) and preferably from 0.2% to 6% relative to the total weight of the composition(s) containing it or them, and even more preferentially from 0.2% to 3% by weight.
  • the process according to the invention uses at least one chemical oxidizing agent, it may be used by extemporaneous addition to one of the compositions, preferably to the dye composition Cii), just before applying said composition to the keratin fibres, or, independently, into a third composition not comprising any dye during an additional oxidation step. According to another embodiment, the process according to the invention does not use any chemical oxidizing agent.
  • the process according to the invention does not use any hydrogen peroxide.
  • the process according to the invention does not use any chemical oxidizing agent.
  • the dye composition Cii) preferably comprises one or more dyes chosen from synthetic direct dyes and/or dyes of natural origin.
  • the dyeing process may use one or more basifying agents f).
  • the basifying agent(s) are in the dye composition with the dye(s) c) as defined previously.
  • bases may be mineral or organic.
  • the bases are alkali metal hydroxides, such as sodium hydroxide, which results in sodium salts.
  • basifying agents are bases that can increase the pH of the composition(s) in which they are present.
  • the basifying agent is a Bronsted, Lowry or Lewis base. It may be mineral or organic.
  • said agent is chosen from i) (bi)carbonates, ii) aqueous ammonia, iii) alkanolamines such as monoethanolamine, diethanolamine, triethanolamine and derivatives thereof, iv) oxyethylenated and/or oxypropylenated ethylenediamines, v) mineral or organic hydroxides, vi) alkali metal silicates such as sodium metasilicates, vii), amino acids, preferably basic amino acids such as arginine, lysine, ornithine, citrulline and histidine, and viii) the compounds of formula (II) below: N - W- N
  • W is a divalent (CrC 8 )alkylene radical optionally substituted with at least one hydroxyl group or at least one (CrC 4 )alkyl radical and/or optionally interrupted with at least one heteroatom, such as oxygen or sulfur, or with an -N(R e )- group;
  • R a , R b , R c , R d and R e which may be identical or different, represent a hydrogen atom or a (C C 4 )alkyl or hydroxy(d-C 4 )alkyl radical; preferably, W represents a propylene radical.
  • 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, quaternary ammonium hydroxides and guanidinium hydroxide.
  • the hydroxide may be formed in situ, for instance guanidine hydroxide, formed by reacting calcium hydroxide with guanidine carbonate.
  • bicarbonates also known as hydrogen carbonates, of the following formulae:
  • R' + , HC0 3 " with R' representing a hydrogen atom, an alkali metal, an ammonium group R" 4 N + - or a phosphonium group R" P + -, where R", which may be identical or different, represents a hydrogen atom or an optionally substituted (CrC 6 )alkyl group, such as hydroxyethyl, and, when R' represents a hydrogen atom, the hydrogen carbonate is then known as dihydrogen carbonate (C0 2 , H 2 0); and
  • the basifying agent is chosen from alkali metal or alkaline-earth metal (bi)carbonates and amino acids such as arginine; preferentially alkali metal (bi)carbonates and amino acids.
  • the basifying agent(s) are chosen from aqueous ammonia and alkanolamines such as monoethanolamine, preferably aqueous ammonia. According to a particularly advantageous embodiment, the basifying agent(s) are chosen from aqueous ammonia, carbonates, bicarbonates and arginine, and mixtures thereof.
  • the basifying agent(s) as defined previously preferably represent from 0.001 % to 10% by weight relative to the weight of the composition(s) containing them, and more particularly from 0.005% to 8% by weight of the composition.
  • compositions used in the process 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.
  • organic solvent means an organic substance that is capable of dissolving or dispersing another substance without chemically modifying it.
  • additional organic solvent other than the liquid organic compound(s) with a Hansen solubility parameter value ⁇ of greater than 0 and less than 16 MPa 1/2
  • additional organic solvent include CrC 4 lower alkanols, such as ethanol and isopropanol; polyols and polyol ethers.
  • composition Ci) and/or the dye composition Cii) comprises at least one d- C 4 lower alkanol, such as ethanol and isopropanol.
  • composition Ci) and/or the dye composition Cii) comprises ethanol.
  • the additional organic solvents may be present in a total content preferably between 1 % and 40% by weight approximately relative to the total weight of the dye composition Cii), and even more preferentially between 5% and 30% by weight approximately.
  • compositions 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 zwitterionic
  • 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) used according to the process 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 foam. pH of the compositions:
  • the pH of at least one of the cosmetic compositions comprising at least one of the ingredients a) to e) is acidic, i.e. it has a pH of 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, preferably between 1 and 3.
  • composition Ci) is acidic (i.e. it has a pH of less than 7.0), preferably has a pH of less than 5.0, particularly at a pH of between 0 and 4, more particularly between 0.5 and 3.5 and preferably between 1 and 3.
  • the pH of the cosmetic composition(s) comprising one or more alkaline agents is alkaline, is greater than 7, preferably between 8 and 12 and more particularly between 8 and 11 inclusive.
  • composition i) containing the titanium salt(s) a) and not containing any basifying agent e) has a pH of less than 7 and preferably of less than 5, in particular a pH between 0 and 4.
  • the pH of these compositions may be adjusted to the desired value by means of basifying agents as defined previously in e) 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, and carboxylic acids, for instance acetic acid.
  • the process for dyeing keratin fibres of the invention uses
  • the process according to the invention uses at least two steps that are different from each other: at least one treating step and at least one dyeing step.
  • the step of treating with composition Ci) is performed after the step of dyeing with composition Cii).
  • the step of treating with composition Ci) is performed before the step of dyeing with composition Cii).
  • the process according to the invention uses an intermediate rinsing step.
  • the intermediate rinsing step iii) is performed between step i) of treating with composition Ci) and step ii) of dyeing with composition Cii), or between step ii) of dyeing with composition Cii) and step i) of treating with composition Ci).
  • the process according to the invention may comprise an intermediate rinsing step iii).
  • said rinsing step is performed between step i) and ii) or between step ii) and i), depending on the order in which said steps i) and ii) are performed.
  • the intermediate rinsing step iii) when it is present, it is performed with a composition comprising water.
  • said intermediate rinsing step iii) is performed exclusively with water, without adding an additional compound.
  • the composition used for performing the rinsing step may also comprise one or more additional compounds.
  • the process according to the invention comprises the implementation of a step of pretreating keratin fibres via the application thereto of a composition Ci), preferably followed by a step of rinsing these fibres, preferably with water, followed by performing a dyeing step via the application of a dye composition Cii) to the fibres, in which:
  • the cosmetic composition Ci) comprises a) one or more titanium salts; in particular, preferably, the titanium atom of said salt(s) is of oxidation state 2, 3 or 4, denoted Ti(ll), Ti(lll) or Ti(IV), preferably Ti(IV); and b) optionally one or more carboxylic acids of formula (I); and
  • the cosmetic composition Cii) comprises c) one or more dyes chosen from oxidation dyes, synthetic direct dyes and dyes of natural origin, preferably chosen from ortho- diphenols; and d) at least one liquid organic compound with a Hansen solubility parameter value ⁇ of greater than 0 and less than 16 MPa 1/2 .
  • the dyeing process according to the invention uses a step of pretreating with composition Ci) preferably followed by a step of rinsing the fibres before the step of dyeing with composition Cii).
  • the process according to the invention comprises the implementation of a step of treating keratin fibres via the application thereto of a dye composition Cii), followed by a step of rinsing these fibres, preferably with water, followed by performing a post-treatment step via the application of a composition Ci) to the fibres,
  • the cosmetic composition Ci) comprises a) one or more titanium salts; in particular, preferably, the titanium atom of said salt(s) is of oxidation state 2, 3 or 4, denoted Ti(ll),
  • the cosmetic composition Cii) comprises c) one or more dyes chosen from oxidation dyes, synthetic direct dyes and dyes of natural origin, preferably chosen from ortho- diphenols; and d) at least one liquid organic compound with a Hansen solubility parameter value ⁇ of greater than 0 and less than 16 MPa 1/2 .
  • composition Ci) of the dyeing process of the invention also comprises b) one or more carboxylic acids of formula (I) below 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 zero 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 (d-C 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.
  • organic titanium salt(s) of composition Ci) of the process of the invention are chosen from those of formulae (l-A), (l-B) or the salts of dihydroxybis(lactato)titaniumlV as defined previously.
  • the dyeing process involves the application to said fibres of composition Ci) as defined previously, followed by rinsing said fibres, preferably with water, followed by the application to said fibres of composition Cii) as defined previously.
  • the leave-on time of composition Ci) as defined previously on the keratin fibres is between 5 minutes and 2 hours, more particularly between 15 minutes and 1 hour, preferably between 30 and 45 minutes.
  • the leave-on time of composition Ci) on the keratin fibres is performed at a temperature of between 20°C and 50°C, more preferentially between room temperature (27°C) and 40°C.
  • compositions i) and ii) or ii) and i) are sequentially applied to the process of the invention.
  • composition Cii) of the dyeing process of the invention also comprises one or more chemical oxidizing agents chosen especially from hydrogen peroxide and one or more hydrogen peroxide-generating systems as defined previously.
  • composition Cii comprises at least one oxidation dye and when it comprises at least one chemical oxidizing agent, it is also known as a "ready-to-use" oxidation dye composition.
  • This ready-to-use dye composition is preferably prepared a few minutes before application, in particular between 1 minute and 20 minutes, more particularly between 5 minutes and 10 minutes before application.
  • the ready-to-use composition is prepared by uniformly mixing the dye composition comprising c) at least one oxidation base as defined previously and optionally at least one coupler as defined previously, with an oxidizing composition comprising d) at least one chemical oxidizing agent as defined previously.
  • the ready-to-use dye composition is preferably applied immediately to the keratin fibres.
  • the leave-on time of composition Cii) and in particular of the ready-to-use dye composition, on the keratin fibres is between 1 minute and 2 hours, preferably between 5 minutes and 1 hour, more preferentially, the leave-on time is from 15 to 30 minutes.
  • the leave-on time of composition Cii) on the keratin fibres is performed at a temperature of between 20°C and 50°C, preferentially between room temperature (27°C) and 40°C.
  • composition Ci is at acidic pH, i.e. less than 7.0, preferably less than 5, in particular at a pH of between 0 and 4 inclusive, more particularly between 0.5 and 3.5 and more preferentially between 1 and 3.
  • composition Ci is at acidic pH, preferably less than 5, in particular at a pH of between 0 and 4 inclusive, more particularly between 0.5 and 3.5 and more preferentially between 1 and 3.
  • the compositions used in the process of the invention are aqueous.
  • the dye composition Cii) comprising the oxidation dye(s) as defined previously also comprises one or more basifying agents f) as defined previously, preferably aqueous ammonia.
  • the pH of the composition comprising one or more basifying agents, preferably composition ii) is between 8 and 12, particularly between 8 and 1 1.
  • the dyeing process of the invention may involve one or more shampoo washes, followed by one or more rinses of the keratin fibres with water, optionally followed by drying via a heat treatment by heating to a temperature of between 30 and 60°C.
  • this operation may be performed using a styling hood, a hairdryer, an infrared ray dispenser and other standard heating appliances.
  • Use may also be made, as a means for both heating and for straightening 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.
  • 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 and 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.
  • Example 1 pretreatment with a composition comprising a titanium salt before dyeing with a natural dye
  • compositions were prepared from the following ingredients in the following proportions, indicated in grams per 100 grams of composition:
  • the pretreatment composition Ci) with the titanium salt was applied to:
  • Composition Ci) is left to stand for 15 minutes on each lock at 40°C, and each of the locks is then rinsed with running tap water according to the same experimental protocol.
  • the dye composition Cii) is then applied to each lock and left to stand for 30 minutes at 40°C.
  • the locks dyed according to the process of the invention were washed with Elvive Multivitamin shampoo, rinsed and then dried under a hood.
  • the colorimetric measurements were performed using a Minolta CM3600D spectrocolorimeter (illuminant D65, angle 10°, specular component included) in the CIELab system.
  • L * represents the lightness. The smaller the value of L * , the darker and more powerful the colouring obtained.
  • the colour build-up is represented by the colour difference ⁇ between the non-dyed lock and the dyed lock: the greater the value of ⁇ , the greater the colour build-up. This value is calculated from the following equation (i):
  • Example 2 pretreatment with a composition comprising a titanium salt before dyeing with a natural dye
  • compositions were prepared from the following ingredients in the following proportions, indicated in grams per 100 grams of composition:
  • the pretreatment composition Ci) with the titanium salt was applied to:
  • composition Ci is left to stand for 15 minutes on each lock at 40°C, and each of the locks is then rinsed with running tap water according to the same experimental protocol.
  • composition Cii) is then applied to each lock and left to stand for 30 minutes at 40°C, and then rinsed out.
  • Composition Ciii) is applied to each of the locks and left to stand for 15 minutes at 40°C.
  • the locks dyed according to the process of the invention and according to the comparative process were washed with Elvive Multivitamin shampoo, rinsed and then dried under a hood.
  • compositions were prepared from the following ingredients in the following proportions, indicated in grams per 100 grams of composition:
  • a dye composition Cii) in accordance with the invention comprising at least one liquid organic compound with a Hansen solubility parameter value ⁇ of greater than 0 and less than 16 MPa 1/2 , and a comparative dye composition Cii') not comprising any liquid organic compound with a Hansen solubility parameter value ⁇ of greater than 0 and less than 16 MPa 1/2 were prepared.
  • the study relates to three types of locks of hair:
  • composition Ci comprising the titanium salt in a proportion of 3.33 g of composition per gram of hair.
  • composition Ci) is left to stand for 20 minutes on each lock at 40°C, and each lock is then rinsed with running tap water and drained dry.
  • the dye composition Cii) is then applied to each of the three locks in a proportion of 3.33 g of composition per gram of hair and left to stand for 45 minutes at 40°C.
  • composition Ci comprising the titanium salt in a proportion of 3.33 g of composition per gram of hair.
  • composition Ci is left to stand for 20 minutes on each lock at 40°C, and each lock is then rinsed with running tap water and drained dry.
  • the comparative dye composition Cii') not comprising any liquid organic compound with a Hansen solubility parameter value ⁇ of greater than 0 and less than 16 MPa 1/2 is then applied to each of the three locks in a proportion of 3.33 g of composition per gram of hair and left to stand for 45 minutes at 40°C.
  • composition Ci is not pretreated with composition Ci), but are only moistened.
  • the dye composition Cii) is then applied to each of the three locks in a proportion of 3.33 g of composition per gram of hair and left to stand for 45 minutes at 40°C.
  • L * represents the lightness. The smaller the value of L * , the darker and more powerful the colouring obtained.
  • the colour build-up is represented by the colour difference ⁇ between the non-dyed lock and the dyed lock: the greater the value of ⁇ , the greater the colour build-up. This value is calculated from the following equation:
  • L * , a * and b * represent the values measured on non-dyed locks of hair and LO * , aO * and bO * represent the values measured on dyed locks of hair.
  • Pretreatment 90 NW Dark blue composition Ci) + rinsing + Caucasian 31.84 46.88
  • compositions were prepared from the following ingredients in the following proportions, indicated in grams per 100 grams of composition:
  • the study relates to locks of natural Caucasian hair containing 90% white hairs (90 NW).
  • composition Ci comprising the titanium salt in a proportion of 3.33 g of composition per gram of hair.
  • composition Ci) is left to stand for 45 minutes on a lock at 40°C, and the lock is then rinsed with running tap water and drained dry.
  • the dye composition Cii) is then applied to the lock in a proportion of 3.33 g of composition per gram of hair and left to stand for 45 minutes at 40°C.
  • the lock is not pretreated with composition Ci), but is only moistened.
  • the dye composition Cii) is then applied to the lock in a proportion of 3.33 g of composition per gram of hair and left to stand for 45 minutes at 40°C. After these leave-on times, the lock is washed with Elvive Multivitamin shampoo, rinsed and then dried under a hood.
  • the colorimetric measurements were performed using a Minolta CM3600D spectrocolorimeter (illuminant D65, angle 10°, specular component included) in the CIELab system.
  • L * represents the lightness. The smaller the value of L * , the darker and more powerful the colouring obtained.
  • the colour build-up is represented by the colour difference ⁇ between the non-dyed lock and the dyed lock: the greater the value of ⁇ , the greater the colour build-up. This value is calculated from the following equation (i):
  • L * , a * and b * represent the values measured on non-dyed locks of hair and L 0 * , a 0 * and b 0 * represent the values measured on dyed locks of hair.
  • Example 5 The following compositions were prepared from the following ingredients in the following proportions, indicated in grams per 100 grams of composition:
  • Pretreatment composition C(i) identical to that of Example 4 (composition Ci) 1 )
  • Dye compositions C(ii) the three dye compositions C3, C4 and C5 below each comprising a different anionic direct dye were prepared:
  • the study relates to locks of natural Caucasian hair containing 90% white hairs (90 NW).
  • composition Ci) 1 comprising the titanium salt in a proportion of 3.33 g of composition per gram of hair.
  • composition Ci) is left to stand for 15 minutes on each lock at 40°C, and each lock is then rinsed with running tap water and drained dry.
  • Each of the dye compositions Cii) 3, 4 and 5 is then applied separately to each of the three locks in a proportion of 3.33 g of composition per gram of hair and left to stand for 15 minutes at 40°C.
  • the three different locks are not pretreated with composition Ci) 1 , but are preferably moistened.
  • the dye compositions Cii) 3, 4 and 5 are then applied separately to each of the three locks in a proportion of 3.33 g of composition per gram of hair and left to stand for 15 minutes at 40°C. According to this dyeing process, there is therefore no step of pretreating the locks with composition Ci) 1.
  • Example 6 The following 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).
  • the locks are rinsed and then dried under a hood.

