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WO2009037348A1 - Colorant thiol/disulfure dérivé d'indolium, composition colorante comprenant ledit colorant, procédé d'éclaircissement de matériaux à base de kératine au moyen de ce colorant - Google Patents

Colorant thiol/disulfure dérivé d'indolium, composition colorante comprenant ledit colorant, procédé d'éclaircissement de matériaux à base de kératine au moyen de ce colorant Download PDF

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Publication number
WO2009037348A1
WO2009037348A1 PCT/EP2008/062570 EP2008062570W WO2009037348A1 WO 2009037348 A1 WO2009037348 A1 WO 2009037348A1 EP 2008062570 W EP2008062570 W EP 2008062570W WO 2009037348 A1 WO2009037348 A1 WO 2009037348A1
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alkyl
group
formula
representing
dye
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Andrew Greaves
Nicolas Daubresse
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LOreal SA
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LOreal SA
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/14—Styryl dyes
    • C09B23/145—Styryl dyes the ethylene chain carrying an heterocyclic residue, e.g. heterocycle-CH=CH-C6H5
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/4906—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom
    • A61K8/4913—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom having five membered rings, e.g. pyrrolidone carboxylic acid
    • A61K8/492—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom having five membered rings, e.g. pyrrolidone carboxylic acid having condensed rings, e.g. indol
    • 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
    • A61Q5/06—Preparations for styling the hair, e.g. by temporary shaping or colouring
    • A61Q5/065—Preparations for temporary colouring the hair, e.g. direct dyes
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/10—The polymethine chain containing an even number of >CH- groups
    • C09B23/102—The polymethine chain containing an even number of >CH- groups two heterocyclic rings linked carbon-to-carbon
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
    • C09B62/44—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring
    • C09B62/78—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring with other reactive groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
    • C09B62/44—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring
    • C09B62/78—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring with other reactive groups
    • C09B62/82—Azo dyes
    • C09B62/83—Disazo or polyazo dyes
    • 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
    • A61K2800/42—Colour properties
    • A61K2800/43—Pigments; Dyes
    • A61K2800/434—Luminescent, Fluorescent; Optical brighteners; Photosensitizers

Definitions

  • the invention relates to the dyeing of keratin materials using indolinium thiol and disulfide fluorescent dyes.
  • the direct dyes which are conventionally used are, for example, dyes of the nitrobenzene type, anthraquinone dyes, nitropyridine dyes, or dyes of the azo, xanthene, acridine, azine or triarlymethane type.
  • a chemical bleaching process comprises treating the keratin fibers, such as the hair, with a strong oxidizing system, generally composed of hydrogen peroxide, possibly in combination with persalts, generally in an alkaline medium.
  • This bleaching system has the drawback of damaging the keratin fibers and of detrimentally affecting their cosmetic properties.
  • the fibers in fact have a tendency to become rough, more difficult to disentangle and more brittle.
  • the lightening or the bleaching of keratin fibers with oxidizing agents is incompatible with the treatments for modifying the shape of said fibers, particularly in hair straightening treatments.
  • Another lightening technique comprises applying fluorescent direct dyes to dark hair. This technique, described in particular in documents WO 03/028685 and WO 2004/091473, makes it possible to retain the quality of the keratin fiber during the treatment. However, these fluorescent direct dyes do not exhibit satisfactory fastness with respect to outside agents.
  • disulfide dyes in particular azaimidazolium chromophore dyes in patent applications WO 2005/097051 or EP 1647580, and pyridinium/indolinium styryl chromophore dyes in patent applications WO 2006/134043 and WO 2006/136617.
  • the aim of the present invention is to provide new systems for dyeing keratin materials, in particular human keratin fibers, especially the hair, which do not have the drawbacks of the existing bleaching processes.
  • one aim of the invention is to provide direct dyeing systems for obtaining lightening effects, especially on naturally or artificially dark keratin fibers, which are resistant to successive shampooing operations, which do not damage the keratin fibers and which do not detrimentally affect their cosmetic properties .
  • Another aim of the invention is to dye keratin materials chromatically and in a manner which is persistent with respect to outside attacks.
  • a subject of which is a process for dyeing keratin materials, in particular keratin fibers, especially human keratin fibers such as the hair, more particularly dark hair, comprising applying, to the keratin materials, a dye composition comprising, in a suitable cosmetic medium, at least one indolinium- derived disulfide or thiol fluorescent dye, chosen from the dyes of formulae (I), (II) or (III) below:
  • > p or p' represent an integer between 0 and 4 inclusive; in particular, p or p' is 0 or 1 ; > R 1 represents a halogen atom, or a (Ci-C 6 ) alkyl, (Ci-C 6 ) alkoxy, (Ci-C 6 ) alkylthio, (di) (Ci-C 6 ) (alkyl) - amino, (Ci-C 6 ) polyhaloalkyl, hydroxyl, (Ci-C 6 )poly- hydroxyalkyl, polyhydroxy (Ci-C 6 ) alkoxy, cyano, R-G-C(G')-, R-C(C)-G-, R 1 S(O) 2 -N(R)- or RR 1 N-S(O) 2 - group with G or G', which may be identical or different, representing an oxygen or sulphur atom or a group NR', and R and R', which may be identical or different,
  • R 2 and R 3 which may be identical or different, represent a (Ci-C 6 ) alkyl group; in particular, R 2 and R 3 are identical and represent a methyl group; > R 4 and R 5 represent an alkyl or aryl (Ci-C 6 ) alkyl group, it being understood that R 4 represents a ⁇ bond when the radical -L-S- of the disulphide dye of formula (I) is linked to R 4 ;
  • B represents an optionally substituted aryl or optionally substituted heteroaryl group, such as phenyl, naphthyl or indolyl optionally substituted in particular with one or more groups chosen from (di) (Ci-C 4 ) (hydroxyalkyl) amino, (di) (Ci-C 4 ) (carboxy- alkyl) amino, (di) (Ci-C 4 ) (alkyl) amino, hydroxyl- piperidino, hydroxyl and phenyl; advantageously substituents are chosen from (di) (Ci- C 4 ) (hydroxyalkyl) amino, (di) (Ci-C 4 ) (carboxyalkyl) - amino, (di) (Ci-C 4 ) (alkyl) amino, hydroxylpiperidino;
  • L represents an optionally substituted Ci-C 20 divalent hydrocarbon-based chain which is optionally interrupted and/or optionally terminated at one or the other of its ends i) with one or more divalent groups or combinations thereof chosen from: -N(RJ-; -N + (R a ) (R b ) -, An' " ; -O-, -S-, -C(O)- and -S(O) 2 - with R a and R b , which may be identical or different, chosen from hydrogen, and a (Ci-C 6 ) alkyl, hydroxy (Ci-C 6 ) alkyl or
  • ⁇ Y represents: i) a hydrogen atom; ii) an alkali metal; iii) an alkaline earth metal; iv) an ammonium group: N + RTR 1 R , or a phosphonium group: P + R ⁇ R ⁇ R ⁇ R ⁇ , with R ⁇ , R ⁇ , R ⁇ and R ⁇ , which may be identical or different, representing a hydrogen atom or a (Ci-C 4 ) alkyl group, or v) a thiol- function-protecting group; preferably Y cannot represent Au metal when L is (C2-C5) alkylene group; ⁇ An " represents an anionic counterion; it being understood that: when p is between 2 and 4, the groups R 1 are identical or different, when p' is between 2 and 3, the groups R 1 are identical or different, - when the dye of formula (II) contains a group Y representing a hydrogen atom or an alkali metal, then the radical L cannot
  • Another subject of the invention is a dye composition for dyeing keratin fibers with a lightening effect, comprising, in a cosmetic medium, at least one indolinium-derived disulfide or thiol fluorescent dye of formula (I) , (II) or (III) as defined above, and optionally a reducing agent.
