WO2009109457A2 - Composition pour colorer des fibres de kératine comprenant au moins un colorant direct comprenant une fonction disulfure/thiol protégée et au moins un composé siliceux comprenant une fonction thiol et procédé utilisant la composition - Google Patents

Composition pour colorer des fibres de kératine comprenant au moins un colorant direct comprenant une fonction disulfure/thiol protégée et au moins un composé siliceux comprenant une fonction thiol et procédé utilisant la composition Download PDF

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WO2009109457A2
WO2009109457A2 PCT/EP2009/051786 EP2009051786W WO2009109457A2 WO 2009109457 A2 WO2009109457 A2 WO 2009109457A2 EP 2009051786 W EP2009051786 W EP 2009051786W WO 2009109457 A2 WO2009109457 A2 WO 2009109457A2
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group
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alkyl
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optionally substituted
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WO2009109457A3 (fr
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Alain Lagrange
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LOreal SA
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LOreal SA
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    • 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
    • A61K8/494—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom
    • A61K8/4946—Imidazoles or their condensed derivatives, e.g. benzimidazoles
    • 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
    • A61K8/46—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur
    • 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
    • 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
    • A61K8/4926—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom having six membered rings
    • 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
    • A61K8/494—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/4973—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with oxygen as the only hetero atom
    • 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
    • A61K8/58—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing atoms other than carbon, hydrogen, halogen, oxygen, nitrogen, sulfur or phosphorus
    • A61K8/585—Organosilicon compounds
    • 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
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/89—Polysiloxanes
    • A61K8/896—Polysiloxanes containing atoms other than silicon, carbon, oxygen and hydrogen, e.g. dimethicone copolyol phosphate
    • A61K8/899—Polysiloxanes containing atoms other than silicon, carbon, oxygen and hydrogen, e.g. dimethicone copolyol phosphate containing sulfur, e.g. sodium PG-propyldimethicone thiosulfate copolyol
    • 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
    • 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
    • A61K2800/432—Direct dyes
    • A61K2800/4322—Direct dyes in preparations for temporarily coloring the hair further containing an oxidizing agent

Definitions

  • the subject of the invention is a composition comprising at least one direct dye comprising a disulphide or protected-thiol function and at least one siliceous compound comprising a thiol function, used for dyeing keratin fibres, in particular human keratin fibres such as the hair.
  • a subject of the invention is also the method for dyeing keratin fibres using said composition and the use of direct dyes comprising a disulphide function associated with the siliceous compound comprising a thiol function in the dyeing and lightening of keratin fibres.
  • Direct dyeing or semi-permanent dyeing comprises providing the colour through a coloured molecule which is adsorbed at the surface of the hair or penetrates into the hair.
  • the method conventionally used in direct dyeing comprises applying, to the keratin fibres, direct dyes which are coloured or colouring molecules having an affinity for the fibres, leaving the fibres in contact with the colouring molecules and then rinsing the fibres.
  • this technology produces chromatic colourings.
  • the reducing agents described in these documents are reducing agents that are small in size and have a low molecular molar mass, such as thioglycolic acid, thiolactic acid and their associated salts, cysteine, and borohydrides, and have a tendency to migrate inside the fibre, thereby impairing the integrity of this fibre and result in it becoming brittle. Furthermore, the prior art reducing agents have the drawback of generating unpleasant odours.
  • the objective of the present invention is to provide new hair dyeing systems for obtaining colourings which are virtually odourless, homogeneous, very intense and fast with respect to external agents, and which do not impair the cosmetic properties of keratin fibres.
  • Another objective of the invention is to provide dyeing systems for obtaining colourings that are visible on dark hair and lightening effects on naturally or artificially dark keratin fibres without degradation of the fibre.
  • Another object of the invention is to make it possible to efface the colouring on light hair or on dark hair at the moment this is desired, while at the same time limiting the detrimental effects thereof on the quality of the fibre.