Landscapes

  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Veterinary Medicine (AREA)
  • Public Health (AREA)
  • Animal Behavior & Ethology (AREA)
  • Birds (AREA)
  • Epidemiology (AREA)
  • Emergency Medicine (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Cosmetics (AREA)
  • Coloring (AREA)

Abstract

The present invention relates to a multi-step process for dyeing keratin fibres, in particular human keratin fibres such as the hair, in which said fibres are treated with: i) at least one step i) of treating said fibres with a cosmetic composition Ci) comprising a) one or more titanium salts and b) optionally one or more particular carboxylic acids; ii) at least one step of dyeing with a cosmetic dye composition Cii) comprising c) one or more dyes chosen from oxidation dyes, synthetic direct dyes and dyes of natural origin, preferably chosen from ortho-diphenols; d) at least one liquid organic compound with a Hansen solubility parameter value δΗ of greater than 0 and less than 16 MPa1/2 and optionally e) one or more chemical oxidizing agents such as hydrogen peroxide or one or more hydrogen peroxide-generating systems; iii) optionally at least one step of intermediate rinsing of said fibres, said step being performed between step i) and ii) or between step ii) and i), depending on the order in which said steps i) and ii) are performed.

Description

Hair dyeing process using a titanium salt, a dye and a particular solvent
The present invention relates to a multi-step process for dyeing keratin fibres, in particular human keratin fibres such as the hair, in which said fibres are treated with:
i) at least one step i) of treating said fibres with a cosmetic composition Ci) comprising a) one or more titanium salts and b) optionally one or more particular carboxylic acids;
ii) at least one step of dyeing with a cosmetic dye composition Cii) comprising c) one or more dyes chosen from oxidation dyes, synthetic direct dyes and dyes of natural origin, preferably chosen from ortho-diphenols; d) at least one liquid organic compound with a Hansen solubility parameter value δΗ of greater than 0 and less than 16 MPa½ and optionally e) one or more chemical oxidizing agents such as hydrogen peroxide or one or more hydrogen peroxide-generating systems, iii) optionally at least one step of intermediate rinsing of said fibres,
said step being performed between step i) and ii) or between step ii) and i), depending on the order in which said steps i) and ii) are performed.
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.
It is sought to increase the efficacy of the reaction of the oxidation dyes used in the course of this process especially in terms of power, colour build-up, persistence of the colour on keratin fibres especially with respect to light, successive washing and sweat, and/or the selectivity of the colour between the root and the end of said fibres. Indeed, such improvement(s) would make it possible in particular to decrease the contents of the oxidation dyes present in the dye compositions, to reduce the leave-on time on keratin fibres and/or to use other dye families which have weak dyeing power but which are capable of exhibiting a good toxicological profile. Furthermore, this would make it possible to afford novel shades or to give colourings that are more persistent with respect to external agents such as light or shampoo washing, or finally to lead to better working qualities such as less staining of the scalp or clothing, or alternatively less colouring of the dye mixture (cleaner) during 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 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.
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 oxidation dyes, direct dyes and/or natural dyes, especially ODPs, in particular 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 and to have suitable working qualities.
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, comprising:
i) at least one step i) of treating said fibres using a cosmetic composition Ci) containing: a) one or more titanium salts: in particular, the titanium atom of said salt(s) is of oxidation state 2, 3 or 4, denoted Ti(ll), Ti(lll) or Ti(IV), preferably Ti(IV);
b) optionally one or more carboxylic acid(s) of formula (I) below or a salt thereof:
Figure imgf000004_0001
in which formula (I):
- A represents a monovalent group when n has the value zero or a polyvalent group when n is greater than or equal to 1 , saturated or unsaturated, cyclic or non-cyclic and aromatic or non-aromatic hydrocarbon-based group comprising from 1 to 50 carbon atoms which is optionally interrupted with one or more heteroatoms and/or optionally substituted, in particular with one or more hydroxyl and/or amino groups; preferably, A represents a monovalent (d-C6)alkyl group or a polyvalent (CrC6)alkylene group optionally substituted with one or more hydroxyl and/or amino groups;
- n represents an integer between 0 and 10 inclusive; preferably, n is between 0 and 5, such as between 0 and 2; and
ii) at least one step of dyeing said fibres using a cosmetic dye composition Cii) containing:
c) one or more dyes chosen from oxidation dyes, synthetic direct dyes and dyes of natural origin, preferably chosen from ortho-diphenols;
d) at least one liquid organic compound with a Hansen solubility parameter value δΗ of greater than 0 and less than 16 MPa½ and
e) optionally one or more chemical oxidizing agents chosen especially from hydrogen peroxide or one or more hydrogen peroxide-generating systems;
iii) optionally at least one step of intermediate rinsing of said fibres,
said step being performed between step i) and ii) or between step ii) and i), depending on the order in which said steps i) and ii) are performed.
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, sebum and light without impairing the fibres. The resistance to perspiration is particularly good, as is the homogeneity of the colour between the root and the end of the fibres. Furthermore, the dyeing process used can induce very satisfactory "build-up" and/or strength 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) titanium salt(s):
The cosmetic composition Ci) used according to the treatment step i) of the process according to the invention comprises at least one or more titanium salts: in particular, the titanium atom of said salt(s) is of oxidation state 2, 3 or 4, denoted Ti(ll), Ti(lll) or Ti(IV), preferably Ti(IV).
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 which may be of oxidation state 1 , 2, 3 or 4, preferably of oxidation state 4, denoted Ti(IV).
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 C C2o 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) a) of the invention are chosen from those of formula (l-A) below:
Figure imgf000006_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;
• M1 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 m1+m2 = n".
Preferentially, the radical A of compound (l-A) as defined previously represents a monovalent (CrC6)alkyl or polyvalent (CrC6)alkylene group optionally substituted with one or more hydroxyl groups or one or more amino groups, preferably 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 a-hydroxy acids and a-amino acids; preferably, the acid is chosen from citric acid, lactic acid, malic acid, tartaric acid, glycolic acid and serine, more preferentially chosen from lactic acid and glycolic acid.
Preferentially, the organic titanium salt(s) a) of the invention are chosen from those of formula (l-B) below:
Figure imgf000006_0002
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)(CrC4)(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 (d-C4)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 (CrC4)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) a) of the dyeing process are dihydroxybis(lactato)titaniumlV salts such as those having the following formula:
Figure imgf000007_0001
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.
According to a particular embodiment of the invention, the titanium salt(s) a) are mineral. They are in particular chosen from titanium halides, titanium sulfates and titanium phosphates. Preferably, the mineral titanium salts are Ti(ll), Ti(lll) or Ti(IV) salts.
Preferably, the mineral titanium salts are Ti(lll) or Ti(IV) salts.
Particularly preferably, the mineral titanium salts are Ti(IV) salts.
According to a preferred embodiment of the invention, the titanium salt(s) a) 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) a) are present in the cosmetic composition i) of the dyeing process according to the invention in a content ranging from 0.001% to 20% by weight relative to the total weight of said composition i) as defined previously.
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. b) one or more carboxylic acids
The cosmetic composition Ci) used according to the treatment step i) of the process according to the invention may also comprise one or more carboxylic acids.
According to an advantageous variant, the cosmetic composition Ci) used according to the treatment step i) of the process according to the invention may also comprise b) one or more carboxylic acids of formula (I) as defined previously.
More preferentially, the carboxylic acid(s) b) are other than the carboxylic acids complexed to the Ti salts, preferably glycolic acid, lactic acid, citric acid or a salt thereof.
In particular, the carboxylic acid(s) b) are 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 a) is lactic acid or the carboxylate salt thereof (lactate), the second acid b) is other than lactic acid or lactate, and may be, for example, glycolic acid.
The acid salts of formula (I) may be salts of organic or mineral bases or basifying agents e) as defined below. Preferably, the salts are sodium, ammonia or potassium salts or salts of organic amines such as alkanolamines.
The acids of formula (I) or salts thereof may be present in composition Ci) in a content ranging from 0.1% to 20% by weight relative to the total weight of said composition Ci). a) dve(s)
In accordance with the present invention, the cosmetic dye composition Cii) used in the dyeing step ii) of the process according to the invention comprises c) one or more dyes chosen from oxidation dyes, synthetic direct dyes and dyes of natural origin, preferably chosen from ortho-diphenols.
Preferably, the total content of dyes in the dye composition Cii) is preferably between 0.001% and 20% by weight, preferably between 0.001 % and 10% by weight, preferably between 0.001% and 5% by weight, relative to the weight of composition Cii). According to a first embodiment of the invention, the dye composition Cii) comprises one or more 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, N- ( ,y-dihydroxypropyl)-para-phenylenediamine, N-(4'-aminophenyl)-para- phenylenediamine, N-phenyl-para-phenylenediamine, 2-p-hydroxyethyloxy-para- phenylenediamine, 2- -acetylaminoethyloxy-para-phenylenediamine, Ν-(β- methoxyethyl)-para-phenylenediamine, 4-aminophenylpyrrolidine, 2-thienyl-para- phenylenediamine, 2-p-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- -hydroxyethyl-para- phenylenediamine, 2- -hydroxyethyloxy-para-phenylenediamine, 2,6-dimethyl-para- phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,3-dimethyl-para- phenylenediamine, N,N-bis( -hydroxyethyl)-para-phenylenediamine, 2-chloro-para- phenylenediamine, 2- -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 N,N'-bis( -hydroxyethyl)-N,N'-bis(4'-aminophenyl)-1 ,3-diaminopropanol, N,N'-bis( - hydroxyethyl)-N,N'-bis(4'-aminophenyl)ethylenediamine, N,N'-bis(4- aminophenyl)tetramethylenediamine, N,N'-bis( -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-( -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-( -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 especially 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.
According to a second embodiment of the invention, the dye composition Cii) comprises one or more synthetic direct dyes.
The synthetic direct dye(s) that may be used in the context of the invention may be fluorescent or non-fluorescent, anionic direct dyes (also known as acid dyes), cationic direct dyes (also known as basic dyes) or neutral direct dyes.
These direct dyes are chosen in particular from those conventionally used in direct dyeing, any commonly used aromatic and/or non-aromatic dyes such as neutral, anionic (also known as acid dyes) or cationic (also known as basic dyes) nitrobenzene direct dyes, neutral, anionic (also known as acid dyes) or cationic (also known as basic dyes) azo direct dyes, neutral, anionic (also known as acid dyes) or cationic (also known as basic dyes) quinone and in particular anthraquinone direct dyes, azine, polyarylmethane such as triarylmethane, indoamine, polymethines such as styryl, porphyrin, metalloporphyrin, phthalocyanine, methine cyanine direct dyes.
In the context of the present invention, the synthetic direct dye(s) are preferably present in a total amount ranging from 0.001% to 20% by weight, preferably from 0.001 % to 10% by weight approximately of the total weight of the dye composition, preferably ranging from 0.005% to 5% by weight relative to the total weight of the dye composition.
According to this second embodiment, the synthetic direct dye is preferably 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 dyes" 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.
Preferably, the anionic direct dye(s) are chosen from acidic nitro direct dyes, acidic azo dyes, acidic azine dyes, acidic triarylmethane dyes, acidic indoamine dyes, acidic anthraquinone dyes and indigoids; 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; and mixtures thereof.
The term "anionic direct dyes" means any direct dye comprising a structure at least one C02R or S03R substituent with R denoting a hydrogen atom or a cation originating from a metal or an amine, or an ammonium ion. The anionic dyes may be chosen from acidic nitro direct dyes, acidic azo dyes, acidic azine dyes, acidic triarylmethane dyes, acidic indoamine dyes, acidic anthraquinone dyes and indigoids; and mixtures thereof.
More particularly, the dye(s) of the invention are chosen from the direct dyes of formula (VI):
Col( >m (Q+)n (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 charge(s): ■ 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 dyes of formula (VI) of the invention are chosen from acidic nitro direct dyes, acidic azo dyes, acidic azine dyes, acidic triarylmethane 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:
c3a) the diaryl anionic azo dyes of formula (VII) or (VII'):
Figure imgf000015_0001
in which formulae (VII) and (VII'):
R7, R8, R9, R10, R'7, R'8, R'9 and R'10, 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) cycloalkyi; 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, an oxygen or sulfur atom, or a divalent radical i) - N(R)- 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 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 (II), 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 117, 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 (VII'), mention may be made of: Acid Red 11 1 , Acid Red 134, Acid yellow 38;
c3b) the pyrazolone anionic azo dyes of formulae (VIII) and (VIII'):
Figure imgf000016_0001
in which formulae (VIII) and (VIII'): • Rii, Ri2 and Ri3, 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-, IVTwith 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 Ri6 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'i6, R'i9 and R'2o, 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 (0)C(0 , 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 an example of dyes of formula (VIII'), mention may be made of Acid Yellow 17; c3c) the anthraquinone dyes of formulae (IX) and (IX'):
Figure imgf000018_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 NR28 29 with R28 and R29, which may be identical or different, representing a hydrogen atom or a group chosen from i) alkyl, ii) polyhydroxyalkyi such as hydroxyethyl, iii) aryl optionally substituted with one or more groups, particularly 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 an example of dyes of formula (IX'), mention may be made of Acid
Black 48; c3d) the nitro dyes of formulae (X) and Χ'):
Figure imgf000019_0001
(X) (Χ')
in which formulae (V) and (V):
R30, R31 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 -, IvT with M+ as defined previously, x) (di)(alkyl)amino, xi) (di)(hydroxyalkyl)amino, xii) heterocycloalkyl such as piperidino, piperazino or morpholino; in particular, R30, R31 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 inclusively;
q represents an integer between 1 and 4 inclusively;
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+;
Figure imgf000019_0002
, 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; c3e) the triarylmethane dyes of formula (XI):
Figure imgf000020_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 -, IvT 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 R41 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; c3f) the xanthene-based dyes of formula (XII):
Figure imgf000021_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 -, IVT 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+;
L' represents an oxygen or sulfur atom or an ammonium group: N+RfRg, with Rf 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) ses 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;
c3g) the indigoid dyes of formula (XIII):
Figure imgf000022_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 (0)C(0 , 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. c3h) the quinoline-based dyes of formula (XIV):
Figure imgf000022_0002
■ R6i 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 R61 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 (IX) comprises at least one sulfonate group (0)2S(0 , Q+ with Q+ as defined previously;
As examples of dyes of formula (IX), 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 salts:
(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
(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- acetamidonaphthalene-3,6-disulfonic acid / Acid Violet 7 / Food Red 1 1 (VII)
(C.I. 18130) Acid Red 135 (VII) (C.I. 19130) Acid Yellow 27(VIII)
(C.I. 19140) Acid Yellow 23 / Food Yellow 4 (VIII)