  • a subject of the invention is also novel indolinium- derived disulfide or thiol fluorescent dyes of formula (I), (II) or (III) as defined above.
  • the dyeing process according to the invention makes it possible to visibly color dark keratin materials, in particular dark human keratin fibers, especially dark hair. Furthermore, the process of the invention makes it possible to obtain a coloring of the hair without damaging it, which is persistent with respect to shampooing operations, everyday attacks (sunlight, perspiration) and hair treatments. The process of the invention also makes it possible to obtain lightening of keratin materials such as keratin fibers, in particular dark keratin fibers, and more particularly dark hair.
  • This process also makes it possible to dye keratin fibers in a strong, relatively nonselective and homogeneous manner without observing any notable change in color over time.
  • the dye compositions according to the invention are particularly stable during the conservation or the storage thereof.
  • the tone heights range from 1 (black) to 10 (very light blond), one unit corresponding to one tone; the higher the figure, the lighter the shade.
  • An artificially colored hair is a hair whose color has been modified by a dyeing treatment, for example dyeing with direct dyes or oxidation dyes.
  • the term "bleached hair” is intended to mean hair whose tone height is greater than 6 and preferably greater than 8.
  • One means for measuring the lightening effect given to the hair after application of the fluorescent dyes of the invention is to use the phenomenon of hair reflectance .
  • the composition should, after application to dark hair, lead to the results below.
  • Interest is focused on the hair reflectance performance levels when said hair is irradiated with visible light in the wavelength range from 400 to 700 nanometers.
  • the curve corresponding to the treated hair should show a reflectance in the wavelength range of from 500 to 700 nanometers which is higher than the curve corresponding to the untreated hair.
  • “higher” is intended to mean a difference of at least 0.05% in reflectance, and preferably of at least 0.1%. All the same, there may be, in the wavelength range of from 540 to 700 nanometers, at least one range where the reflectance curve corresponding to the treated hair is superimposable on or lower than the reflectance curve corresponding to the untreated hair.
  • the wavelength where the difference is at a maximum between the reflectance curve of the treated hair and that of the untreated hair is within the wavelength range of from 500 to 650 nanometers, and preferably within the wavelength range of from 550 to 620 nanometers.
  • aryl or heteroaryl radicals or the aryl or heteroaryl part of a radical may be substituted with at least one substituent chosen from:
  • Ci-Cs alkyl radical optionally substituted with one or more radicals chosen from the radicals: hydroxyl, C1-C2 alkoxy,
  • Ci-C 4 alkyl radicals which may be identical or different, optionally bearing at least one hydroxyl group, or the two radicals possibly forming, with the nitrogen atom to which they are attached, a heterocycle comprising from 5 to 7 members, preferably 5 or 6 members, which is saturated or unsaturated, which is optionally substituted, and which optionally comprises another heteroatom which may be identical or different from the nitrogen;
  • a halogen atom such as chlorine, fluorine or bromine
  • a 5- or 6-membered heterocycloalkyl radical which may be substituted with 1 to 3 groups, which may be identical or different, chosen from hydroxyl, amino, (di) alkylamino and Ci-C 4 hydroxyalkyl, such as morpholino, (hydroxyethyl) piperazino, (di) (hydroxy) -pyrrolidino, (di) (hydroxy) piperi- dino;
  • an optionally cationic 5- or 6-membered heteroaryl radical preferably imidazolium, optionally substituted with a Ci-C 4 alkyl radical, preferably methyl;
  • an amino radical substituted with one or two Ci-C ⁇ alkyl radicals which may be identical or different, optionally bearing at least: i) one hydroxyl group, ii) one amino group optionally substituted with one or two optionally substituted C1-C3 alkyl radicals, said alkyl radicals possibly forming, with the nitrogen atom to which they are attached, a heterocycle comprising from 5 to 7 members, which is saturated or unsaturated, which is optionally substituted, and which optionally comprises at least one other heteroatom which may or may not be different from nitrogen,
  • R radical is a hydrogen atom or a C1-C4 alkyl radical optionally bearing at least one hydroxyl group, and the R' radical is a C1-C2 alkyl radical;
  • R' S (0) 2-N (R) - in which the R radical represents a hydrogen atom or a C1-C4 alkyl radical optionally bearing at least one hydroxyl group, and the R' radical represents a Ci-C 4 alkyl radical or a phenyl radical;
  • R 2 N-S(O) 2 - in which the R radicals, which may or may not be identical, represent a hydrogen atom or a C1-C4 alkyl radical optionally bearing at least one hydroxyl group, • a carboxylic radical in acid or salified form (preferably with an alkali metal or an ammonium, which is substituted or unsubstituted) ;
  • R' radical is a hydrogen atom or a Ci-C 4 alkyl radical optionally bearing at least one hydroxyl group
  • R radical is a Ci-C 2 alkyl radical or an amino radical substituted with two Ci-C 4 alkyl groups, which may be identical or different, optionally bearing at least one hydroxyl group;
  • .RC(O)-O- in which the R radical is a Ci-C 4 alkyl radical or an amino radical substituted with one or two Ci-C 4 alkyl groups, which may be identical or different, optionally bearing at least one hydroxyl group, said alkyl radicals possibly forming, with the nitrogen atom to which they are attached, a heterocycle comprising from 5 to 7 members, which is saturated or unsaturated, which is optionally substituted, and which optionally comprises at least one other heteroatom which may or may not be different from nitrogen; .RO-C(O)- in which the R radical is a Ci-C 4 alkyl radical optionally bearing at least one hydroxyl group; a cyclic or heterocyclic radical or a nonaromatic part of an aryl or heteroaryl radical may also be substituted with one or more oxo or thioxo groups; an "aryl" radical represents a condensed or noncondensed, monocyclic or polycyclic group containing from 6 to 22 carbon atoms, and
  • a "saturated or unsaturated, optionally substituted C1-C30 hydrocarbon-based chain” represents a hydrocarbon-based, in particular Ci-Cs, chain optionally comprising one or more ⁇ double bonds, which may or may not be conjugated; in particular, the hydrocarbon-based chain is saturated; said chain is optionally substituted with one or more, identical or different, halogen atoms or groups chosen from hydroxyl, alkoxy,
  • the indolinium-derived disulfide or thiol fluorescent dyes of formula (I) , (II) or (III) as defined above are fluorescent dyes, i.e. are capable of absorbing in the UV radiation or visible range at a wavelength ⁇ abs of between 250 and 800 nm and capable of re-emitting in the visible range at an emission wavelength ⁇ em of between 400 and 800 nm.