  • a dye composition comprising, in a suitable cosmetic medium, i) one or more dyes chosen from direct dyes comprising a disulphide function or functions, or comprising a protected-thiol function or functions, and ii) one or more siliceous compound (s) comprising a thiol function or functions.
  • a subject of the invention is also a method for dyeing keratin fibres, in particular human keratin fibres, such as the hair, comprising applying, to the fibres, the dye composition mentioned above.
  • Another subject of the invention is the use, for dyeing keratin fibres, in particular the hair, of one or more direct dye(s) comprising a disulphide function or functions, or comprising a protected-thiol function or functions, and of one or more siliceous compound (s) comprising a thiol function or functions.
  • composition according to the invention makes it possible in particular to powerfully and homogeneously dye human keratin fibres such as the hair, while at the same time observing the integrity of the fibres.
  • siliceous compounds comprising a thiol function that are of use in the present invention can reduce the cysteine molecules present at the surface of the hairs, thus allowing the appearance of thiol functions at the surface of the hair and then the covalent bonding of the direct dyes comprising a disulphide, thiol or protected-thiol function, directly to the hair, while at the same time avoiding penetrating into the hairs.
  • siliceous compounds can themselves bind to the cysteine-unit-rich proteins of the surface of the hairs and establish other bonds with the dyes comprising disulphide, thiol or protected-thiol units, through "sulphur-sulphur" bond exchanges.
  • the establishment of asymmetric disulphide bonds between the surface of the hair, the polymers and the colouring chromophores derived from the dyes of the invention can be aided by an oxidizing agent which bonds together two thiol functions belonging to two different species.
  • siliceous compounds comprising a thiol function or functions thus perform a mordanting role for the surface bonding of the disulphide or thiol or protected-thiol dyes.
  • keratin fibre degradation is very limited.
  • the colourings obtained are aesthetic, very intense and very fast with respect to common attacks such as sunlight, perspiration or sebum, and to other hair treatments such as successive shampooing operations, while at the same time being kind to the keratin fibres.
  • the intensity obtained is particularly notable. The same is true with regard to the homogeneity of the colour.
  • Another advantage of the invention concerns the effacing of the colouring, as desired, which is made possible with a minimum detrimental effect on the quality of the keratin fibre.
  • a "direct dye comprising a disulphide function or functions” is a direct dye comprising one or more chromophores which absorb (s) light in the visible spectrum, and comprising one or more disulphide bonds: -S-S- between two carbon atoms, directly or indirectly linked to the chromophore (s) of the dye.
  • a single disulphide bond is indirectly linked to the chromophore (s) ; the -S-S- bond being capable of being reduced in a cosmetically acceptable medium; when the direct dye contains several chromophores, the chromophores may be identical or different;
  • a "direct dye comprising a protected-thiol function" is a direct dye comprising a chromophore, and comprising one or more protected- thiol functions -SY' where Y' is a protective group known to those skilled in the art, for instance those described in the books "Protective Groups in Organic Synthesis", T. W. Greene, John Willey & Sons ed., NY, 1981, pp.
  • chromophore is a radical derived from a dye, i.e. a radical derived from a molecule which absorbs light in the visible range of radiation visually and physiologically perceptible by humans, i.e. at an absorption wavelength ⁇ abs of between 400 and 800 nm, limits included; the chromophore may be fluorescent, i.e. it is capable of absorbing in the UV or visible radiation 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 disulphide dyes according to the invention contain one or more chromophores, and these disulphide dyes are capable of absorbing light at a wavelength ⁇ abs in particular between 400 and 700 nm, limits included;
  • the "fluorescent" disulphide dyes according to the invention are dyes containing at least one fluorescent chromophore, and these disulphide dyes are capable of absorbing in the visible range at a wavelength ⁇ abs of particularly between 400 and 800 nm and of re-emitting in the visible range at a wavelength ⁇ em that is higher than that absorbed, of between 400 and 800 nm.
  • the difference between the absorption wavelength and the emission wavelength, also known as Stoke' s shift, is between 1 nm and 100 nm.