(C.I. 20170) 4'-(sulfonato-2",4"-dimethyl)bis(2,6-phenylazo)-1 ,3-dihydroxybenzene
/ Acid Orange 24 (VII)
(C.I. 20470) ammonium salt of 1 -amino-2-(4'-nitrophenylazo)-7-phenylazo-8- hydroxynaphthalene-3,6-disulfonic acid / Acid Black 1 (VII)
(C.I. 23266) (4-((4-methylphenyl)sulfonyloxy)phenylazo)-2,2'-dimethyl-4-((2- hydroxy-5,8-disulfonato)naphthylazo)biphenyl / Acid Red 111 (VII')
(C.I. 27755) Food Black 2 (VII)
(C.I. 25440) 1 -(4'-sulfonatophenylazo)-4-((2"-hydroxy-3"-acetylamino-6",8"- disulfonato)naphthylazo)-6-sulfonatonaphthalene (tetrasodium salt) / Food Black 1 (VII)
(C.I. 42090) Acid Blue 9 (XI)
(C.I. 60730) Acid Violet 43 (IX)
(C.I. 61570) Acid Green 25 (IX)
(C.I. 62045) ammonium salt of 1 -amino-4-cyclohexylamino-9,10-anthraquinone-2- sulfonic acid / Acid Blue 62 (IX)
(C.I. 62105) Acid Blue 78 (IX)
(C.I. 14710) ammonium salt of 4-hydroxy-3-((2-methoxyphenyl)azo)-1 - naphthalenesulfonic acid / Acid Red 4 (VII)
2-piperidino 5-nitro benzenesulfonic acid (Χ')
2-(4'-N,N-(2"-hydroxyethyl)amino-2'-nitro)aniline ethane sulfonic acid
(Χ')
4-p-hydroxyethylamino-3-nitrobenzene
sulfonic acid (Χ')
(C.I. 42640) Acid Violet 49 (XII)
(C.I. 42080) Acid Blue 7 (XI)
(C.I. 58005) 1 ,2-dihydroxy-3-sulfoanthraquinone / Mordant Red 3 (IX)
(C.I. 62055) 1 -amino-9,10-dihydro-9,10-dioxo-4-(phenylamino) 2- anthracenesulfonic acid / Acid Blue 25 (IX)
(C.I. 14710) 4-hydroxy-3-((2-methoxyphenyl)azo)-1 -naphthalenesulfonic acid /
Acid Red 4 (VII)
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, BD1 2JBN 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).
The composition used according to the invention may of course comprise a mixture of dyes of formulae (VII), (VII'), (VIII), (VIII'), (IX), (ΙΧ'), (X), (Χ'), (XI), (XII), (XIII) and (XIV).
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), (VIII), (IX) and (XIII), and mixtures thereof, preferably chosen from those of formula (XIII).
Preferably, the anionic direct dye(s) are chosen from the dyes of formula (XIII), and in particular carmine indigo. Preferably, the anionic direct dye(s) are chosen from the direct dyes of formula (VI):
Col( )m (Q+)n (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+;
on condition that when a), b) and c) are present in the same composition, then c) is other than an azo anionic direct dye comprising a 1 ,8-dihydroxynaphthalene-3,5-disulfonate group; in particular, c) are chosen from the following anionic direct dyes:
the diaryl anionic azo dyes of formula (VII):
Figure imgf000026_0001
in which formula (VII):
· R7, R8, R9, R10, R'7, R'8, R'9 and R'10, 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 -, IVTwith 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;
it being understood that:
- formula (VII) comprises at least one sulfonate (0)2S(0 , Q+ or carboxylate (0)C(0 , Q+ radical on one of the rings A or B; preferentially alkali metal, alkaline-earth metal or ammonium sulfonate or carboxylate;
- when a), b) and c) are present in the same composition, then c) is other than an azo anionic direct dye comprising a 1 ,8-dihydroxynaphthalene-3,5-disulfonate group;
the anthraquinone dyes of formula (IX):
Figure imgf000027_0001
in which formula (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 NR28 29 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, in particular 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 formula (IX) comprises at least one sulfonate group (0)2S(0 , Q+;
the indigoid dyes of formula (XIII):
Figure imgf000027_0002
in which formula (XIII):
■ R53, R54, R55, R56, R57, Res, 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+ representing a cationic counterion; vii) (O)CO -, M+ 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;
■ Ri and Rh, which may be identical or different, represent a hydrogen atom or an alkyl group;
it being understood that at least one of the groups R53J R54J R55J R56J R57J R58J R59 or R60, represents a sulfonate group (0)2S(0~)-, M+ or carboxylate group (O)C(O )-, M+.
Preferably, the synthetic direct dye(s) according to the invention are chosen from anionic direct dyes.
Preferably, the anionic direct dye(s) are chosen from the dyes of formulae (VII), (IX) and (XIII), and mixtures thereof. They are preferably chosen from carmine indigo, Acid Blue 62, Acid Red 18 and Acid Black 1 , and mixtures thereof.
According to this embodiment, the total content of anionic direct dyes in the dye composition Cii) is preferably between 0.001 % and 20% by weight, preferably between 0.001 % and 10% by weight, preferably between 0.001 % and 5% by weight, relative to the weight of composition Cii).
According to another particular embodiment of the invention, the direct 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 (Va) and (V'a), the azo dyes (Via) and (Vl'a) and the diazo dyes (Vila) below:
Het+-C(Ra)=N-N(Rb)-Ar, 0/ Het+-N(Ra)-N=C(Rb)-Ar, 0/ Het+-N=N-Ar, Q"
(Va) (V'a) (Via)
Ar+-N=N-Ar", Q" and Het+-N=N-Ar'-N=N-Ar, Q"
(Vl'a) (Vila) formulae (Va), (V'a), (Via), (Vl'a) and (Vila) with:
> Het+ 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(C1-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 (d-C8)alkyl, ii) optionally substituted (C C8)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-/V-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 (CrC8)alkyl, hydroxyl, (di)(Ci-C8)(alkyl)amino, (Ci-C8)alkoxy or phenyl groups;
> Ra and Rb, which may be identical or different, represent a hydrogen atom or a (CrC8)alkyl group, which is optionally substituted, preferentially with a hydroxyl group;
or alternatively the substituent Ra with a substituent of Hef 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 (Vllla)and (Vlll'a) below:
W+-[C(Rc)=C(Rd)]m-Ar', Q" Ar-[C(Rd)=C(Rc)]m-W'+, Q"
(Vllla) (Vlll'a)
formulae (Villa) or (Vlll'a) with:
• W+ representing a cationic heterocyclic or heteroaryl group, particularly comprising a quaternary ammonium optionally substituted with one or more groups (CrC8)alkyl 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 (CrC8)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 has the value 1 or 2; more preferentially 1 ;
• R°, Rd, which may be identical or different, represent a hydrogen atom or an optionally substituted (CrC8)alkyl group, preferentially of CrC4, 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 (Va), (V'a), (Via) and (Vl'a) as defined previously. More particularly those of formulae (Va), (V'a) and (Via) derived from the dyes described in patent applications WO 95/15144, WO 95/01772 and EP-714954. Preferentially, the catio :
Figure imgf000030_0001
(Va-1) (Vla-1)
formulae (Va-1) and (Vla-1) with:
- R1 representing a (CrC4)alkyl group such as methyl;
- R2 and R3, which may be identical or different, represent a hydrogen atom or a (C
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)(CrC8)(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 formula (llla-1 ) and (IVa- 1 ) is chosen from Basic Red 51 , Basic Yellow 87 and Basic Orange 31 or derivatives thereof:
Figure imgf000030_0002
Q- Q- Basic Red 51 Basic Orange 31 Basic Yellow 87 with Q" as defined previously, preferably represents a halide or a mesylate. Preferably, the cationic synthetic direct dye(s) are present in the dye composition Cii) in a total content ranging from 0.001% to 10% by weight, preferably from 0.001 % to 5% of the total weight of composition Cii). Preferably, the synthetic direct dye(s) are present in the dye composition Cii) in a total content ranging from 0.001% to 10% by weight, preferably from 0.001% to 5% of the total weight of composition Cii).
According to a third embodiment of the invention, the dye composition Cii) comprises one or more dyes of natural origin.
The dyes of natural origin may be chosen especially from lawsone, juglone, indigo, isatin, curcumin, spinulosin, apigenidin, orceins, polyphenols or ortho-diphenols (also known as ODPs in the remainder of the description) and any extract rich in ODPs. Use may also be made of extracts or decoctions comprising these natural dyes and especially henna-based and/or indigo-based extracts or poultices.
According to a preferred embodiment of the invention, at least one dye of natural origin is chosen from lawsone (or henna), and/or from indigo.
According to a particularly preferred embodiment of the invention, the dye(s) are chosen from ortho-diphenol(s) (also known as ODP(s)).
The invention relates to one or more ODPs or mixtures of 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 being 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.
The ODP(s) 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.
More particularly, the ODP(s) a) represent a compound of formula (II), or an oligomer, tautomer, optical isomer or geometrical isomer thereof, and also salts or solvates thereof, such as hydrates:
Figure imgf000032_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) (Ci-C20)alkyl carboxylate or (CrC2o)alkoxycarbonyl, vi) optionally substituted amino, vii) optionally substituted linear or branched (CrC20)alkyl, viii) optionally substituted linear or branched (C2-C20)alkenyl, ix) optionally substituted cycloalkyl, x) (CrC20)alkoxy, xi) (Ci-C2o)alkoxy(Ci-C2o)alkyl, xii) (Ci-C20)alkoxyaryl, xiii) aryl which may optionally be substituted, xiv) aryl, xv) substituted aryl, xvi) heterocyclic 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, 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 d-
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
CrC10 alkyl, such as methoxy, ethoxy, propoxy and butoxy;
the "alkoxyalkyf radicals are (C1-C2o)alkoxy(C1-C2o)alkyl radicals, such as methoxymethyl, ethoxymethyl, methoxyethyl, ethoxyethyl, etc.;
the "cycloalkyr 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 "alkyf or "alkenyf 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) a 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 (CrC4)alkyl radical, preferably methyl; x) acylamino (-N(R)-C(0)-R') in which the radical R is a hydrogen atom or a (CrC4)alkyl radical optionally bearing at least one hydroxyl group and the R' radical is a C C2 alkyl radical; a carbamoyl ((R)2N-C(0)-) radical in which the radicals R, which may be identical or different, represent a hydrogen atom or a (Ci-C4)alkyl radical optionally bearing at least one hydroxyl group; xi) alkylsulfonylamino (R'-S(0)2-N(R)-) in which the radical R represents a hydrogen atom or a (CrC4)alkyl radical optionally bearing at least one hydroxyl group and the R' radical represents a (CrC4)alkyl radical, a phenyl radical; xii) aminosulfonyl ((R)2N- S(0)2-) in which the radicals R, 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, (d-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) C1-C2 alkoxy; v) C1-C10 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 (CrC4)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 C1-C3 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) 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 CrC4 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 radicals R, 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 CrC4 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.
The ODP(s) that are useful in the process of the invention may be natural or synthetic. Among the natural ODPs are compounds that may be present in nature and that are reproduced by chemical (semi)synthesis.
The salts of the ODPs 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 a particular embodiment of the invention, the composition comprises, as ingredient c), one or more synthetic ortho-diphenols.
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 ODPs. More particularly, the ODP(s) that may be used in the process of the invention according to a) are in particular:
- flavanols, for instance 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 ,
- chroman and chromene compounds,
- proanthocyanins,
- tannic acid,
- ellagic acid,
- and mixtures of the preceding compounds.
According to the invention, the term "chromene or chroman" ODP compounds means ODPs which comprise in their structure at least one bicycle of formula (A) below:
Figure imgf000036_0001
(A)
the endocyclic bond — representing a carbon-carbon single bond or else a carbon- carbon double bond, as illustrated by formula (A1) below, denoting the chromene family, and formula (A2) below, denoting the chroman family:
Figure imgf000036_0002
(A1) (A2)
More particularly, the ODPs of the invention are of formula (A) and are preferably chosen from the dyes of the following formulae: > formula (III), comprising, in its structure, the bicycle of formula (A2):
Figure imgf000037_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 (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 ou 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 (A1):
Figure imgf000037_0002
(IV)
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):
• R11 ; R12, Ri3, Ri6, Rig and R20, which may be identical or different, represent a hydrogen atom or a CrC4 alkyl radical, and
• Ri4, Ri5, Ri7 and Ri8, which may be identical or different, represent a hydrogen atom, a hydroxyl radical or a Ci-C4 alkoxy radical.
As regards the ortho-diphenols of formula (III) as defined above, they may be found in two tautomeric forms denoted (Ilia) and (1Mb):
Figure imgf000038_0001
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 CrC2 alkoxy group; iv) a C1-C10 alkoxycarbonyl group; v) a (poly)hydroxy(C2-C4)alkoxy group; vi) an amino group; vii) a 5- or 6-membered heterocycloalkyi 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 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, preferably imidazolium, optionally substituted with a (d-C4)alkyl radical, preferably methyl; x) an acylamino (-NR-COR') radical in which the radical R 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; xi) a carbamoyl ((R)2N-CO-) radical in which the radicals R, which may be identical or different, represent a hydrogen atom or a d-C4 alkyl radical optionally bearing at least one hydroxyl group; xii) an alkylsulfonylamino (R'S02-NR-) radical in which the radical R represents a hydrogen atom or a CrC4 alkyl radical optionally bearing at least one hydroxyl group and the R' radical represents a C C4 alkyl radical, a phenyl radical; xiii) an aminosulfonyl ((R)2N-S02-) radical 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; 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.
The term "glycosyl radical" means a radical derived from a monosaccharide or polysaccharide.
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 ODPs of formula (III) for which the radical Ri represents a hydrogen atom or a hydroxyl group.
More particularly, the composition according to the invention may comprise one or more ODPs of formula (III) chosen from haematox lin, haematein, brazilin and brazilein.
Figure imgf000039_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 imgf000040_0001
Brazilein
Among the ODPs 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 ODPs of formula (III) may be used in the form of extracts. Use may be made of the following plant extracts (genus and species): Haematoxylon campechianum, Haematoxylon brasiletto, Caesalpinia echinata, Caesalpinia sappan, Caesalpinia spinosa and Caesalpinia brasiliensis.
The extracts are obtained by extracting the various plant parts, for instance the roots, the wood, the bark or the leaves.
According to one particular embodiment of the invention, the natural ODP(s) are of formula (I) and are obtained from logwood, pernambuco wood, sappan wood and Brazil wood.
According to a particular embodiment of the invention, the ODPs are of formula (IV), preferably those for which Rn and R13 represent an alkyl radical, preferably methyl.
Preferably, R12, Rie, 19 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 ODPs that are suitable for use in the present invention is that of the dyes corresponding to formula (II) above for which R12, Ri5, Ri6, R17, Rig and R20 each represent a hydrogen atom. R^ and R13 each represent a methyl radical and R14 represents a methoxy radical.
The preferred ODPs of this first family include those for which R18 represents a methoxy radical (santalin B) or a hydroxyl radical (santalin A).
A second particularly preferred family of ODPs that are suitable for use in the present invention is that of the dyes corresponding to the 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, R2o, R12, R14, Ris 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 R1 8, R20, R12, Ri4 and R1 6 represent a hydrogen atom, R15 represents a methoxy radical and R19 represents a methyl radical (santarubin B).
A third preferred family of ODPs of this second family is that for which R2o, R12, R14, Ris, R16 and R19 represent hydrogen and R18 represents a hydroxyl radical (santarubin C).
The preferred ODP(s) of this second family is 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 ODP(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 ODPs of formula (II), 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 ODP salts 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.
Preferably, the ODP(s) of formulae (III) and (IV) included in the composition according to the invention are derived from plant extracts. Use may also be made of mixtures of plant extracts. The natural extracts of ODPs according to the invention may be in the form of powders or liquids. Preferably, the extracts are in powder form.
In particular, the ODPs of the invention are included among 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 ODPs of the invention are chromenes or chromans and are chosen from haematein, haematoxylin, brazilein, brazilin and santalin A.
The term " carboxylate" is understood to mean 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 ODPs 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 ODPs as defined above.
Preferably, the natural ODP(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.
Among the plant extracts, mention may be made of extracts of tea leaves 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.
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.
More preferentially, the ODP(s) of the invention are chosen from:
- haematein, brazilein, gallic acid or tannic acid, when the dyeing process does not use a chemical oxidizing agent;
or else
- haematoxylin, brazilin, gallic acid or tannic acid, when the dyeing process uses a chemical oxidizing agent.
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.