  • the fluorescent compounds of formula (I) , (II) or (III) of the invention are dyes capable of absorbing in the visible range ⁇ abs of between 400 and 800 nm and of re-emitting in the visible range ⁇ em of between 400 and 800 nm. More preferably, the dyes of formula (I) , (II) or (III) are dyes capable of absorbing at a ⁇ abs of between 420 and 550 nm and of re- emitting in the visible range at a ⁇ em of between 470 and 600 nm.
  • the fluorescent compounds of the invention of formula (II) or (III) contain an SY function which may be in the covalent form -S-Y or ionic form -S ⁇ Y + depending on the nature of Y and on the pH of the medium.
  • a specific embodiment relates to the indolinium-derived disulfide or thiol fluorescent dyes of formula (II) or (III) where Y represents a hydrogen atom or an alkali metal.
  • Y represents a hydrogen atom.
  • Y is a protecting group known to those skilled in the art, for instance those described in the books
  • Y as protective group cannot constitute with the sulphur atom on which it is linked a disulfide dye i.e. cannot represent a group directly linked to the sulphur atom of formula (II) and (III) via another non oxidized sulphur atom.
  • Y represents a thiol-function- protecting group
  • Y is chosen from the following radicals :
  • arylcarbonyl such as phenylcarbonyl
  • aryl such as phenyl, dibenzosuberyl or 1, 3, 5-cycloheptatrienyl
  • heteroaryl including in particular the cationic or noncationic heteroaryl comprising from 1 to 4 heteroatoms below: i) monocyclic comprising 5, 6 or 7 members, such as furanyl or furyl, pyrrolyl or pyrryl, thiophenyl or thienyl, pyrazolyl, oxazolyl, oxazolium, isoxazolyl, isoxazolium, thiazolyl, thiazolium, isothiazolyl, isothiazolium, 1, 2, 4-triazolyl, 1,2,4- triazolium, 1, 2, 3-triazolyl, 1,2,3- triazolium, 1, 2, 4-oxazolyl, 1, 2, 4-oxazolium, 1,2, 4-thiadiazolyl, 1,2, 4-thiadiazolium, pyrylium, thiopyridyl, pyridinium, pyrimidinyl, pyrimidinium, pyrazinyl, pyrazin
  • heterocycloalkyl group represents in particular a saturated or partially saturated, 5-, 6- or 7-membered monocyclic group comprising from 1 to 4 heteroatoms chosen from oxygen, sulfur and nitrogen, such as di/tetrahydrofuranyl, di/tetrahydrothiophenyl, di/tetrahydropyrrolyl, di/tetrahydropyranyl, di/tetra/hexahydrothiopyranyl, dihydropyridyl, piperazinyl, piperidinyl, tetramethylpiperidinyl, morpholinyl, di/tetra/hexahydroazepinyl or di/tetrahydropyrimidinyl, these groups being optionally substituted with one or more groups such as (Ci-C
  • R' c , R' d , R' e , R' f , R' g and R' h which may be identical or different, represent a hydrogen atom or a (Ci-C 4 ) alkyl group, or else two groups R' g with R' h , and/or R' e with R' f , form an oxo or thioxo group, or else R' g with R' e together form a cycloalkyl; and v represents an integer between 1 and 3 inclusive; preferably, R' c to R' h represent a hydrogen atom; and An' ' ' represents a counterion;
  • aryl (Ci-C 4 ) alkyl such as 9-anthracenylmethyl, phenylmethyl or diphenylmethyl optionally substituted with one or more groups in particular chosen from (Ci-C 4 ) alkyl, (Ci-C 4 ) alkoxy such as methoxy, hydroxyl, alkylcarbonyl and (di) (Ci-C 4 ) (alkyl) amino such as dimethy1amino;
  • R 1 , R 2 and R 3 which may be identical or different, representing a halogen atom or a group chosen from: - (Ci-C 4 ) alkyl;
  • (Ci-C 4 ) alkoxy optionally substituted aryl, such as phenyl optionally substituted with one or more groups such as (Ci-C 4 ) alkyl, (Ci- C4)alkoxy or hydroxyl; optionally substituted heteroaryl, such as thiophenyl, furanyl, pyrrolyl, pyranyl or pyridyl, optionally substituted with a (Ci-C 4 ) alkyl group; P (Z 1 ) R' 1 R' 2 R' 3 with R' 1 and R' 2 , which may be identical or different, representing a hydroxyl, (Ci-C 4 ) alkoxy or alkyl group, R' 3 representing a hydroxyl or (Ci-
  • alkoxyalkyl such as methoxymethyl (MOM) , ethoxyethyl (EOM) or isobutoxymethyl .