  • the fluorescents dyes are dyes capable of absorbing at a wavelength ⁇ abs of between 420 nm and 550 nm and of re-emitting in the visible range at a wavelength ⁇ em of between 470 and 600 nm;
  • the chromophores are said to be "different" when they differ by virtue of their chemical structure, and may be chromophores derived from different families or from the same family provided that they have different chemical structures: for example, the chromophores may be chosen from the family of azo dyes, but differ by virtue of the chemical structure of the radicals of which they are formed or by virtue of the respective position of these radicals;
  • an "alkylene chain” represents a C1-C20 divalent chain; particularly C 1 -C 6 , more particularly C1-C2 when the chain is linear; optionally substituted with one or more groups, which may be identical or different, chosen from hydroxyl, (C1-C2) alkoxy,
  • a "C1-C30 divalent, saturated or unsaturated, optionally substituted hydrocarbon-based chain” represents a hydrocarbon-based chain, particularly a Ci-Cs hydrocarbon-based chain, comprising optionally one or more double bonds ⁇ , which are conjugated or nonconjugated, particularly the hydrocarbon-based chain is saturated; said chain is optionally substituted by one or more, identical or different, groups chosen from hydroxyl, (Ci-C 2 ) alkoxy, (poly) hydroxy (C 2 -C 4 ) - alkoxy, (di) (Ci-C 2 ) (alkyl) amino, R a -Z a -C(Z b )- and R a -Z a -S(O) t - with Z a and Z b , which may be identical or different, representing an oxygen or sulphur atom or an NR a ' group, R a representing an alkali metal, a hydrogen atom or an alkyl group or
  • - a 5- or 6-membered heteroaryl radical which is optionally cationic, preferably imidazolium, and optionally substituted with a (C1-C4) alkyl radical, preferably methyl; - an amino radical substituted with one or two C 1 -C 6 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, it being possible for said alkyl radicals to form, with the nitrogen atom to which they are attached, a saturated or unsaturated, optionally substituted heterocycle comprising from 5 to 7 ring members, optionally comprising at least one other heteroatom identical to or different from nitrogen, iii) 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 C1-C
  • R radicals which may or may not be identical, represent a hydrogen atom, or a Ci-C 4 alkyl radical optionally bearing at least one hydroxyl group; an alkylsulphonylamino radical (R' SO 2 -
  • R radical represents a hydrogen atom, or a Ci-C 4 alkyl radical optionally bearing at least one hydroxyl group
  • R' radical represents a Ci-C 4 alkyl radical or a phenyl radical
  • an aminosulphonyl radical ((R) 2 N-SO 2 -) in which the R radicals, which may or may not be identical, represent a hydrogen atom or a Ci-C 4 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, substituted or unsubstituted
  • cyclic or heterocyclic part of a nonaromatic radical may be substituted with at least one substituent chosen from the groups:
  • RCO-NR'- - alkylcarbonylamino
  • the R' radical is a hydrogen atom, or a Ci-C 4 alkyl radical optionally bearing at least one hydroxyl group
  • the R radical is a C1-C2 alkyl radical or an amino radical which is optionally substituted with one or two identical or different Ci-C 4 alkyl groups, themselves optionally bearing at least one other hydroxyl group, it being possible for said alkyl radicals to form, with the nitrogen atom to which they are attached, a saturated or unsaturated, optionally substituted heterocycle comprising from 5 to 7 ring members, optionally comprising at least one other heteroatom atom identical to or different from nitrogen;
  • RCO-O- - alkylcarbonyloxy
  • the R radical is a Ci-C 4 alkyl radical or an amino group which is optionally substituted with one or two identical or different Ci-C 4 alkyl groups, themselves optionally bearing at least one hydroxyl group, it being possible for said alkyl radicals to form, with the nitrogen atom to which they are attached, a saturated or unsaturated, optionally substituted heterocycle comprising from 5 to 7 ring members, optionally comprising at least one other heteroatom identical to or different from nitrogen;
  • R radical is a C1-C4 alkoxy radical