Preferably, the dye(s) of natural origin are present in the dye composition Cii) in a total content ranging from 0.001% to 10% by weight, preferably from 0.001% to 5% of the total weight of composition Cii).
As regards the pure dyes, especially the pure ODPs, the content in the dye composition(s) containing them (preferably the dye composition Cii)) is preferably between 0.001 % and 5% by weight of each of the compositions containing them.
As regards the extracts, the content in the composition(s) (preferably the dye composition Cii)) containing the extracts per se is preferably between 0.1 % and 20% by weight of each of these compositions, and better still between 0.5% and 10% by weight of the compositions containing them.
According to the invention, the synthetic direct dye(s), and/or the dyes of natural origin, and/or the natural extract(s) used, present in the dye composition Cii), preferably represent from 0.001% to 20% by weight relative to the total weight of the composition(s) containing them. d) Liquid organic compound(s) with a Hansen solubility parameter value δΗ of greater than 0 and less than 16 MPa½.
The dye composition Cii) used in the process according to the invention comprises at least one liquid organic compound with a Hansen solubility parameter δΗ of greater than 0 and less than 16 MPa1/2.
In the context of the present invention, such a compound is also known as a hydrotropic compound.
For the purposes of the present invention, the term "hydrotropic compound" means a compound that is capable of increasing the solubility of hydrophobic compounds in aqueous phases. Said liquid compounds more preferentially have a Hansen solubility parameter δΗ of between 5 and 15.8 MPa1/2, even more preferentially between 8 and 15.8 MPa1/2 and better still between 8 and and 15 MPa1/2.
These compounds are liquid at a temperature of 25°C and at atmospheric pressure (760 mmHg; i.e. 1.013 χ 105 Pa).
The compound(s) with a Hansen solubility parameter value δΗ as defined previously are, for example, described in the reference publication "Hansen Solubility Parameters: A User's Handbook" by Charles M. Hansen, CRC Press, 2000, pages 167 to 185, or in the publication "Handbook of Solubility Parameters and Other Cohesion Parameters", CRC Press, pages 95 to 121 and pages 177 to 185.
This solubility parameter value δΗ is associated with the formation of hydrogen bonds. It may be recalled that there are three major types of interaction in organic compounds: non-polar interactions, permanent dipole-dipole interactions and interactions of hydrogen bonding type, the latter forming the subject of the parameter defining the hydrotropic compound present in the composition used in accordance with the invention.
In particular, the book "Handbook of Solubility Parameters and Other Cohesion Parameters", CRC Press, pages 95 to 121 and pages 177 to 185, gives the equation δΗ = (∑-zUh/V)1/2
in which zUh (in J.mol"1) describes the contributions of the functional group considered in the solubility parameters associated with the hydrogen bonds (values in Table 14, page 183), this parameter zUh also being described in the book "The relation between surface tension and solubility parameter in liquids", Bagda, E, Farbe Lack, 84, 212, 1978; and V is the volume of the molecule.
It should be noted that the solubility parameter value δΗ is usually given for a temperature of 25°C and at atmospheric pressure (760 mmHg, i.e. 1.013 χ 105 Pa).
In particular, the liquid organic compounds with a Hansen solubility parameter value δΗ of greater than 0 and less than 16 MPa1/2 are nonionic compounds.
Said liquid organic compound(s) with a Hansen solubility parameter value δΗ of greater than 0 and less than 16 MPa1/2 may be chosen from:
• alcohol ethers, in particular CrC4 ethers of C5-C30 alcohols, which are preferably saturated, linear or branched, optionally interrupted with one or more non- adjacent ether functions;
• aliphatic esters of CrC4 carboxylic acids and of C3-C10 monoalcohols or polyhydroxylated, interrupted with one or more non-adjacent ether functions;
• aromatic ethers, in particular of C6-C10, of a CrC6 alkyl optionally bearing a hydroxyl group, • (C6-C10)aryl(C1-C6) alkyl ethers, of a CrC6 alkyl optionally bearing a hydroxyl group,
• alkanols bearing an aryl substituent, preferably for which the aryl part is C6-C10, advantageously C6, and the alkyl part of the alkanol is C C4, this alkyl part possibly ending or being interrupted with a heteroatom, advantageously oxygen or a hydroxyl group, preferably such as benzyl alcohol;
• lactones preferably of formula (iii), and also mixtures thereof, with:
Figure imgf000045_0001
in which R' represents a hydrogen, a linear or branched CrC8 alkyl, a linear or branched CrC4 hydroxyalkyi, n being equal to 1 , 2 or 3, and preferably R' represents a hydrogen, a linear or branched CrC6 alkyl or a linear or branched CrC2 hydroxyalkyi.
A particularly advantageous example of lactones that may be mentioned is γ- butyrolactone.
Mention may also be made of certain liquid alkanols, for instance 1 -pentanol.
Preferably, said liquid organic compound(s) with a Hansen solubility parameter value δΗ of greater than 0 and less than 16 MPa1/2 are chosen from alcohol ethers, aliphatic esters, aromatic ethers and alkanols bearing aryl substituents, and mixtures thereof.
Even more preferentially, said liquid organic compound(s) according to the invention are chosen from dipropylene glycol monomethyl ether acetate, dipropylene glycol methyl ether, dipropylene glycol mono-n-butyl ether (the INCI name of which is PPG-2 Butyl Ether), tripropylene glycol methyl ether, propylene glycol n-butyl ether, propylene glycol n-propyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether and monoethyl ether, 3-phenyl-1 -propanol, 2-phenyl-1 -propanol, benzyl alcohol, benzyloxyethanol and phenoxyethanol, and mixtures of these compounds.
The liquid organic compound(s) with a Hansen solubility parameter value δΗ of greater than 0 and less than 16 MPa1/2 are even more preferentially chosen from alkanols bearing aryl substituents and even more preferentially benzyl alcohol.
Preferably, the liquid organic compound(s) with a Hansen solubility parameter value δΗ of greater than 0 and less than 16 MPa1/2 represent a total content ranging from 0.5% to 35% by weight, preferably from 0.5% to 20% by weight and better still from 0.5% to 10% by weight relative to the total weight of the dye composition Cii). In one variant of the invention, composition Ci) also comprises one or more liquid organic compounds with a Hansen solubility parameter value δΗ of greater than 0 and less than 16 MPa1/2.
The preferences concerning the nature of the liquid organic compound with a Hansen solubility parameter value δΗ of greater than 0 and less than 16 MPa1/2 are the same as those indicated in the context of composition Cii).
In particular, the liquid organic compound(s) with a Hansen solubility parameter value δΗ of greater than 0 and less than 16 MPa1/2 are preferably chosen from alcohol ethers, aliphatic esters, aromatic ethers and alkanols bearing aryl substituents, and mixtures thereof.
Preferably, the liquid organic compound(s) with a Hansen solubility parameter value δΗ of greater than 0 and less than 16 MPa1/2 represent a total content ranging from 0.1% to 35% by weight, preferably from 0.1% to 20% by weight and better still from 0.5% to 10% by weight relative to the total weight of composition Ci).
Preferably, the liquid organic compound(s) with a Hansen solubility parameter value δΗ of greater than 0 and less than 16 MPa1/2 represent a total content ranging from 0.5% to 10% by weight relative to the total weight of composition Ci). e) chemical oxidizing agent (s)
According to a particular embodiment of the invention, the dyeing process also uses one or more chemical oxidizing agents.
This embodiment is particularly preferred in the case where the dye composition Cii) used in the process according to the invention comprises at least one oxidation dye.
The term "chemical oxidizing agent" means an oxidizing agent other than atmospheric oxygen. More particularly, the dyeing process uses 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 1 10 and US 5 183 901 ; iv) oxidases in the presence of a suitable substrate (for example glucose in the case of glucose oxidase or uric acid with uricase); v) metal peroxides which generate hydrogen peroxide in water, for instance calcium peroxide or magnesium peroxide; vi) perborates; and/or vii) percarbonates.
According to a preferred embodiment of the invention, the composition 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 preferably represent from 0.01% to 12% by weight of chemical oxidizing agents (preferably of hydrogen peroxide) and preferably from 0.2% to 6% relative to the total weight of the composition(s) containing it or them, and even more preferentially from 0.2% to 3% by weight.
When the process according to the invention uses at least one chemical oxidizing agent, it may be used by extemporaneous addition to one of the compositions, preferably to the dye composition Cii), just before applying said composition to the keratin fibres, or, independently, into a third composition not comprising any dye during an additional oxidation step. According to another embodiment, the process according to the invention does not use any chemical oxidizing agent.
According to a particular embodiment of the invention, the process according to the invention does not use any hydrogen peroxide. Preferably, according to this embodiment, the process according to the invention does not use any chemical oxidizing agent.
According to this embodiment, the dye composition Cii) preferably comprises one or more dyes chosen from synthetic direct dyes and/or dyes of natural origin.
f) basifying agent(s)
According to a particular embodiment of the invention, the dyeing process may use one or more basifying agents f). Preferably, the basifying agent(s) are in the dye composition with the dye(s) c) as defined previously.
The term "basifying agents" means that the bases as defined for e) may be mineral or organic. In particular, the bases are alkali metal hydroxides, such as sodium hydroxide, which results in sodium salts.
These basifying agents are bases that can increase the pH of the composition(s) in which they are present. The basifying agent is a Bronsted, Lowry or Lewis base. It may be mineral or organic.
Particularly, said agent is chosen from i) (bi)carbonates, ii) aqueous ammonia, iii) alkanolamines such as monoethanolamine, diethanolamine, triethanolamine and derivatives thereof, iv) oxyethylenated and/or oxypropylenated ethylenediamines, v) mineral or organic hydroxides, vi) alkali metal silicates such as sodium metasilicates, vii), amino acids, preferably basic amino acids such as arginine, lysine, ornithine, citrulline and histidine, and viii) the compounds of formula (II) below: N - W- N
/ \
Rc Rd (M)
in which formula (II) W is a divalent (CrC8)alkylene radical optionally substituted with at least one hydroxyl group or at least one (CrC4)alkyl radical and/or optionally interrupted with at least one heteroatom, such as oxygen or sulfur, or with an -N(Re)- group; Ra, Rb, Rc, Rd and Re, which may be identical or different, represent a hydrogen atom or a (C C4)alkyl or hydroxy(d-C4)alkyl radical; preferably, W represents a propylene radical. 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, quaternary ammonium hydroxides and guanidinium hydroxide.
The hydroxide may be formed in situ, for instance guanidine hydroxide, formed by reacting calcium hydroxide with guanidine carbonate.
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, representing 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'+, HC03 ", with R' representing a hydrogen atom, an alkali metal, an ammonium group R"4N+- or a phosphonium group R" P+-, where R", which may be identical or different, represents a hydrogen atom or an optionally substituted (CrC6)alkyl group, such as hydroxyethyl, and, when R' represents a hydrogen atom, the hydrogen carbonate is then known as dihydrogen carbonate (C02, H20); and
> Met'2+ (HC03 ~)2, with Met' representing an alkaline-earth metal.
More particularly, the basifying agent is chosen from alkali metal or alkaline-earth metal (bi)carbonates and amino acids such as arginine; preferentially alkali metal (bi)carbonates and amino acids.
Mention may be made of Na, K, Mg and Ca carbonates or hydrogen carbonates and mixtures thereof, and in particular sodium hydrogen carbonate. These hydrogen carbonates 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, the basifying agent(s) are chosen from aqueous ammonia and alkanolamines such as monoethanolamine, preferably aqueous ammonia. According to a particularly advantageous embodiment, the basifying agent(s) are chosen from aqueous ammonia, carbonates, bicarbonates and arginine, and mixtures thereof.
The basifying agent(s) as defined previously preferably represent from 0.001 % to 10% by weight relative to the weight of the composition(s) containing them, and more particularly from 0.005% to 8% by weight of the composition.
The compositions: The compositions used in the process 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.
Additional organic solvents:
As additional organic solvent (other than the liquid organic compound(s) with a Hansen solubility parameter value δΗ of greater than 0 and less than 16 MPa1/2), examples that may be mentioned include CrC4 lower alkanols, such as ethanol and isopropanol; polyols and polyol ethers.
Preferably, composition Ci) and/or the dye composition Cii) comprises at least one d- C4 lower alkanol, such as ethanol and isopropanol.
Preferably, composition Ci) and/or the dye composition Cii) comprises ethanol.
The additional organic solvents (other than the liquid organic compound(s) with a Hansen solubility parameter value δΗ of greater than 0 and less than 16 MPa1/2) may be present in a total content preferably between 1 % and 40% by weight approximately relative to the total weight of the dye composition Cii), and even more preferentially between 5% and 30% by weight approximately.
The adjuvants:
The compositions 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.
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) used according to the process 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 foam. pH of the compositions:
Preferably, the pH of at least one of the cosmetic compositions comprising at least one of the ingredients a) to e) is acidic, i.e. it has a pH of 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, preferably between 1 and 3. Preferably, composition Ci) is acidic (i.e. it has a pH of less than 7.0), preferably has a pH of less than 5.0, particularly at a pH of between 0 and 4, more particularly between 0.5 and 3.5 and preferably between 1 and 3.
According to one embodiment, the pH of the cosmetic composition(s) comprising one or more alkaline agents is alkaline, is greater than 7, preferably between 8 and 12 and more particularly between 8 and 11 inclusive.
According to a particular embodiment of the invention, composition i) containing the titanium salt(s) a) and not containing any basifying agent e) has a pH of less than 7 and preferably of less than 5, in particular a pH between 0 and 4.
The pH of these compositions may be adjusted to the desired value by means of basifying agents as defined previously in e) 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, and carboxylic acids, for instance acetic acid.
Multi-step dyeing process
The process for dyeing keratin fibres of the invention uses
i) at least one step of treating with a composition Ci) as defined previously, ii) at least one step of dyeing with a dye composition Cii) as defined previously, iii) and optionally at least one intermediate rinsing step, said step being performed between step i) and ii) or between step ii) and i), depending on the order in which said steps i) and ii) are performed. Thus, the process according to the invention uses at least two steps that are different from each other: at least one treating step and at least one dyeing step.
According to a first embodiment of the invention, the step of treating with composition Ci) is performed after the step of dyeing with composition Cii).
According to a second embodiment of the invention, the step of treating with composition Ci) is performed before the step of dyeing with composition Cii).
Preferably, according to one or another of these embodiments, the process according to the invention uses an intermediate rinsing step. Thus, the intermediate rinsing step iii) is performed between step i) of treating with composition Ci) and step ii) of dyeing with composition Cii), or between step ii) of dyeing with composition Cii) and step i) of treating with composition Ci).
Intermediate rinsing step
According to a preferred embodiment of the invention, the process according to the invention may comprise an intermediate rinsing step iii).
According to this embodiment, said rinsing step is performed between step i) and ii) or between step ii) and i), depending on the order in which said steps i) and ii) are performed.
Particularly preferably, when the intermediate rinsing step iii) is present, it is performed with a composition comprising water. In particular, according to a preferred embodiment of the invention, said intermediate rinsing step iii) is performed exclusively with water, without adding an additional compound. According to another embodiment, the composition used for performing the rinsing step may also comprise one or more additional compounds. This means that, according to a first particular embodiment of the invention, the process according to the invention comprises the implementation of a step of pretreating keratin fibres via the application thereto of a composition Ci), preferably followed by a step of rinsing these fibres, preferably with water, followed by performing a dyeing step via the application of a dye composition Cii) to the fibres, in which:
- the cosmetic composition Ci) comprises a) one or more titanium salts; in particular, preferably, the titanium atom of said salt(s) is of oxidation state 2, 3 or 4, denoted Ti(ll), Ti(lll) or Ti(IV), preferably Ti(IV); and b) optionally one or more carboxylic acids of formula (I); and