  • the protected thiol dyes of formula (II) or (III) comprise a group Y i) which is a cationic, aromatic 5- or 6-membered monocyclic heteroaryl group comprising from 1 to 4 heteroatoms chosen from oxygen, sulfur and nitrogen, such as oxazolium, isoxazolium, thiazolium, isothiazolium, 1, 2, 4-triazolium, 1, 2, 3-triazolium, 1, 2, 4-oxazolium, 1, 2, 4-thiadiazolium, pyrylium, pyridinium, pyrimidinium, pyrazinyl, pyrazinium, pyridazinium, triazinium, tetrazinium, oxazepinium, thiepinyl, thiepinium or imidazolium; ii) cationic 8- to 11-membered bicyclic heteroaryl group, such as indolinium, benzoimidazolium, benzoxa
  • R' c and R' d which may be identical or different, represent a hydrogen atom or a (Ci-C 4 ) alkyl group; preferably, R' c to R' d represent a (Ci-C 4 ) alkyl group such as methyl; and An''' represents an anionic counterion .
  • Y represents a group chosen from oxazolium, isoxazolium, thiazolium, isothiazolium, 1 , 2 , 4-triazolium, 1, 2, 3-triazolium, 1, 2, 4-oxazolium, 1, 2, 4-thiadiazolium, pyrylium, pyridinium, pyrimidinium, pyrazinium, pyridazinium, triazinium and imidazolium, benzoimidazolium, benzoxazolium, benzothiazolium, these groups being optionally substituted with one or more (Ci-C 4 ) alkyl groups, in particular methyl.
  • Y represents an alkali metal or a protecting group such as:
  • arylcarbonyl such as phenylcarbonyl
  • ⁇ 5- or 6-membered cationic monocyclic heteroaryl such as pyrylium, pyridinium, pyrimidinium, pyrazinium, pyridazinium, triazinium or imidazolium; these groups being optionally substituted with one or more identical or different (Ci-C 4 ) alkyl groups, such as methyl;
  • the fluorescent dyes of the invention are disulphide dyes of formula (I) .
  • disulphide fluorescent dyes of formula (I) of the invention are chosen from those of formulae (I a ) , (Ib) and (I c ) :
  • Pr P' R 1 to R 4 , B and An are as defined above; > n and m, which may be identical or different, represent an integer between 1 and 6 inclusive, with the sum of n+m being between 2 and 4 inclusive, particularly 2 or 3 for (Ib);
  • X represents a radical chosen from: -G-, -G' -C(G)- and -C(G)-G'-, with G and G', which may be identical or different, representing an oxygen or sulphur atom or NR, with R representing a hydrogen atom or a (Ci-C ⁇ ) alkyl group, advantageously X represents a group -NR-, -NR-CO-, -C(O)-NR-, -S(O) 2 -, -S(O) 2 -NR-; or -NR-S(O) 2 -, or -NR-; in particular, X of formula (I 0 ) is linked at position 5 on A or the X of formula (I a ) is in the para- position of B when B represents a phenyl group;
  • T a represents a ⁇ covalent bond, a group -N(R' a )-; -N + (R 1 J (R'b)-, An " ; -C(O)-N(R 1 J- or -N(R 1 J-C(O)-, or a divalent cationic heteroaryl comprising from 5 to 7 members, such as imidazolium, with R' a , R'b, which may be identical or different, representing a hydrogen atom or a (Ci-C 4 ) alkyl radical, An " representing an anionic counte ⁇ on; in particular, T a represents -C (O) -N (R' a ) - and -N (R' a ) -C (0) - .
  • An " which may be identical or different, representing an anionic counterion.
  • the protected thiol fluorescent dyes of formula (II-Y) or (III-Y) can be synthesized in two stages.
  • the first stage consists in preparing the nonprotected thiol dye (II-H) or (III-H) according to the methods known to those skilled in the art, for instance "Thiols and organic sulfides", “Thiocyanates and isothiocyanates, organic", Ullmann' s Encyclopedia, Wiley-VCH, Weinheim, 2005.
  • the second step consists in protecting the thiol function according to the conventional methods known to those skilled in the art in order to produce the protected thiol dyes of formula (II-Y) or (III-Y) .
  • This method can be illustrated by means of the method consisting i) in generating indolinium-derived thiol fluorescent dyes of formula (II—H) or (III—H) by reduction of an indolinium-derived two-chromophore fluorescent dye bearing a disulfide function -S-S- such as (I') and ii) in protecting said thiol function of (II—H) or (III—H) , according to the conventional methods, with the reactant 1_ Y' R in order to obtain the protected thiol fluorescent dyes of formula (I' ) .
  • the thiol compound (II-H) or (III-H) may also be metallated with an alkali metal or alkaline earth metal Met* so as to produce the thiolate fluorescent dye of formula (II- Met) or (Ill-Met) .
  • Y' representing a thiol-function-protecting group
  • Met* representing an alkali metal or an alkaline earth metal, particularly sodium or potassium, it being understood that, when the metal is an alkaline earth metal, 2 chromophores comprising a thiolate -S ⁇ function can be associated with 1 Metal 2+ ; with R 1 to R 5 , A, B, An " , and p being as defined above; Y' represents a thiol-function-protecting group; and R represents a nucelofuge leaving group, for instance mesylate, tosylate, triflate or halide.
  • the indolinium-derived styryl thiol fluorescent dyes formed which are converted to -SY' protected thiol fluorescent dyes by protection of the thiol-SH using the conventional protecting groups.
  • the indolinium- derived styryl thiol fluorescent dyes are metalated by also using the conventional methods known to those skilled in the art, such as those described in Advanced Organic Chemistry, "Reactions, Mechanisms and Structures", J. March, 4th Ed. John Willey & Sons, NY, 1992.