  • G is an oxygen atom, or an amino group that is optionally substituted with a Ci-C 4 alkyl group, itself optionally bearing at least one hydroxyl group, it being possible for said alkyl radical to form, with the nitrogen atom to which it is attached, a saturated or unsaturated, optionally substituted heterocycle comprising from 5 to 7 ring members, optionally comprising at least one other heteroatom identical to or different from nitrogen;
  • a cyclic or heterocyclic radical, or a nonaromatic part of an aryl or heteroaryl radical may also be substituted with one or more oxo groups;
  • ⁇ a hydrocarbon-based chain is unsaturated when it comprises one or more double bonds and/or one or more triple bonds;
  • an "aryl” radical represents a condensed or noncondensed, monocyclic or polycyclic carbon- based group containing from 6 to 22 carbon atoms, and at least one ring of which is aromatic; preferably, the aryl radical is a phenyl, biphenyl, naphthyl, indenyl, anthracenyl or tetra- hydronaphthyl ;
  • heteroaryl radical represents a condensed or noncondensed, optionally cationic, monocyclic or polycyclic group comprising from 5 to 22 ring members, and from 1 to 6 heteroatoms chosen from nitrogen, oxygen, sulphur and selenium atoms, and at least one ring of which is aromatic; preferably, a heteroaryl radical is chosen from acridinyl, benzimidazolyl, benzobistriazolyl, benzopyrazolyl, benzopyridazinyl, benzoquinolyl, benzothiazolyl, benzotriazolyl, benzoxazolyl, pyridinyl, tetrazolyl, dihydrothiazolyl, imidazopyridinyl, imidazolyl, indolyl, isoquinolyl, naphthaimidazolyl, naphthooxazolyl, naphthopyrazolyl, oxadiazolyl, oxazo
  • heterocyclic radical is a radical which may contain one or two unsaturations but which is nonaromatic, monocyclic or polycyclic and condensed or noncondensed, containing from 5 to 22 ring members, and comprising from 1 to 6 hetero- atoms chosen from nitrogen, oxygen, sulphur and selenium atoms;
  • heterocycloalkyl radical is a saturated heterocyclic radical
  • an "alkyl radical” is a linear or branched, C1-C20, preferably Ci-Cs, hydrocarbon-based radical;
  • the expression "optionally substituted” attributed to the alkyl radical implies that said alkyl radical may be substituted with one or more radicals chosen from the radicals i) hydroxyl, ii) C1-C4 alkoxy, iii) acylamino, iv) amino which is optionally substituted with one or two Ci-C 4 alkyl radicals, which may be identical or different, it being possible for said alkyl radicals to form, with the nitrogen atom which bears them, a heterocycle comprising from 5 to 7 ring members, optionally comprising another heteroatom identical to or different from nitrogen
  • an "alkoxy radical” is an alkyl-oxy radical for which the alkyl radical is a linear or branched, C1-C16, preferably Ci-Cs, hydrocarbon-based radical;
  • ⁇ "naturally or artificially dark” hair is hair of which the tone height is less than or equal to 6
  • the direct dyes comprising a protected-thiol or disulphide function are chosen from the dyes of formula (I) :
  • U represents a radical chosen from: ii) -S- Cat - (X' ) P' - D; and iii) -Y;
  • a and A' which may be identical or different, represent a radical containing one or more cationic or noncationic, fluorescent or nonfluorescent chromophore (s) ;
  • Y represents a thiol-function-protecting group
  • X and X' which may be identical or different, represent a linear or branched, saturated or unsaturated, C1-C30 divalent hydrocarbon-based chain, optionally interrupted and/or optionally terminated at one or two of its ends with one or more divalent groups or combinations thereof chosen from:
  • R which may be identical or different, chosen from a hydrogen and a C 1 -C 4 alkyl, hydroxyalkyl or aminoalkyl radi cal ;
  • ⁇ a condensed or noncondensed, saturated or unsaturated, aromatic or nonaromatic (hetero) cyclic radical optionally comprising one or more heteroatoms, which may be identical or different, and optionally substituted;
  • • p and p' which may be identical or different, are 0 or 1; • C sat and C' sat , which may be identical or different, represent a linear or branched, optionally substituted, optionally cyclic Ci-Cis alkylene chain;
  • D corresponds to a radical chosen from hydroxyl, hydroxyalkyl, alkoxy, carboxylic, carboxylate, amino, alkylamino and dialkyl- amino radicals.