- the cosmetic composition Cii) comprises c) one or more dyes chosen from oxidation dyes, synthetic direct dyes and dyes of natural origin, preferably chosen from ortho- diphenols; and d) at least one liquid organic compound with a Hansen solubility parameter value δΗ of greater than 0 and less than 16 MPa1/2.
In other words, according to this embodiment, the dyeing process according to the invention uses a step of pretreating with composition Ci) preferably followed by a step of rinsing the fibres before the step of dyeing with composition Cii).
According to a second embodiment of the invention, the process according to the invention comprises the implementation of a step of treating keratin fibres via the application thereto of a dye composition Cii), followed by a step of rinsing these fibres, preferably with water, followed by performing a post-treatment step via the application of a composition Ci) to the fibres,
in which:
- the cosmetic composition Ci) comprises a) one or more titanium salts; in particular, preferably, the titanium atom of said salt(s) is of oxidation state 2, 3 or 4, denoted Ti(ll),
Ti(lll) or Ti(IV), preferably Ti(IV); and b) optionally one or more carboxylic acids of formula (I); and
- the cosmetic composition Cii) comprises c) one or more dyes chosen from oxidation dyes, synthetic direct dyes and dyes of natural origin, preferably chosen from ortho- diphenols; and d) at least one liquid organic compound with a Hansen solubility parameter value δΗ of greater than 0 and less than 16 MPa1/2.
According to a particular embodiment, composition Ci) of the dyeing process of the invention also comprises b) one or more carboxylic acids of formula (I) below or a salt thereof;
Figure imgf000053_0001
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 zero 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 (d-C6)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.
Preferentially, the organic titanium salt(s) of composition Ci) of the process of the invention are chosen from those of formulae (l-A), (l-B) or the salts of dihydroxybis(lactato)titaniumlV as defined previously.
According to a preferred embodiment of the invention, the dyeing process involves the application to said fibres of composition Ci) as defined previously, followed by rinsing said fibres, preferably with water, followed by the application to said fibres of composition Cii) as defined previously.
In particular, in the dyeing process of the invention, the leave-on time of composition Ci) as defined previously on the keratin fibres is between 5 minutes and 2 hours, more particularly between 15 minutes and 1 hour, preferably between 30 and 45 minutes. Preferentially, the leave-on time of composition Ci) on the keratin fibres is performed at a temperature of between 20°C and 50°C, more preferentially between room temperature (27°C) and 40°C.
Between the application of compositions i) and ii) or ii) and i), at least one rinsing step is performed in the process of the invention.
According to a particular embodiment, composition Cii) of the dyeing process of the invention also comprises one or more chemical oxidizing agents chosen especially from hydrogen peroxide and one or more hydrogen peroxide-generating systems as defined previously.
When composition Cii) comprises at least one oxidation dye and when it comprises at least one chemical oxidizing agent, it is also known as a "ready-to-use" oxidation dye composition. This ready-to-use dye composition is preferably prepared a few minutes before application, in particular between 1 minute and 20 minutes, more particularly between 5 minutes and 10 minutes before application. The ready-to-use composition is prepared by uniformly mixing the dye composition comprising c) at least one oxidation base as defined previously and optionally at least one coupler as defined previously, with an oxidizing composition comprising d) at least one chemical oxidizing agent as defined previously.
Once the ready-to-use dye composition has been prepared, it is preferably applied immediately to the keratin fibres. The leave-on time of composition Cii) and in particular of the ready-to-use dye composition, on the keratin fibres is between 1 minute and 2 hours, preferably between 5 minutes and 1 hour, more preferentially, the leave-on time is from 15 to 30 minutes. Preferentially, the leave-on time of composition Cii) on the keratin fibres is performed at a temperature of between 20°C and 50°C, preferentially between room temperature (27°C) and 40°C.
Preferably, at least one of the compositions used in the dyeing process is at acidic pH, i.e. less than 7.0, preferably less than 5, in particular at a pH of between 0 and 4 inclusive, more particularly between 0.5 and 3.5 and more preferentially between 1 and 3. In particular, composition Ci) according to the invention is at acidic pH, preferably less than 5, in particular at a pH of between 0 and 4 inclusive, more particularly between 0.5 and 3.5 and more preferentially between 1 and 3.
Preferably, the compositions used in the process of the invention are aqueous. According to a particular embodiment of the invention, the dye composition Cii) comprising the oxidation dye(s) as defined previously also comprises one or more basifying agents f) as defined previously, preferably aqueous ammonia. In particular, the pH of the composition comprising one or more basifying agents, preferably composition ii), is between 8 and 12, particularly between 8 and 1 1.
After applying the compositions Ci), optionally rinsing the keratin fibres and applying composition Cii), and vice versa, the dyeing process of the invention may involve one or more shampoo washes, followed by one or more rinses of the keratin fibres with water, optionally followed by drying via 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, a hairdryer, an infrared ray dispenser and other standard heating appliances.
Use may also be made, as a means for both heating and for straightening 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 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 and 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.
The examples that follow serve to illustrate the invention without, however, being limiting in nature.
Example 1 : pretreatment with a composition comprising a titanium salt before dyeing with a natural dye
The following compositions were prepared from the following ingredients in the following proportions, indicated in grams per 100 grams of composition:
Pretreatment composition Ci):
Figure imgf000055_0001
Dye composition Cii):
Figure imgf000055_0002
Water qs 100
The pretreatment composition Ci) with the titanium salt was applied to:
- a lock of natural Caucasian hair containing 90% white hairs (90 NW);
- a lock of permanent-waved white hairs (90 PWW);
- a lock of natural Chinese hair containing 100% white hairs (100 NW).
During this pretreatment step, a bath ratio of 1 gram of composition i) per 1 gram of treated lock is adhered to.
Composition Ci) is left to stand for 15 minutes on each lock at 40°C, and each of the locks is then rinsed with running tap water according to the same experimental protocol. The dye composition Cii) is then applied to each lock and left to stand for 30 minutes at 40°C.
After these leave-on times, the locks dyed according to the process of the invention were washed with Elvive Multivitamin shampoo, rinsed and then dried under a hood.
Dyeing results
Very intensely coloured black locks were obtained with the locks of hair that had undergone the pretreatment with the titanium salts, which is confirmed by the colorimetric measurements below. In addition, it is seen that the colouring is very homogeneous with the process according to the invention.
These results are confirmed with the L, a and b spectrophotometer measurements. The colorimetric measurements were performed using a Minolta CM3600D spectrocolorimeter (illuminant D65, angle 10°, specular component included) in the CIELab system.
In this system, L* represents the lightness. The smaller the value of L*, the darker and more powerful the colouring obtained.
The colour build-up is represented by the colour difference ΔΕ between the non-dyed lock and the dyed lock: the greater the value of ΔΕ, the greater the colour build-up. This value is calculated from the following equation (i):
AE = (L*-Lo *)2 +(a*-a0 *)2 +(b*-b0 *)2
(i)
In the equation i), L*, a* and b* represent the values measured on non-dyed locks of hair and l_o*, a0 * and b0 * represent the values measured on dyed locks of hair. The results L and ΔΕ of colour build-up are collated in the table below:
Intense blueish-black colourings were obtained, as shown by the colorimetric measurements:
Figure imgf000057_0002
It is seen from the above results that very intense colouring was obtained with the dyeing process according to the invention, since the value of L decreases greatly. Furthermore, good colour build-up ΔΕ is obtained.
Example 2: pretreatment with a composition comprising a titanium salt before dyeing with a natural dye
The following compositions were prepared from the following ingredients in the following proportions, indicated in grams per 100 grams of composition:
Pretreatment composition Ci):
Figure imgf000057_0001
Dye compositi
Figure imgf000058_0001
The pretreatment composition Ci) with the titanium salt was applied to:
- a lock of natural Caucasian hair containing 90% white hairs (90 NW);
- a lock of permanent-waved white hairs (90 PWW);
- a lock of natural Chinese hair containing 100% white hairs (100 NW). During this pretreatment step, a bath ratio of 10 grams of composition i) per 1 gram of treated lock is adhered to. Composition Ci) is left to stand for 15 minutes on each lock at 40°C, and each of the locks is then rinsed with running tap water according to the same experimental protocol.
The dye composition Cii) is then applied to each lock and left to stand for 30 minutes at 40°C, and then rinsed out. Composition Ciii) is applied to each of the locks and left to stand for 15 minutes at 40°C.
After these leave-on times, the locks dyed according to the process of the invention and according to the comparative process were washed with Elvive Multivitamin shampoo, rinsed and then dried under a hood.
Dyeing results
Very intensely coloured black locks were obtained with the locks of hair that had undergone the pretreatment with composition Ci) comprising the titanium salts, which is confirmed by the colorimetric measurements below. In addition, it is seen that the colouring obtained is visually very homogeneous with the process according to the invention. These results are confirmed by the colorimetric measurements of L and ΔΕ (colour buildup) with a Minolta CM3600D spectrophotometer (illuminant D65, angle 10°, specular component included) in the CIELab system, which are collated in the table below:
Figure imgf000059_0001
It is seen from the above results that very intense colouring was obtained with the dyeing process according to the invention, since the value of L decreases greatly. Furthermore, good colour build-up ΔΕ is obtained.
Example 3:
The following compositions were prepared from the following ingredients in the following proportions, indicated in grams per 100 grams of composition:
■ Pretreatment composition Ci):
Figure imgf000060_0001
Dye composition Cii):
A dye composition Cii) in accordance with the invention comprising at least one liquid organic compound with a Hansen solubility parameter value δΗ of greater than 0 and less than 16 MPa1/2, and a comparative dye composition Cii') not comprising any liquid organic compound with a Hansen solubility parameter value δΗ of greater than 0 and less than 16 MPa1/2 were prepared.
Figure imgf000060_0002
The study relates to three types of locks of hair:
- natural Caucasian hair containing 90% white hairs (90 NW);
- permanent-waved Caucasian hair containing 90% white hairs (90
PWW);
- natural 100% white hairs (100 NW).
According to a first treatment process P1 according to the invention, these various locks are pretreated with composition Ci) comprising the titanium salt in a proportion of 3.33 g of composition per gram of hair. During this pretreatment step, composition Ci) is left to stand for 20 minutes on each lock at 40°C, and each lock is then rinsed with running tap water and drained dry. The dye composition Cii) is then applied to each of the three locks in a proportion of 3.33 g of composition per gram of hair and left to stand for 45 minutes at 40°C.
In parallel, according to a second comparative treatment process P2 outside the invention, the three different locks are pretreated with composition Ci) comprising the titanium salt in a proportion of 3.33 g of composition per gram of hair. During this pretreatment step, composition Ci) is left to stand for 20 minutes on each lock at 40°C, and each lock is then rinsed with running tap water and drained dry. The comparative dye composition Cii') not comprising any liquid organic compound with a Hansen solubility parameter value δΗ of greater than 0 and less than 16 MPa1/2 is then applied to each of the three locks in a proportion of 3.33 g of composition per gram of hair and left to stand for 45 minutes at 40°C.
Finally, in parallel, according to a third comparative treatment process P3 outside the invention, the three different locks are not pretreated with composition Ci), but are only moistened. The dye composition Cii) is then applied to each of the three locks in a proportion of 3.33 g of composition per gram of hair and left to stand for 45 minutes at 40°C.
After the leave-on time, all the locks are washed with Elvive Multivitamin shampoo, rinsed and then dried under a hood.
Dyeing results:
Visual evaluation
It is found that with process P1 of the invention (pretreatment with composition Ci, rinsing and then treatment with the dye composition Cii), locks intensely dyed black were obtained.
In the case of the comparative treatment P2 outside the invention of the locks with composition Ci, followed by rinsing and then dyeing with composition Cii', locks with less intense colourings and dyed dark blue were obtained.
Finally, in the case of the comparative treatment P3 outside the invention of the locks, without pretreatment with composition Ci), dyed with composition Cii), locks with less intense colouring and dyed brown were obtained.
These results were confirmed by the following colorimetric measurements:
Colorimetric measurements
For each of the locks, colorimetric measurements of the parameters L*, a* and b* and ΔΕ* of the colour build-up were taken with a Minolta CM3600D spectrophotometer (illuminant D65, angle 10°, specular component included, in the CIELab system).
In this system:
L* represents the lightness. The smaller the value of L*, the darker and more powerful the colouring obtained.
The colour build-up is represented by the colour difference ΔΕ between the non-dyed lock and the dyed lock: the greater the value of ΔΕ, the greater the colour build-up. This value is calculated from the following equation:
AE = V(L*-L0 *)2 +(a*-a0 *)2 +(b*-b0 *)2
In the preceding equation, L*, a* and b* represent the values measured on non-dyed locks of hair and LO*, aO* and bO* represent the values measured on dyed locks of hair.
The results obtained were as follows:
Figure imgf000062_0001
Comparative process P3 outside Caucasian 36.06 42.53
the invention: rinsing followed by 90 NW Coppery dye composition Cii) without Caucasian 37.91 43.67 brown pretreatment 90 PWW
Chinese 42.03 49.16
100 NW
Comparative process P2 outside Caucasian 30.23 47.27
the invention: Pretreatment 90 NW Dark blue composition Ci) + rinsing + Caucasian 31.84 46.88
Comparative dye composition Cii) 90 PWW
Chinese 31.28 62.19
100 NW
It is seen from the above results that, with process P1 according to the invention (pretreatment composition Ci) + rinsing + dye composition Cii)), very intense colouring was obtained with the dyeing process according to the invention, since the value of L decreases greatly relative to that for the non-dyed natural hair. Furthermore, very good colour build-up ΔΕ is obtained.
With comparative process P3 not involving pretreatment with composition Ci), and also with comparative process P2 using a dye composition (ϋ') not comprising any hydrotropic solvent, significantly less powerful colouring in terms of dyeing intensity and also in terms of colour build-up was obtained in the two cases than with process P1 according to the invention.
Example 4:
The following compositions were prepared from the following ingredients in the following proportions, indicated in grams per 100 grams of composition:
Pretreatment composition Ci):
Figure imgf000063_0001
Dye composition Cii):
Figure imgf000064_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, these various locks are pretreated with composition Ci) comprising the titanium salt in a proportion of 3.33 g of composition per gram of hair. During this pretreatment step, composition Ci) is left to stand for 45 minutes on a lock at 40°C, and the lock is then rinsed with running tap water and drained dry. The dye composition Cii) is then applied to the lock in a proportion of 3.33 g of composition per gram of hair and left to stand for 45 minutes at 40°C. In parallel, according to a second comparative treatment process P2 outside the invention, the lock is not pretreated with composition Ci), but is only moistened. The dye composition Cii) is then applied to the lock in a proportion of 3.33 g of composition per gram of hair and left to stand for 45 minutes at 40°C. After these leave-on times, the lock is washed with Elvive Multivitamin shampoo, rinsed and then dried under a hood.
Dyeing results With the locks of hair dyed according to the process of the invention, i.e. with pretreatment with the titanium salts, very intensely coloured locks were obtained, whereas those which did not receive the titanium pretreatment are weakly dyed.
These results are confirmed with the L, a and b spectrophotometer measurements.
The colorimetric measurements were performed using a Minolta CM3600D spectrocolorimeter (illuminant D65, angle 10°, specular component included) in the CIELab system. In this system, L* represents the lightness. The smaller the value of L*, the darker and more powerful the colouring obtained.