  • a protected thiol compound (b) protected with a protecting group Y' as defined above, prepared according to one of the procedures described in the books described above, said protected thiol compound comprising at least one nucleophilic function, can be reacted with a sufficient, preferably equimolar, amount of an indoliium-derived styryl chromophore (a) or (ai) which comprises an electrophilic function so as to form a ⁇ covalent bond; see below, the preparation of dyes of formulae (II' -Y) and (III' -Y):
  • ⁇ covalent bonds that can be generated are listed in the table below based on condensation of electrophiles with nucleophiles :
  • Electrophiles E Nucleophiles Nu ⁇ Covalent bonds Activated esters* Amines Carboxamides Acyl nitrides** Amines Carboxamides Acyl halides Amines Carboxamides Acyl halides Alcohols Esters Acyl cyanides Alcohols Esters Acyl cyanides Amines Carboxamides Alkyl halides Amines Alkylamines Alkyl halides Carboxylic acids Esters Alkyl halides Thiols Thioesters Alkyl halides Alcohols Ethers Sulfonic acids Thiols Thioethers and salts thereof Sulfonic acids Carboxylic acids Esters and salts thereof Sulfonic acids Alcohols Ethers and salts thereof Anhydrides Alcohols Esters
  • a thiol reactant ( ⁇ ) Y' -SH comprising a Y' group as defined above, the nucleophilic SH function of which can react with the carbon atom of the radical L in the ⁇ -position with respect to the halogen atom borne by an indolinium- derived styryl chromophore of (a' ) or (a' ' 1) so as to give the protected thiol dye of formula (II-Y) or (III- Y) as defined above:
  • R 1 to R 5 A, B, An " , L, p, (II-Y) and (III-Y) as defined above, and Hal representing a nucleofuge halogen atom such as bromine, iodine or chlorine.
  • Another variant may make it possible to obtain the compound (11''-Y) or (111''-Y) using the cyclic thiourea derivative of imidazoline type (b' ) , followed by alkylation of said imidazole using R' d -Lg, with Lg being a leaving group such as chloride, bromide, tosylate or mesylate:
  • a variant is to use, in place of the halide comprising the fluorescent chromophore (a' ) or (a' 1) , a chromophore comprising another type of nucleofuge such as tosylate or mesylate.
  • certain protected thiol dyes (II' -Y) or (III' -Y) can be obtained by reacting a protected thiol compound with a compound bearing two carboxylic acid functions that are activated, according to the conventional methods (for example, reaction with a carbodiimide or with thionyl chloride) .
  • the resulting product (d) is subsequently reacted with an indolinium-derived styryl chromophore (c) or (cl) , the ketone functions of which are optionally protected beforehand as seen above, and which bears a nucleophilic function, for example of primary or secondary amine type, or of aliphatic alcohol type.
  • R 1 to R 5 A, B, An , L, p, n' , m' , E, Nu, (II' -Y) and (III' -Y) as defined above.
  • Another variant is to use a thiolactone derivative based on specific nucleophilic chromophores (c' ) and (c' i) so as to give the derivatives (II' -H) or (III' -H) comprising a linker L interrupted with an amide function as represented by the scheme below:
  • G' representing an oxygen or sulfur atom or an NR' group with R' representing a hydrogen atom or a alkyl radical, and R representing a hydrogen atom, a Ci-C 4 alkyl radical, a Ci-C 4 hydroxyalkyl radical or an aryl (Ci-C 4 ) alkyl .
  • the indolinium- derived styryl thiol fluorescent dyes of formula (II) or (III) according to the invention can be obtained by reaction of a compound comprising a thiol group optionally protected with Y' as defined above and an electrophilic group (e) , with an aryl or heteroaryl derivative comprising an electrophilic group.
  • a compound comprising a thiol group optionally protected with Y' as defined above and an electrophilic group (e) with an aryl or heteroaryl derivative comprising an electrophilic group.
  • This reaction is commonly known as "Knoevenagel" condensation:
  • R 1 to R 5 , B An " , L, p, G', (H-Y) and (HI-Y) as defined above.
  • indolinium-derived styryl protected thiol fluorescent dyes can be deprotected by conventional pathways such as those described in the books "Protective Groups in Organic Synthesis", T. W. Greene, John Willey & Sons Ed., NY, 1981; “Protecting Groups”, P. Kocienski, Thieme, 3rd Ed., 2005.
  • the starting reactants are commercially available or accessible by conventional methods known to those skilled in the art.
  • compositions for dyeing keratin fibers with a lightening effect comprising, in a cosmetic medium, at least one indolinium-derived disulphide, thiol or protected thiol fluorescent dye of formula (I) , (ii) or (III) as defined above.
  • the composition of the invention may also contain a reducing agent.
  • This reducing agent may be chosen from thiols, for example cysteine, homocysteine or thiolactic acid, the salts of these thiols, phosphines, bisulfite, sulfites, thioglycolic acid, and also its esters, in particular glyceryl monothioglycolate, and thioglycerol .
  • This reducing agent may also be chosen from borohydrides and derivatives thereof, for instance the salts of borohydride, of cyanoborohydride, of triacetoxyborohydride or of trimethoxyborohydride : sodium salts, lithium salts, potassium salts, calcium salts, quaternary ammonium (tetramethylammonium, tetraethylammonium, tetra-n-butylammonium or benzyltriethylammonium) salts; and catechol borane.
  • borohydrides and derivatives thereof for instance the salts of borohydride, of cyanoborohydride, of triacetoxyborohydride or of trimethoxyborohydride : sodium salts, lithium salts, potassium salts, calcium salts, quaternary ammonium (tetramethylammonium, tetraethylammonium, tetra-n-butylammonium or benzyltriethylammoni
  • the dye composition that can be used in the invention generally contains an amount of dye of formula (I) , (II) or (III) of between 0.001% and 50% relative to the total weight of the composition. Preferably, this amount is between 0.005% and 20% by weight, and even more preferably between 0.01% and 5% by weight, relative to the total weight of the composition.
  • the dye composition may also contain additional direct dyes.
  • These direct dyes are, for example, chosen from neutral, acidic or cationic nitrobenzene direct dyes, neutral, acidic or cationic azo direct dyes, tetraazapentamethine dyes, neutral, acidic or cationic quinone, in particular anthraquinone dyes, azine direct dyes, triarylmethane direct dyes, indoamine direct dyes and natural direct dyes.
  • the dye composition may contain one or more oxidation bases and/or one or more couplers conventionally used for dyeing keratin fibers.
  • oxidation bases mention may be made of para- phenylenediamines, bisphenylalkylenediamines, para- aminophenols, bis-para-aminophenols, ortho- aminophenols, heterocyclic bases, and addition salts thereof .