  • One particular embodiment of the invention concerns the dye compositions comprising, as dye comprising a disulphide function, a dye of formula (I) as defined above.
  • Another particular embodiment of the invention focuses on the dye compositions comprising one or more fluorescent dye(s) comprising a disulphide or protected-thiol function or functions with a view to dyeing and/or lightening dark keratin fibres. More particularly, the fluorescent dye(s) comprise (s) a disulphide function or functions.
  • Y is a protective group known to those skilled in the art, for instance those described in the books "Protective Groups in Organic Synthesis” , T. W. Greene, John Willey & Sons ed., NY, 1981, pp. 193-217; "Protecting Groups”, P. Kocienski, Thieme, 3rd ed., 2005, chap. 5, and Ullmann' s Encyclopedia, "Peptide Synthesis” , p. 4-5, 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 10.1002/14356007. al9 157.
  • Y represents a thiol-function- protecting group
  • the latter is chosen from the following radicals:
  • arylcarbonyl such as phenylcarbonyl
  • M + with M + representing an alkali metal such as sodium or potassium, or else a counterion of the cationic chromophore A and
  • aryl such as phenyl, dibenzosuberyl or 1, 3, 5-cycloheptatrienyl
  • heteroaryl including, in particular, the cationic or noncationic heteroaryls comprising from 1 to 4 heteroatoms, below: i) 5-, 6- or 7-membered monocyclic heteroaryls, 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-tri- azolium, 1, 2, 3-triazolyl, 1, 2, 3-triazolium, 1, 2, 4-oxazolyl, 1, 2, 4-oxazolium, 1, 2, 4-thia- diazolyl, 1, 2, 4-thiadiazolium, pyrylium, thiopyridyl, pyridinium, pyrimidinyl, pyrimidin
  • 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, sulphur and nitrogen, such as di/tetrahydrofuranyl, di/tetrahydrothiophenyl, di/tetrahydro- pyrrolyl, di/tetrahydropyranyl, di/tetra/ hexahydrothiopyranyl, dihydropyridyl, piperazinyl, piperidinyl, tetramethyl- piperidinyl, morpholinyl, di/tetra/hexa- hydroazepinyl or di/tetrahydropyrimidinyl, these groups being optionally substituted with one or more groups such as (C 1 -C 4 ) alkyl, oxo or thioxo; or the heterocycle represents the following group:
  • 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 (C 1 -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, limits included; preferably, R' c to R' h represent a hydrogen atom; and An'" ⁇ represents a counterion;
  • R' c , R' d , R' e and R' f which may be identical or different, representing a hydrogen atom or a (C 1 -C 4 ) alkyl group; preferably, R' c to R' f represent a hydrogen atom; and An'" ⁇ represents a counterion;
  • NR' c R' d NR' e
  • R' c , R' d and R' e being as defined above
  • optionally substituted (di) aryl (C 1 -C 4 ) alkyl, such as 9-anthracenylmethyl, phenylmethyl or diphenylmethyl, optionally substituted with one or more groups in particular chosen from (C 1 -C 4 ) alkyl, (C 1 -C 4 ) alkoxy such as methoxy, hydroxyl, alkylcarbonyl, and (di) (C 1 -C 4 )- (alkyl) amino such as dimethylamino;
  • heteroaryl group is in particular cationic or noncationic, and monocyclic, comprising 5 or 6 ring members and from 1 to
  • heteroatoms chosen from nitrogen, oxygen and sulphur, such as the groups pyrrolyl, furanyl, thiophenyl, pyridyl, pyridyl N-oxide, such as 4-pyridyl or 2-pyridyl N-oxide, pyrylium, pyridinium or triazinyl, optionally substituted with one or more groups such as alkyl, in particular methyl; advantageously, the (di) heteroaryl (C 1 -C 4 ) alkyl is (di) heteroarylmethyl or (di) heteroaryl- ethyl;