The colour build-up is represented by the colour difference ΔΕ between the non-dyed lock and the dyed lock: the greater the value of ΔΕ, the greater the colour build-up. This value is calculated from the following equation (i):
ΔΕ = V(L*-U, *)2 +(a*-a0 *)2 +(b*-b„ *f (i)
In the equation i), L*, a* and b* represent the values measured on non-dyed locks of hair and L0 *, a0 * and b0 * represent the values measured on dyed locks of hair.
The results L and ΔΕ of colour build-up are collated in the table below:
Intense blueish-black colourings were obtained, as shown by the colorimetric measurements:
Figure imgf000065_0001
It is clearly seen that the lock dyed according to the process of the invention with composition Ci) 1 and then rinsed with the dye composition Cii) 2 is dyed much more intensely and with significantly greater colour build-up than that obtained with the lock dyed according to the comparative process without pretreatment with the composition comprising the titanium salt, since the value of L decreases greatly according to the invention and the value of the colour build-up ΔΕ is higher according to the invention.
Example 5: The following compositions were prepared from the following ingredients in the following proportions, indicated in grams per 100 grams of composition:
Pretreatment composition C(i): identical to that of Example 4 (composition Ci) 1 )
Figure imgf000066_0001
■ Dye compositions C(ii): the three dye compositions C3, C4 and C5 below each comprising a different anionic direct dye were prepared:
Figure imgf000066_0002
Protocol
The study relates to locks of natural Caucasian hair containing 90% white hairs (90 NW).
According to a first dyeing process P1 according to the invention, three locks are pretreated with composition Ci) 1 comprising the titanium salt in a proportion of 3.33 g of composition per gram of hair. During this pretreatment step, composition Ci) is left to stand for 15 minutes on each lock at 40°C, and each lock is then rinsed with running tap water and drained dry. Each of the dye compositions Cii) 3, 4 and 5 is then applied separately to each of the three locks in a proportion of 3.33 g of composition per gram of hair and left to stand for 15 minutes at 40°C.
In parallel, according to a second comparative treatment process P2 outside the invention, the three different locks are not pretreated with composition Ci) 1 , but are preferably moistened. The dye compositions Cii) 3, 4 and 5 are then applied separately to each of the three locks in a proportion of 3.33 g of composition per gram of hair and left to stand for 15 minutes at 40°C. According to this dyeing process, there is therefore no step of pretreating the locks with composition Ci) 1.
The following results are obtained according to the same evaluation protocol as that used in the preceding example.
Figure imgf000067_0001
It is clearly seen that the locks dyed according to the process of the invention with composition Ci) 1 and then rinsed with the dye compositions Cii) 3, 4 or 5 are dyed much more intensely and with significantly greater colour build-up than that obtained with the locks dyed according to the comparative process without pretreatment with composition Ci) 1 comprising the titanium salt, since the value of L decreases greatly according to the invention and the value of the colour build-up ΔΕ is higher according to the invention.
Example 6: The following compositions are prepared from the following ingredients in the following proportions, indicated in grams:
■ Pretreatment composition Cii) :
Figure imgf000068_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 imgf000069_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, ie 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, comprising:
i) at least one step of treating said fibres with a cosmetic composition Ci) comprising: a) one or more titanium salts: in particular, the titanium atom of said salt(s) is of oxidation state 2, 3 or 4, denoted Ti(ll), Ti(lll) or Ti(IV), preferably Ti(IV);
b) optionally one or more carboxylic acid(s) of formula (I) below or a salt thereof:
Figure imgf000071_0001
in which formula (I):
- A represents a monovalent group when n has the value zero or a polyvalent group when n is greater than or equal to 1 , saturated or unsaturated, cyclic or non-cyclic and aromatic or non-aromatic hydrocarbon-based group comprising from 1 to 50 carbon atoms which is optionally interrupted with one or more heteroatoms and/or optionally substituted, in particular with one or more hydroxyl and/or amino groups; preferably, A represents a monovalent (d-C6)alkyl group or a polyvalent (CrC6)alkylene group optionally substituted with one or more hydroxyl and/or amino groups;
- n represents an integer between 0 and 10 inclusive; preferably, n is between 0 and 5, such as between 0 and 2; and
ii) at least one step of dyeing said fibres with a cosmetic dye composition Cii) comprising: c) one or more dyes chosen from oxidation dyes, synthetic direct dyes and dyes of natural origin, preferably chosen from ortho-diphenols;
d) at least one liquid organic compound with a Hansen solubility parameter value δΗ of greater than 0 and less than 16 MPa1/2; and
e) optionally one or more chemical oxidizing agents chosen especially from hydrogen peroxide or one or more hydrogen peroxide-generating systems;
iii) optionally at least one step of intermediate rinsing of said fibres, preferably with water, said step being performed between step i) and ii) or between step ii) and i), depending on the order in which said steps i) and ii) are performed.
2. Dyeing process according to the preceding claim, characterized in that a) the titanium salt(s) are chosen from organic Ti(IV) salts; more preferentially chosen from those of formula (l-A) belo
Figure imgf000072_0001
in which formula (l-A):
• A is identical to that of formula (I) as defined in the preceding claim;
• 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 m1+m2 = n".
3. Dyeing process according to the preceding claim, characterized in that a) the titanium salt(s) are chosen from those of formula (l-A) in which the radical A represents a monovalent (CrC6)alkyl or polyvalent (CrC6)alkylene group optionally substituted with one or more hydroxyl groups or one or more amino groups, preferably 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 a-hydroxy acids and a-amino acids; preferably, the acid is chosen from citric acid, lactic acid, malic acid, tartaric acid, glycolic acid and serine, more preferentially chosen from lactic acid and glycolic acid.
4. Dyeing process according to any one of the preceding claims, characterized in that a) the titanium salt(s) are chosen from those of formula (l-B) below:
Figure imgf000072_0002
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)(CrC4)(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 (d-C4)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 (CrC4)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.
5. Dyeing process according to any one of the preceding claims, characterized that a) the titanium salt(s) are chosen from salts of dihydroxybis(lactato)titaniumlV, particular those of the following formula:
Figure imgf000073_0001
6. Dyeing process according to Claim 1 , characterized in that a) the titanium salt(s) are chosen from inorganic salts, in particular from inorganic salts of Ti(ll), Ti(lll) or Ti(IV), preferentially of Ti(lll) or Ti(IV); preferably of Ti(IV), the titanium salt(s) a) are preferentially chosen from titanium halides, titanium sulfates and titanium phosphates.
7. Dyeing process according to any one of the preceding claims, characterized in that a) the titanium salt(s) are present in composition Ci) in a content ranging from 0.001% to 20% by weight relative to the total weight of composition Ci).
8. Dyeing process according to any one of the preceding claims, characterized in that composition Ci) comprises b) one or more carboxylic acids of formula (I) or a salt thereof as defined in Claim 1 ; in particular, the carboxylic acid(s) b) are other than the carboxylic acids complexed to Ti salts as defined in any one of Claims 1 to 5, preferably the carboxylic acid(s) present in composition Ci) are chosen from glycolic acid, lactic acid and citric acid or a salt thereof.
9. Dyeing process according to any one of the preceding claims, characterized in that composition Ci) comprises b) one or more carboxylic acids of formula (I) or a salt thereof as defined in Claim 1 , in a content ranging from 0.1% to 20% by weight relative to the total weight of composition Ci).
10. Dyeing process according to any one of the preceding claims, characterized in that composition Ci) is acidic, and in particular has a pH of less than 5.0, more particularly a pH of between 0 and 4, preferentially between 0.5 and 3.5 and more preferentially between 1 and 3.
11. Dyeing process according to any one of the preceding claims, characterized in that the dye(s) present in the dye composition Cii) are oxidation dye(s) preferably chosen from oxidation bases, and optionally one or more couplers; the oxidation base(s) are preferably chosen from para-phenylenediamines, bis(phenyl)alkylenediamines, para- aminophenols, ortho-aminophenols, heterocyclic bases and addition salts thereof, and the coupler(s) are preferably chosen from meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalene-based couplers and heterocyclic couplers, and also the addition salts thereof.
12. Dyeing process according to any one of Claims 1 to 10, characterized in that the dye(s) present in the dye composition Cii) are synthetic direct dye(s) preferably chosen from neutral, acidic or cationic nitrobenzene direct dyes, neutral, anionic or cationic azo direct dyes, neutral, anionic or cationic quinone and in particular anthraquinone direct dyes, azine, polyarylmethane such as triarylmethane, indoamine, polymethines such as styryl, porphyrin, metalloporphyrin, phthalocyanine and methine cyanine direct dyes, and mixtures thereof.
13. Dyeing process according to the preceding claim, characterized in that the synthetic direct dye(s) are anionic direct dye(s), preferably chosen from acidic nitro direct dyes, acidic azo dyes, acidic azine dyes, acidic triarylmethane dyes, acidic indoamine dyes, acidic anthraquinone dyes and indigoids; 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, and mixtures thereof;
in particular, the anionic direct dye(s) are chosen from the direct dyes of formula (VI): CoK-)m (Q+)n (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 charge(s):
■ 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+;
on condition that when a), b) and c) are present in the same composition, then c) is other than an azo anionic direct dye comprising a 1 ,8-dihydroxynaphthalene-3,5-disulfonate group;
in particular, c) are chosen from the following anionic direct dyes:
the diaryl anionic az
Figure imgf000075_0001
in which formula (VII):
• R7, R8, R9, R10, R'7, R'8, R'9 and R'10, 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 -, IVTwith 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'io 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;
it being understood that:
- formula (VII) comprises at least one sulfonate (0)2S(0 , Q+ or carboxylate (0)C(0 , Q+ radical on one of the rings A or B; preferentially alkali metal, alkaline-earth metal or ammonium sulfonate or carboxylate;
- when a), b) and c) are present in the same composition, then c) is other than an azo anionic direct dye comprising a 1 ,8-dihydroxynaphthalene-3,5-disulfonate group;
the anthraquinone dyes of formula (IX):
Figure imgf000076_0001
in which formula (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 R28and 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, particularly 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 formula (IX) comprises at least one sulfonate group (0)2S(0 , Q+;
the indigoid dyes of formula (XIII):
Figure imgf000077_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+ representing a cationic counterion; vii) (O)CO -, M+ 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;
■ Ri and Rh, which may be identical or different, represent a hydrogen atom or an alkyl group;
it being understood that at least one of the groups R53J R54J R55J R56J R57J R58J R59 or R60, represents a sulfonate group (0)2S(0 )-, M+ or carboxylate group (O)C(O )-, M+.
14. Dyeing process according to any one of Claims 1 to 10, characterized in that the dye(s) are chosen from dyes of natural origin, preferably chosen from ortho-diphenols, and mixtures thereof.
15. Dyeing process according to the preceding claim, characterized in that the dye(s) are chosen from ortho-diphenols bearing an aromatic ring, this aromatic ring being chosen from benzene, naphthalene, tetrahydronaphthalene, indane, indene, anthracene, phenanthrene, 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 contiguous adjacent atoms of the aromatic ring; and mixtures thereof.
16. Dyeing process according to either of Claims 14 and 15, characterized in that the dye(s) are chosen from the ortho-diphenol(s) of formula (II) below, or an oligomer, tautomer, optical isomer or geometrical isomer thereof, and also salts or solvates thereof, such as the hydrates:
Figure imgf000078_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) (Ci-C20)alkyl carboxylate or (CrC2o)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) (C C2o)alkoxy, xi) (Ci-C2o)alkoxy(Ci-C2o)alkyl, xii) (Ci-C20)alkoxyaryl, xiii) aryl which may optionally be substituted, xiv) aryl, xv) substituted aryl, xvi) heterocyclic 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.
17. Dyeing process according to any one of Claims 14 to 16, characterized in that the dye(s) are ortho-diphenol derivatives chosen from:
- flavanols, for instance 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 derivative(s) are chosen from haematein, brazilein, gallic acid, tannic acid, haematoxylin, brazilin and mixtures thereof.
18. Dyeing process according to any one of the preceding claims, characterized in that the total content of dyes in the dye composition Cii) is between 0.001% and 10% and preferably between 0.001 % and 5% by weight relative to the weight of composition Cii).
19. Dyeing process according to any one of the preceding claims, characterized in that composition Cii) comprises e) one or more chemical oxidizing agents; in particular, the chemical oxidizing agent(s) are chosen from hydrogen peroxide and urea peroxide; polymeric complexes that can release hydrogen peroxide, such as polyvinylpyrrolidone/H202, oxidases in the presence of a suitable substrate (for example glucose in the case of glucose oxidase or uric acid with uricase), metal peroxides which generate hydrogen peroxide in water, for instance calcium peroxide, magnesium peroxide, perborates and percarbonates; in particular, the chemical oxidizing agent(s) are chosen from hydrogen peroxide.
20. Dyeing process according to any one of the preceding claims, characterized in that the dyeing process uses f) one or more basifying agents; preferentially, the basifying agent(s) are in the dye composition Cii); preferentially, the basifying agent(s) e) are chosen from i) (bi)carbonates, ii) aqueous ammonia, iii) alkanolamines such as monoethanolamine, diethanolamine, triethanolamine and derivatives thereof, iv) oxyethylenated and/or oxypropylenated ethylenediamines, v) mineral or organic hydroxides, vi) alkali metal silicates such as sodium metasilicates, vii) amino acids, preferably basic amino acids such as arginine, lysine, ornithine, citrulline and histidine, and viii) the compounds of formula (II) below:
N - W- N
Rc Rd (ID
in which formula (II) W is a divalent (d-C8)alkylene radical optionally substituted with at least one hydroxyl group or at least one (CrC4)alkyl radical and/or optionally interrupted with at least one heteroatom, such as oxygen or sulfur, or with an -N(Re)- group; Ra, RD, Rc, Rd and Re, which may be identical or different, represent a hydrogen atom or a (C C4)alkyl or hydroxy(CrC4)alkyl radical; preferably, W represents a propylene radical. 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, quaternary ammonium hydroxides and guanidinium hydroxide; more preferentially, the basifying agent(s) are chosen from aqueous ammonia and alkanolamines such as monoethanolamine, even more preferentially aqueous ammonia.
21. Dyeing process according to any one of the preceding claims, characterized in that it comprises at least one step iii) of intermediate rinsing of said fibres, preferably with water, the intermediate rinsing step iii) being performed between step i) and ii) or between step ii) and i), depending on the order in which steps i) and ii) are performed.
22. Dyeing process according to any one of the preceding claims, characterized in that the treatment step i) involving the application of composition Ci) to keratin fibres is performed first, optionally followed by step iii) of intermediate rinsing of said fibres, preferably with water, finally followed by the dyeing step ii) involving the application of composition Cii) to said fibres.
23. Dyeing process according to any one of the preceding claims, characterized in that the leave-on time of composition Ci) on the keratin fibres is between 5 minutes and 2 hours, particularly between 15 minutes and 1 hour, preferably between 30 and 45 minutes and/or the leave-on time of composition Ci) on the keratin fibres is maintained at a temperature of between 20°C and 50°C, preferentially between room temperature (27°C) and 40°C;
and in that the leave-on time of composition Cii) on the keratin fibres is between 1 minute and 2 hours, preferably between 5 minutes and 1 hour, more preferentially, the leave-on time is between 15 and 30 minutes and/or the leave-on time of composition Cii) on the keratin fibres is maintained at a temperature of between 20°C and 50°C, preferentially between room temperature (27°C) and 40°C.
PCT/EP2016/063367 2015-06-12 2016-06-10 Hair dyeing process using a titanium salt, a dye and a particular solvent WO2016198648A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR1555395A FR3037241B1 (en) 2015-06-12 2015-06-12 A CAPILLARY COLORING PROCESS USING A TITANIUM SALT, A COLOR, AND A PARTICULAR SOLVENT
FR1555395 2015-06-12