  • couplers mention may in particular be made of meta-phenylenediamines, meta-aminophenols, meta- diphenols, naphthalene couplers, heterocyclic couplers, and addition salts thereof.
  • the coupler (s) is (are) each generally present in an amount of between 0.001% and 10% by weight of the total weight of the dye composition, preferably between 0.005% and 6%.
  • the oxidation base(s) present in the dye composition is (are) in general each present in an amount of between 0.001% and 10% by weight of the total weight of the dye composition, preferably between 0.005% and 6% by weight .
  • addition salts of the oxidation bases and of the couplers that can be used in the context of the invention are in particular chosen from addition salts with an acid, such as hydrochlorides, hydrobromides, sulfates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates, and addition salts with a base, such as hydroxides of an alkali metal such as sodium or potassium, aqueous ammonia, amines or alkanolamines .
  • the medium suitable for dyeing also called dye support, is a cosmetic medium generally constituted of water or of a mixture of water and at least one organic solvent.
  • organic solvent By way of organic solvent, mention may, for example, be made of Ci-C 4 lower alkanols, such as ethanol and isopropanol; polyols and polyol ethers, such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and diethylene glycol monomethyl ether, and also aromatic alcohols such as benzyl alcohol or phenoxyethanol, and mixtures thereof.
  • Ci-C 4 lower alkanols such as ethanol and isopropanol
  • polyols and polyol ethers such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and diethylene glycol monomethyl ether
  • aromatic alcohols such as benzyl alcohol or phenoxyethanol, and mixtures thereof.
  • the solvents when they are present, are preferably present in proportions of preferably between 1% and 40% by weight approximately, relative to the total weight of the dye composition, and even more preferably between 5% and 30% by weight approximately.
  • the solvents, including the water are preferably present in proportions of preferably between 1% and 99% by weight approximately, relative to the total weight of the dye composition, and even more preferably between 5% and 95% by weight approximately.
  • the dye composition may also contain various adjuvants conventionally used in hair-dyeing compositions, such as anionic, cationic, nonionic, amphoteric or zwitterionic surfactants or mixtures thereof, anionic, cationic, nonionic, amphoteric or zwitterionic polymers, or blends thereof, mineral or organic thickeners, and in particular anionic, cationic, nonionic and amphoteric associative polymer thickeners, antioxidants, penetrating agents, sequestering agents, fragrances, buffers, dispersing agents, conditioning agents such as, for example, modified or unmodified, volatile or nonvolatile silicones, such as amino silicones, film-forming agents, ceramides, preservatives, opacifiers or conductive polymers.
  • the above adjuvants are in general present in an amount, for each of them, of between 0.01% and 20% by weight relative to the weight of the composition.
  • the pH of the dye composition is generally between 3 and 14 approximately, and preferably between 4 and 10 approximately. It may be adjusted to the desired value by means of acidifying or basifying agents normally used in the dyeing of keratin fibers or else by means of conventional buffer systems.
  • acidifying agents mention may, by way of example, be made of mineral or organic acids, such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids, for instance acetic acid, tartaric acid, citric acid or lactic acid, or sulfonic acids.
  • mineral or organic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids, for instance acetic acid, tartaric acid, citric acid or lactic acid, or sulfonic acids.
  • basifying agents mention may, by way of example, be made of aqueous ammonia, alkali carbonates, alkanolamines such as mono-, di- and triethanolamines, and also derivatives thereof, sodium hydroxide or potassium hydroxide and the compounds of formula ( ⁇ ) below:
  • W a is a propylene residue optionally substituted with a hydroxyl group or a Ci-C 4 alkyl radical
  • R ai , R a2 , R a3 and R a4 which may be identical or different, represent a hydrogen atom, a Ci-C 4 alkyl radical or a Ci-C 4 hydroxyalkyl radical.
  • the dye composition may be in various forms, such as in the form of a liquid, a cream or a gel, or in any other form suitable for dyeing keratin fibers, and in particular the hair.
  • Another subject of the invention is a process for dyeing keratin materials, in particular keratin fibers such as dark hair, consisting in applying a dye composition comprising, in a cosmetic medium, at least one indolinium-derived disulfide, thiol or protected thiol fluorescent dye of formula (I) , (II) or (III) as define above to the keratin materials.
  • the reducing agent may be applied as a pretreatment before the application of the composition containing at least one indolinium-derived disulfide, thiol or protected thiol fluorescent dye of formula (I), (II) or (III) .
  • This pretreatment may be of short duration, in particular from 1 second to 30 minutes, preferably from 1 minute to 15 minutes, with a reducing agent as mentioned above.
  • the composition comprising at least one indolinium-derived disulfide, thiol or protected thiol fluorescent dye of formula (I) , (II) or (III) also contains at least one reducing agent as defined above. This composition is then applied to the hair.
  • an indolinium-derived thiol or protected thiol fluorescent dye of formula (II) or (III) comprises a thiol-function-protecting group Y
  • the process of the invention may be preceded by a deprotection step aimed at restoring the SH function in situ.
  • the deprotection step can also be carried out during a hair pretreatment step, for instance reducing pretreatment of the hair.
  • the reducing agent is added to the dye composition containing at least one indolinium-derived disulfide, thiol or protected thiol fluorescent dye of formula (I) , (II) or (III) at the time of use.
  • the reducing agent is added to the dye composition containing at least one fluorescent dye of formula (I) .
  • composition comprising at least one indolinium-derived disulfide, thiol or protected thiol fluorescent dye of formula
  • composition (I) , (II) or (III) also contains at least one reducing agent as defined above. This composition is then applied to the hair.
  • the composition containing at least one dye of formula (I) also contains a reducing agent.
  • the reducing agent is applied as a post-treatment, after the application of the composition containing at least one indolinium- derived disulfide, thiol or protected thiol fluorescent dye of formula (I) , (II) or (III) .
  • the reducing agent is applied as a post-treatment.
  • the duration of the post-treatment with the reducing agent may be short, for example from 0.1 second to 30 minutes, preferably from 1 minute to 15 minutes, with a reducing agent as described above.
  • the reducing agent is an agent of thiol or borohydride type as described above .
  • a specific embodiment of the invention relates to a process in which the indolinium-derived thiol or protected thiol fluorescent dye of formula (II) or (III) can be applied directly to the hair without reducing agents, free of reducing pretreatment or reducing post-treatment.