  • R 1 , R 2 and R 3 which may be identical or different, representing a halogen atom or a group chosen from:
  • aryl such as phenyl optionally substituted with one or more groups such as (C 1 -C 4 ) alkyl, (C 1 -C 4 ) alkoxy or hydroxyl ;
  • heteroaryl such as thiophenyl, furanyl, pyrrolyl, pyranyl or pyridyl, optionally substituted with a (C 1 -C 4 ) alkyl group;
  • R' 1 R' 2 R' 3 with R' 1 and R' 2 which may be identical or different, representing a hydroxyl, (C 1 -C 4 ) alkoxy or alkyl group, R' 3 representing a hydroxyl or (C 1 -C 4 ) alkoxy group, and Z 1 representing an oxygen or sulphur atom; - a sterically hindered cyclic radical; and
  • the protected-thiol fluorescent dyes of formula (I) comprise a group Y which is a i) cationic, aromatic, 5- or 6-membered monocyclic heteroaryl group comprising from 1 to 4 heteroatoms chosen from oxygen, sulphur 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
  • R' c and R' d which may be identical or different, represent a hydrogen atom or a (C 1 -C 4 ) alkyl group; preferably, R' c to R' d represent a (C 1 -C 4 ) alkyl group such as methyl; and An'" ⁇ represents a 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, imidazolium, benzoimidazolium, benzoxazolium and benzothiazolium, these groups being optionally substituted with one or more (C 1 -C 4 ) alkyl groups, in particular methyl.
  • Y represents a protective group such as :
  • 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 (C 1 -C 4 ) alkyl groups, such as methyl;
  • C sa t and C sat independently of one another, represent a linear or branched, optionally substituted, optionally cyclic C 1 -C 18 alkylene chain.
  • substituent By way of substituent, mention may be made of amino, (C 1 -C 4 ) alkylamino or (C 1 -C 4 ) dialkylamino groups or the group R a -Z a -C(Z b )- (in which Z a and Z b , which may be identical or different, represent an oxygen or sulphur atom or an NR a ' group, and R a ' represents an alkali metal, a hydrogen atom or a Ci-C 4 alkyl group, and R a ' represents a hydrogen atom or a Ci-C 4 alkyl group) preferably present on the carbon in the beta- or gamma-position with respect to the sulphur atoms.
  • C sa t and C sat represent a - (CH 2 ) k ⁇ chain with k being an integer between 1 and 8, limits included.
  • T and T' which may be identical or different, represent one or more radicals or combinations thereof chosen from: -0-; -S-; -N(R)-; -N + (R) (R 0 )-; -SO-; -SO 2 -; -CO-; with R and R°, which may be identical or different, representing a hydrogen atom, or a Ci-C 4 alkyl, Ci-C 4 hydroxyalkyl or aryl (C 1 -C 4 ) alkyl radical; and a cationic or noncationic, preferably monocyclic, heterocycloalkyl or heteroaryl radical, preferably containing two heteroatoms (more preferably, two nitrogen atoms) and preferably comprising from 5 to 7 ring members, more preferably imidazolium; the indices t and t' , which may be identical or different, are 0 or 1; Z represents:
  • M representing a hydrogen atom, an alkali metal or an ammonium group substituted with one or more identical or different, linear or branched, Ci-Cis alkyl radicals, optionally bearing at least one hydroxyl; z is 0 or 1.
  • Z represents:
  • M represents a hydrogen atom, an alkali metal or an ammonium group or an ammonium group substituted with one or more identical or different, linear or branched, C1-C10 alkyl radicals optionally bearing at least one hydroxyl, and 0-4 represents an integer between 0 and 4, limits included.