Publications (1)

Publication Number Publication Date
WO2016198648A1 true WO2016198648A1 (en) 2016-12-15

Family

ID=53801063

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2016/063367 WO2016198648A1 (en) 2015-06-12 2016-06-10 Hair dyeing process using a titanium salt, a dye and a particular solvent

Country Status (2)

Country Link
FR (1) FR3037241B1 (en)
WO (1) WO2016198648A1 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019202140A1 (en) * 2018-04-19 2019-10-24 L'oreal Process for dyeing keratin fibres comprising the application of a chromenol/chromen-2-one derivative, composition and device
FR3104420A1 (en) * 2019-12-17 2021-06-18 L'oreal Hair treatment process using at least one titanium salt, at least one natural dye and at least one carboxylic acid
FR3104964A1 (en) * 2019-12-23 2021-06-25 L'oreal HAIR COLORING PROCESS USING A METAL SALT AND A HENNA EXTRACT

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3075607B1 (en) * 2017-12-22 2020-03-06 L'oreal HAIR COLORING PROCESS COMPRISING A TREATMENT STEP WITH A TITANIUM SALT AND A COLORING STEP COMPRISING THE APPLICATION OF AN AQUEOUS PHASE, A FATTY PHASE AND A DIRECT DYE
FR3076998B1 (en) * 2018-01-19 2019-12-27 L'oreal HAIR DYEING PROCESS USING TITANIUM SALT, OXIDATION DYE AND INTERMEDIATE RINSING
FR3124381B1 (en) * 2021-06-28 2024-05-10 Oreal Process for lightening keratin fibers using a basic pH composition comprising one or more specific metal compounds