  • a treatment with an oxidizing agent may optionally be combined.
  • Any type of oxidizing agent conventional in the field may be used. Thus, it may be chosen from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulfates, and also enzymes, among which mention may be made of peroxidases, 2-electron oxidoreductases such as uricases and 4-electron oxygenases such as laccases.
  • the use of hydrogen peroxide is particularly preferred.
  • the duration of the possible post-treatment with an oxidizing agent is between 1 second and 40 minutes. It is preferably between 1 and 10 minutes.
  • the application of the dye composition according to the invention is generally carried out at ambient temperature. It may, however, be carried out at temperatures ranging from 20 to 180 0 C.
  • a subject of the invention is also a multicompartment dyeing device or dyeing "kit” in which a first compartment contains a dye composition comprising at least one indolinium-derived disulfide, thiol or protected thiol fluorescent dye of formula (I) , (II) or
  • a second compartment contains a reducing agent capable of reducing the disulfide functions of keratin fibers and/or of the indolinium fluorescent dye of formula (I) .
  • One of these compartments may also contain one or more other dyes of direct dye or oxidation dye type.
  • the invention also relates to a multicompartment device in which a first compartment contains a dye composition comprising an indolinium-derived disulfide, thiol or protected thiol fluorescent dye of formula (I) , (II) or (III) ; a second compartment contains a reducing agent capable of reducing the disulfide bond of keratin fibers and/or of the indolinium-derived disulfide fluorescent dye of formula (I) ; a third compartment contains an oxidizing agent.
  • the dyeing device contains a first compartment containing a dye composition which comprises at least one indolinium-derived protected thiol fluorescent dye of formula (II) or (III) , a second compartment containing an agent capable of deprotecting the protected thiol so as to free the thiol, and optionally a third compartment comprising an oxidizing agent.
  • Each of the devices mentioned above may be equipped with a means for delivering the desired mixture to the hair, for example such as the devices described in patent FR 2 586 913.
  • Example 1 Synthesis of 2, 2 ' - ⁇ disulphanediylbis [ethane- 2 , 1-diyl (methylimino) -4 , l-phenyleneethene-2 , 1- diyl] ⁇ bis (1, 3, 3-trimethyl-3H-indolium) dichloride [1]
  • the yellow precipitate obtained is filtered off over celite and solubilized in 200 ml of dichloromethane and the solution obtained is washed with 200 ml of a saturated aqueous solution of sodium chloride. After drying over magnesium sulphate and evaporation of the dichloromethane, the yellow residue (80 g) is purified by silica gel chromatography. After drying, a light yellow powder is recovered. The analyses indicate that the product is in conformity with the expected structure.
  • the mixture is poured into 500 ml of ethyl acetate, and the resulting mixture is filtered and dried.
  • the product is then purified by liquid/liquid water/butanol/tert-butyl methyl ether chromatography. 2.67 g of black powder are recovered after concentration and drying under vacuum. The analyses show that the product is in conformity.
  • Example 2 Synthesis of 5-chloro-2- (2- ⁇ 2- [ (15- ⁇ 2- [-2- (5-chloro-l, 3, 3-trimethyl-3H-indolium-2-yl) vinyl] - phenyl ⁇ -4, 4, 11, ll-tetramethyl-7, 8-dithia-15-aza-4, 11- diazoniahexadec-1-yl) (methyl) amino] phenyl ⁇ vinyl) -1,3,3- trimethyl-3H-indolium tetrabromide [2]
  • Stage 1 Synthesis of 2- [ [3- (dimethylamino) propyl] (methyl) amino] benzaldehyde 1.75 ml of N, N, N' -trimethyl-1 , 3-propanediamine, 1 ml of 2-fluorobenzaldehyde and 1.45 g of potassium carbonate are stirred at 130 0 C for 16 h in 10 ml of dimethyl sulphoxide. After cooling to 75°C, 15 ml of water are added, and the mixture is conserved at 40 0 C for 3 h and then extracted with 3 times 25 ml of ethyl acetate.
  • the product is purified in several stages by sephadex column chromatography and the pure fractions collected are loaded onto an ion exchange resin (Dowex - chloride) and eluted with water. After lyophilization, 1.6 g of dark red powder are recovered. The analyses show that the product is in conformity with the expected structure.
  • Example 3 synthesis of 2, 2 ' - ⁇ disulfanediylbis [ethane- 2, 1-diylimino (2-oxoethane-2, 1-diyl) (2-methyl-lH-indole- 1, 3-diyl) ethene-2, 1-diyl] ⁇ bis (1, 3, 3-trimethyl-3ff- indolium) dichloride [3]
  • Stage 2 synthesis of 2, 2 ' - ⁇ disulfanediylbis [ethane- 5 2, 1-diylimino (2-oxoethane-2, 1-diyl) (2-methyl-lH-indole- 1, 3-diyl) ethene-2, 1-diyl] ⁇ bis- (1, 3, 3-trimethyl-3tf- indolium) dichloride [3]
  • N, N'- (disulfanediyldiethane-2, 1-diyl) bis [2- (3- 10 formyl-2-methyl-lH-indol-l-yl) -acetamide] and 0.52 g of 1, 3, 3-trimethyl-2-methylidene-2, 3-dihydro-lH-indole are mixed in 10 mL ethanol and 5 mL N-methylpyrrolidinone (NMP) . After 10 min. 0.5 mL of hydrochloric acid in isopropanol is added and the mixture is stirred for 15 24h. It is then poured on 100 mL acetone.
  • Stage 1 synthesis of N, N' - (disulfanediyldiethane-2, 1- diyl)bis (2,3, S-trimethyl-Sff-indole-S-carboxamide)
  • Stage 3 of 5, 5 '-[disulfanediylbis (ethane-2, 1-diyl- carbamoyl) ]bis ⁇ 2-[2- ⁇ 4- [bis (2-hydroxyethyl) amino] - phenyl ⁇ ethenyl] -1, 3, 3-trimethyl-3ff-indolium ⁇ bis methylsulfate
  • compositions A (9 ml) and B (1 ml) are mixed, then the formulations are applied to locks of natural white hair containing 90% white hairs (NW) , permanent-waved white hair (PW) or chestnut-brown hair having a tone height of 4 (TH4) .
  • the leave-in time is 20 minutes at ambient temperature AT.
  • a fixer (Dulcia Vital II®) diluted 10-fold with water is applied for 5 minutes at AT. After rinsing with running water and shampooing, the locks are air-dried. During the shampooing operations, there is no visible bleeding of the color; the shampoo foam and the rinsing water are uncolored.
  • PW hair are colored fuchsia.
  • the locks treated are divided into two, half are subjected to 5 successive shampooing operations according to a cycle which comprises wetting the locks with water, washing with a conventional shampoo, rinsing with water, followed by drying.

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Abstract

L'invention concerne la coloration de matériaux à base de kératine au moyen de colorants fluorescents thiol et disulfure dérivés d'indolinium. L'invention concerne une composition colorante comprenant un colorant thiol ou disulfure chromophore dérivé d'indolinium et un procédé de coloration produisant un effet éclaircissant sur des fibres de kératine, par exemple les cheveux, au moyen de ladite composition. L'invention concerne également des nouveaux colorants thiols chromophores dérivés d'indolinium et leurs utilisations dans l'éclaircissement de matériaux à base de kératine. Cette composition permet d'obtenir une coloration avec un effet éclaircissant qui est particulièrement résistant et visible sur des fibres de kératine foncées.
PCT/EP2008/062570 2007-09-21 2008-09-19 Colorant thiol/disulfure dérivé d'indolium, composition colorante comprenant ledit colorant, procédé d'éclaircissement de matériaux à base de kératine au moyen de ce colorant Ceased WO2009037348A1 (fr)

Applications Claiming Priority (4)

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FR0757749A FR2921374A1 (fr) 2007-09-21 2007-09-21 Colorant derive d'indolinium thiol/disulfure, composition tinctoriale comprenant ce colorant, procede d'eclaircissement des matieres keratiniques a partir de ce colorant
FR0757749 2007-09-21
US96063207P 2007-10-09 2007-10-09
US60/960,632 2007-10-09

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US7717964B2 (en) 2007-09-21 2010-05-18 L'oreal S.A. Styryl thiol/disulfide compound with a hydroxy(cyclo)alkylamino unit, process for lightening keratin materials using same
US7727287B2 (en) 2007-09-21 2010-06-01 L'oreal S.A. Hemicyanin styryl thiol/disulfide dye, composition comprising hemicyanin styryl thoil/disulfide dye, and method for lightening keratin materials using hemicyanin styryl thiol/disulfide dye
US7744657B2 (en) 2007-09-21 2010-06-29 L'oreal S.A. Styrl tetrahydroquinolinium thiol/disulfide dye compound and method for lightening keratin materials using the same
US7744658B2 (en) 2007-09-21 2010-06-29 L'oreal S.A. Indole-derived styryl dye comprising an alkylene linker, a dye composition comprising this dye, and a process for lightening keratin materials using this dye
US7780743B2 (en) 2006-03-24 2010-08-24 L'oreal S.A. Fluorescent entity, dyeing composition containing at least one fluorescent entity, and method for lightening keratin materials using said at least one fluorescent entity
US8070830B2 (en) 2006-03-24 2011-12-06 L'oreal S.A. Fluorescent entity, dyeing composition containing at least one fluorescent entity comprising at least one heterocycle, with at least one internal cationic charge, and method for lightening keratin materials using said at least one fluorescent entity
CN102757659A (zh) * 2012-07-24 2012-10-31 大连理工大学 一类咔唑类半菁荧光染料及其应用
US8562693B2 (en) 2006-03-24 2013-10-22 L'oreal Method of dyeing and lightening keratin materials in the presence of a reducing agent comprising a fluorescent deisulphide dye
WO2013174871A1 (fr) 2012-05-23 2013-11-28 L'oreal Procédé de teinture de fibres kératiniques comprenant une teinture/un pigment, un composé photoactif et une source lumineuse

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Cited By (12)

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US7780743B2 (en) 2006-03-24 2010-08-24 L'oreal S.A. Fluorescent entity, dyeing composition containing at least one fluorescent entity, and method for lightening keratin materials using said at least one fluorescent entity
US8070830B2 (en) 2006-03-24 2011-12-06 L'oreal S.A. Fluorescent entity, dyeing composition containing at least one fluorescent entity comprising at least one heterocycle, with at least one internal cationic charge, and method for lightening keratin materials using said at least one fluorescent entity
US8562693B2 (en) 2006-03-24 2013-10-22 L'oreal Method of dyeing and lightening keratin materials in the presence of a reducing agent comprising a fluorescent deisulphide dye
US8685114B2 (en) 2006-03-24 2014-04-01 L'oreal Composition for dyeing and lightening keratin materials comprising a fluorescent deisulphide dye compound
WO2009037325A3 (fr) * 2007-09-21 2010-01-21 L'oreal Colorant styryle dérivé d'indole thiol/disulfure, composition colorante comprenant ledit colorant, procédé d'éclaircissement de matériaux à base de kératine au moyen de ce colorant
US7717964B2 (en) 2007-09-21 2010-05-18 L'oreal S.A. Styryl thiol/disulfide compound with a hydroxy(cyclo)alkylamino unit, process for lightening keratin materials using same
US7727287B2 (en) 2007-09-21 2010-06-01 L'oreal S.A. Hemicyanin styryl thiol/disulfide dye, composition comprising hemicyanin styryl thoil/disulfide dye, and method for lightening keratin materials using hemicyanin styryl thiol/disulfide dye
US7744657B2 (en) 2007-09-21 2010-06-29 L'oreal S.A. Styrl tetrahydroquinolinium thiol/disulfide dye compound and method for lightening keratin materials using the same
US7744658B2 (en) 2007-09-21 2010-06-29 L'oreal S.A. Indole-derived styryl dye comprising an alkylene linker, a dye composition comprising this dye, and a process for lightening keratin materials using this dye
WO2013174871A1 (fr) 2012-05-23 2013-11-28 L'oreal Procédé de teinture de fibres kératiniques comprenant une teinture/un pigment, un composé photoactif et une source lumineuse
US9730876B2 (en) 2012-05-23 2017-08-15 L'oreal Process for dyeing keratin fibres comprising a dye-pigment, a photoactive compound and a light source
CN102757659A (zh) * 2012-07-24 2012-10-31 大连理工大学 一类咔唑类半菁荧光染料及其应用

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