Citations (33)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1026978A (en) 1962-03-30 1966-04-20 Schwarzkopf Verwaltung G M B H Method of dyeing hair
US3376110A (en) 1967-01-30 1968-04-02 Gen Aniline & Film Corp Solid stabilized hydrogen peroxide compositions
GB1153196A (en) 1965-07-07 1969-05-29 Schwarzkopf Verwaltung G M B H Method of Dyeing Hair
DE2359399A1 (en) 1973-11-29 1975-06-12 Henkel & Cie Gmbh Tetraaminopyrimidines as developers in oxidation hair dyes - esp. used with meta aminophenol couplers for blue shading dyes
JPH0219576A (en) 1988-07-07 1990-01-23 Kao Corp Dyeing composition for keratinous fiber
DE3843892A1 (en) 1988-12-24 1990-06-28 Wella Ag OXIDATION HAIR AGENTS CONTAINING DIAMINOPYRAZOL DERIVATIVES AND NEW DIAMINOPYRAZOLE DERIVATIVES
US5008093A (en) 1989-11-08 1991-04-16 Gaf Chemicals Corporation Anhydrous complexes of PVP and hydrogen peroxide
US5183901A (en) 1992-01-24 1993-02-02 Isp Investments Inc. Urea-hydrogen peroxide-polyvinylpyrrolidone
JPH0563124A (en) 1991-09-03 1993-03-12 Mitsubishi Electric Corp Hybrid integrated circuit device
DE4133957A1 (en) 1991-10-14 1993-04-15 Wella Ag HAIR DYE CONTAINING AMINOPYRAZOLE DERIVATIVES AND NEW PYRAZOLE DERIVATIVES
WO1994008969A1 (en) 1992-10-16 1994-04-28 Wella Aktiengesellschaft Process for producing 4,5-diamino pyrazole derivatives, their use for colouring hair and novel pyrazole derivatives
WO1994008970A1 (en) 1992-10-16 1994-04-28 Wella Aktiengesellschaft Oxidation hair dye containing 4,5-diaminopyrazole derivatives and novel 4,5-diaminopyrazole derivatives and process for their production
WO1995001772A1 (en) 1993-07-05 1995-01-19 Ciba-Geigy Ag Process for dyeing keratin-containing fibres
WO1995015144A1 (en) 1993-11-30 1995-06-08 Ciba-Geigy Ag Cationic dyes for keratin-containing fibres
WO1996015765A1 (en) 1994-11-17 1996-05-30 Henkel Kommanditgesellschaft Auf Aktien Oxidation dyes
EP0714954A2 (en) 1994-11-03 1996-06-05 Ciba-Geigy Ag Cationic iminazoleazodyestuffs
FR2733749A1 (en) 1995-05-05 1996-11-08 Oreal COMPOSITIONS FOR DYEING KERATINIC FIBERS CONTAINING DIAMINO PYRAZOLES, DYEING PROCESS, NOVEL DIAMINO PYRAZOLES, AND PREPARATION METHOD THEREOF
EP0770375A1 (en) 1995-10-21 1997-05-02 GOLDWELL GmbH Hair dyeing composition
DE19543988A1 (en) 1995-11-25 1997-05-28 Wella Ag Oxidative hair dye composition
FR2801308A1 (en) 1999-11-19 2001-05-25 Oreal KERATIN FIBER DYEING COMPOSITIONS CONTAINING 3-AMINO PYRAZOLO- [1, (- a] -PYRIDINES, DYEING PROCESS, NOVEL 3-AMINO PYRAZOLO- [1,5-a] -PYRIDINES
FR2814947A1 (en) 2000-10-09 2002-04-12 Oreal Coloring composition for skin and-or keratin fibers, comprises at least one enzyme with pro-pigmentation activity, and catalytic system containing salts or oxides of manganese and-or zinc and alkaline and-or alkaline earth hydrocarbonates
FR2814943A1 (en) 2000-10-09 2002-04-12 Oreal Coloring composition for skin and keratin fibers, comprises color precursor and catalytic system containing salts or oxides of manganese and-or zinc and alkaline hydrocarbonates
FR2814946A1 (en) 2000-10-09 2002-04-12 Oreal Composition for coloring skin and-or keratin matter, comprises color precursor, amino acid containing thiol group and catalytic system containing manganese and-or zinc salts or oxides and alkaline and-or alkaline earth hydrocarbonates
FR2814945A1 (en) 2000-10-09 2002-04-12 Oreal Treatment of grey hair for cosmetics to restore natural pigmentation to grey hair comprises application of composition of catalytic system comprising salt or oxide of manganese and/or zinc and alkaline and/or alkaline earth hydrocarbonate
FR2886136A1 (en) 2005-05-31 2006-12-01 Oreal COMPOSITION FOR DYING KERATIN FIBERS COMPRISING AT LEAST ONE DIAMINO-N, N-DIHYDRO-PYRAZOLONE DERIVATIVE AND A CATIONIC OXIDATION DYE
FR2907672A1 (en) * 2006-10-25 2008-05-02 Oreal Composition useful for dyeing of keratinous fibers, particularly human hair, comprises an anionic direct dye and an ammonium salt
FR2951374A1 (en) 2009-10-16 2011-04-22 Oreal COMPOSITION COMPRISING AT LEAST ONE ANTHRONIC DERIVATIVE, PROCESS FOR COLORING KERATINIC FIBERS FROM THE COMPOSITION
FR2954133A1 (en) * 2009-12-18 2011-06-24 Oreal Composition, useful for coloring keratin fibers, particular human keratin fibers such as hair, comprises one or more dye precursors having fused heterocyclic structure, indoline dione dye compound and liquid organic compound in a medium
WO2011086282A1 (en) 2009-12-23 2011-07-21 L'oreal Composition for dyeing keratin fibers, including at least one ortho-diphenol derivative, one particular metal derivative, and one alkalinizing agent
WO2011086284A1 (en) 2009-12-23 2011-07-21 L'oreal Composition for dyeing keratin fibers, including at least one ortho-diphenol derivative, one chemical oxidizing agent, and one alkalinizing agent
FR2976793A1 (en) 2011-06-23 2012-12-28 Oreal Dyeing keratin fibers, preferably hair, comprises treating fibers with compositions containing ortho-diphenol derivatives, manganese or zinc salts, hydrogen peroxide, (bi)carbonates, basifying agents and titanium salts to keratin fibers
WO2014202792A2 (en) * 2013-06-21 2014-12-24 L'oreal Oxidation dyeing process using a composition comprising an aminobenzimidazolone oxidation base and a metal catalyst
FR3007280A1 (en) * 2013-06-21 2014-12-26 Oreal OXIDATION COLORING PROCESS USING FATTY BODIES, METAL CATALYSTS, AND LESS OXIDATION BASES THAN COUPLERS

Patent Citations (33)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1026978A (en) 1962-03-30 1966-04-20 Schwarzkopf Verwaltung G M B H Method of dyeing hair
GB1153196A (en) 1965-07-07 1969-05-29 Schwarzkopf Verwaltung G M B H Method of Dyeing Hair
US3376110A (en) 1967-01-30 1968-04-02 Gen Aniline & Film Corp Solid stabilized hydrogen peroxide compositions
DE2359399A1 (en) 1973-11-29 1975-06-12 Henkel & Cie Gmbh Tetraaminopyrimidines as developers in oxidation hair dyes - esp. used with meta aminophenol couplers for blue shading dyes
JPH0219576A (en) 1988-07-07 1990-01-23 Kao Corp Dyeing composition for keratinous fiber
DE3843892A1 (en) 1988-12-24 1990-06-28 Wella Ag OXIDATION HAIR AGENTS CONTAINING DIAMINOPYRAZOL DERIVATIVES AND NEW DIAMINOPYRAZOLE DERIVATIVES
US5008093A (en) 1989-11-08 1991-04-16 Gaf Chemicals Corporation Anhydrous complexes of PVP and hydrogen peroxide
JPH0563124A (en) 1991-09-03 1993-03-12 Mitsubishi Electric Corp Hybrid integrated circuit device
DE4133957A1 (en) 1991-10-14 1993-04-15 Wella Ag HAIR DYE CONTAINING AMINOPYRAZOLE DERIVATIVES AND NEW PYRAZOLE DERIVATIVES
US5183901A (en) 1992-01-24 1993-02-02 Isp Investments Inc. Urea-hydrogen peroxide-polyvinylpyrrolidone
WO1994008969A1 (en) 1992-10-16 1994-04-28 Wella Aktiengesellschaft Process for producing 4,5-diamino pyrazole derivatives, their use for colouring hair and novel pyrazole derivatives
WO1994008970A1 (en) 1992-10-16 1994-04-28 Wella Aktiengesellschaft Oxidation hair dye containing 4,5-diaminopyrazole derivatives and novel 4,5-diaminopyrazole derivatives and process for their production
WO1995001772A1 (en) 1993-07-05 1995-01-19 Ciba-Geigy Ag Process for dyeing keratin-containing fibres
WO1995015144A1 (en) 1993-11-30 1995-06-08 Ciba-Geigy Ag Cationic dyes for keratin-containing fibres
EP0714954A2 (en) 1994-11-03 1996-06-05 Ciba-Geigy Ag Cationic iminazoleazodyestuffs
WO1996015765A1 (en) 1994-11-17 1996-05-30 Henkel Kommanditgesellschaft Auf Aktien Oxidation dyes
FR2733749A1 (en) 1995-05-05 1996-11-08 Oreal COMPOSITIONS FOR DYEING KERATINIC FIBERS CONTAINING DIAMINO PYRAZOLES, DYEING PROCESS, NOVEL DIAMINO PYRAZOLES, AND PREPARATION METHOD THEREOF
EP0770375A1 (en) 1995-10-21 1997-05-02 GOLDWELL GmbH Hair dyeing composition
DE19543988A1 (en) 1995-11-25 1997-05-28 Wella Ag Oxidative hair dye composition
FR2801308A1 (en) 1999-11-19 2001-05-25 Oreal KERATIN FIBER DYEING COMPOSITIONS CONTAINING 3-AMINO PYRAZOLO- [1, (- a] -PYRIDINES, DYEING PROCESS, NOVEL 3-AMINO PYRAZOLO- [1,5-a] -PYRIDINES
FR2814947A1 (en) 2000-10-09 2002-04-12 Oreal Coloring composition for skin and-or keratin fibers, comprises at least one enzyme with pro-pigmentation activity, and catalytic system containing salts or oxides of manganese and-or zinc and alkaline and-or alkaline earth hydrocarbonates
FR2814943A1 (en) 2000-10-09 2002-04-12 Oreal Coloring composition for skin and keratin fibers, comprises color precursor and catalytic system containing salts or oxides of manganese and-or zinc and alkaline hydrocarbonates
FR2814946A1 (en) 2000-10-09 2002-04-12 Oreal Composition for coloring skin and-or keratin matter, comprises color precursor, amino acid containing thiol group and catalytic system containing manganese and-or zinc salts or oxides and alkaline and-or alkaline earth hydrocarbonates
FR2814945A1 (en) 2000-10-09 2002-04-12 Oreal Treatment of grey hair for cosmetics to restore natural pigmentation to grey hair comprises application of composition of catalytic system comprising salt or oxide of manganese and/or zinc and alkaline and/or alkaline earth hydrocarbonate
FR2886136A1 (en) 2005-05-31 2006-12-01 Oreal COMPOSITION FOR DYING KERATIN FIBERS COMPRISING AT LEAST ONE DIAMINO-N, N-DIHYDRO-PYRAZOLONE DERIVATIVE AND A CATIONIC OXIDATION DYE
FR2907672A1 (en) * 2006-10-25 2008-05-02 Oreal Composition useful for dyeing of keratinous fibers, particularly human hair, comprises an anionic direct dye and an ammonium salt
FR2951374A1 (en) 2009-10-16 2011-04-22 Oreal COMPOSITION COMPRISING AT LEAST ONE ANTHRONIC DERIVATIVE, PROCESS FOR COLORING KERATINIC FIBERS FROM THE COMPOSITION
FR2954133A1 (en) * 2009-12-18 2011-06-24 Oreal Composition, useful for coloring keratin fibers, particular human keratin fibers such as hair, comprises one or more dye precursors having fused heterocyclic structure, indoline dione dye compound and liquid organic compound in a medium
WO2011086282A1 (en) 2009-12-23 2011-07-21 L'oreal Composition for dyeing keratin fibers, including at least one ortho-diphenol derivative, one particular metal derivative, and one alkalinizing agent
WO2011086284A1 (en) 2009-12-23 2011-07-21 L'oreal Composition for dyeing keratin fibers, including at least one ortho-diphenol derivative, one chemical oxidizing agent, and one alkalinizing agent
FR2976793A1 (en) 2011-06-23 2012-12-28 Oreal Dyeing keratin fibers, preferably hair, comprises treating fibers with compositions containing ortho-diphenol derivatives, manganese or zinc salts, hydrogen peroxide, (bi)carbonates, basifying agents and titanium salts to keratin fibers
WO2014202792A2 (en) * 2013-06-21 2014-12-24 L'oreal Oxidation dyeing process using a composition comprising an aminobenzimidazolone oxidation base and a metal catalyst
FR3007280A1 (en) * 2013-06-21 2014-12-26 Oreal OXIDATION COLORING PROCESS USING FATTY BODIES, METAL CATALYSTS, AND LESS OXIDATION BASES THAN COUPLERS

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
"Colour Index", THE SOCIETY OF DYERS AND COLOURISTS
"Handbook of Solubility Parameters and Other Cohesion Parameters", CRC PRESS, article "pages 95-121,177-185", pages: 95 - 121
"Ullmann's Encyclopaedia", 2005, article "Metal and Dyes", pages: 8
BAGDA, E: "The relation between surface tension and solubility parameter in liquids", FARBE LACK, vol. 84, 1978, pages 212
CHARLES M. HANSEN: "Hansen Solubility Parameters: A User's Handbook", 2000, CRC PRESS, pages: 167 - 185

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019202140A1 (en) * 2018-04-19 2019-10-24 L'oreal Process for dyeing keratin fibres comprising the application of a chromenol/chromen-2-one derivative, composition and device
FR3080284A1 (en) * 2018-04-19 2019-10-25 L'oreal METHOD FOR COLORING KERATIN FIBERS COMPRISING THE APPLICATION OF CHROMENOL / CHROMEN-2-ONE DERIVATIVE, COMPOSITION AND DEVICE
FR3104420A1 (en) * 2019-12-17 2021-06-18 L'oreal Hair treatment process using at least one titanium salt, at least one natural dye and at least one carboxylic acid
FR3104964A1 (en) * 2019-12-23 2021-06-25 L'oreal HAIR COLORING PROCESS USING A METAL SALT AND A HENNA EXTRACT

Also Published As

Publication number Publication date
FR3037241A1 (en) 2016-12-16
FR3037241B1 (en) 2017-06-02

Similar Documents

Publication Publication Date Title
EP3229754B1 (en) Hair dyeing process using at least one dye, a titanium salt and an insoluble silicate
US10524998B2 (en) Hair dyeing process using at least one dye, an organic titanium salt, and a non-cellulosic-based polysaccharide
WO2016198648A1 (en) Hair dyeing process using a titanium salt, a dye and a particular solvent
WO2016091816A1 (en) Hair dyeing process using at least one dye, a titanium salt and a cationic hydrophobic cellulosic polysaccharide
US10010495B2 (en) Hair dyeing process using at least one ortho-diphenol and one organic salt of titanium and of a carboxylic acid
US10052273B2 (en) Hair dyeing method employing at least one ortho-diphenol, one titanium derivative and one carboxylic acid
EP3229756B1 (en) Hair dyeing process using at least one dye, a titanium salt and an anionic thickening polymer
WO2016198656A1 (en) 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
US10716744B2 (en) Multi-step hair dyeing process using at least one titanium salt and a synthetic direct dye
EP3558462B1 (en) Process for dyeing and relaxing curls of keratin fibres, using reducing agents and hair dyes, and associated kit
EP3148648B1 (en) Hair dyeing process using a composition comprising at least one indol(in)e compound and a polycyclic aromatic compound containing at least ten carbon atoms
WO2023247612A1 (en) Process for treating keratin fibres using a carnitine salt or a carnitine derivative
WO2020260629A1 (en) Composition comprising 12-hydroxystearic acid, an organic amine and a liquid fatty substance
WO2023247614A1 (en) Method for the treatment of keratin fibres comprising a pretreatment or post-treatment step
FR3045344A1 (en) USE OF PARTICULAR POLYAMINE COMPOUNDS IN THE PRESENCE OF OXIDANTS FOR TREATING KERATIN FIBERS
WO2014102324A1 (en) Dyeing method employing a dye and a chaotropic salt

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16731069

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 16731069

Country of ref document: EP

Kind code of ref document: A1