  • radicals A and/or A' of the formulae (I) may contain one or more chromophores, which may be identical or different.
  • chromophores A and/or A' that are of use in the present invention, mention may be made of radicals derived from acridine, acridone, anthranthrone, anthrapyrimidine, anthraquinone, azine, azo, azomethine, benzanthrone, benzimidazole, benzimidazolone, benzindole, benzoxazole, benzopyran, benzothiazole, benzoquinone, bisazine, bisisoindoline, carboxanilide, coumarin, cyanin (such as azacarbo- cyanin, diazacarbocyanin, diazahemicyanin, hemicyanin or tetraazacarbocyanin) , diazine, diketopyrrolopyrrole, dioxazine, diphenylamine, diphenylmethane, dithiazine, flavonoid, such
  • fluorescent chromophores A and/or A' that are of use in the present invention, mention may be made of the radicals derived from acridine, acridone, benzanthrone, benzimidazole, benzimidazolone, benzindole, benzoxazole, benzopyran, benzothiazole, coumarin, difluoro- ⁇ 2- [ (2i ⁇ -pyrrol-2-ylidene-kN) methyl] - lH-pyrrolato-kN ⁇ boron (BODIPY®) , diketopyrrolopyrrole, fluorindin, (poly) methine (in particular cyanin and styryl/hemicyanin) , naphthalimide, naphthanilide, naphthylamine (for instance dansyl) , oxadiazole, oxazine, perilone, perinone, perylene, polyene/carotenoid,
  • nitro chromophores A and/or A' that can be used according to the invention, mention may, in a nonlimiting manner, be made of the radicals derived from the following dyes: - 1 , 4-diamino-2-nitrobenzene
  • azo chromophores A and/or A' that can be used according to the invention, mention may be made of the radicals derived from the cationic azo dyes described in patent applications WO 95/15144, WO 95/01772 and EP 714954.
  • azine chromophores A and/or A' those listed in the Colour Index International are suitable, and for example the radicals derived from the following dyes :
  • indoamine chromophores A and/or A' that can be used according to the invention, mention may be made of the radicals derived from the following dyes:
  • the chromophores A and/or A' are chosen from those derived from dyes of azo, anthraquinone and hydrazone type.
  • the fluorescent chromophores A and/or A' are chosen from those derived from dyes of coumarin, (poly) methine (in particular cyanin and styryl/ hemicyanin) and naphthalimide type.
  • a and/or A' of the formulae (I) contain at least one cationic radical borne by or included in at least one of the chromophores .
  • the cationic radical is a quaternary ammonium.
  • cationic radicals are, for example, an alkylammonium, acridinium, benzimidazolium, benzobistriazolium, benzopyrazolium, benzopyridazinium, benzoquinolium, benzothiazolium, benzotriazolium, benzoxazolium, bipyridinium, bistetrazolium, dihydrothiazolium, imidazopyridinium, imidazolium, indolium, isoquinolium, naphthoimidazolium, naphthooxazolium, naphthopyrazolium, oxadiazolium, oxazolium, oxazolopyridinium, oxonium, phenazinium, phenooxazolium, pyrazinium, pyrazolium, pyrazoyltriazolium, pyridinium, pyridinoimidazolium, pyrrolium, pyrylium, quinol
  • the radicals A, A' in the formulae (I) or (II) comprise at least one cationic azo chromophore described, for example, in EP 850636, FR 2788433, EP 920856, WO 9948465, FR 2757385, EP 850637, EP 918053, WO 9744004, FR 2570946, FR 2285851, DE 2538363, FR 2189006, FR 1560664, FR 1540423, FR 1567219, FR 1516943, FR 1221122, DE 4220388, DE 4137005, WO 0166646, US 5708151, WO 9501772, WO 515144, GB 1195386, US 3524842, US 5879413, EP 1062940, EP 1133976, GB 738585, DE 2527638, FR 2275462, GB 1974- 27645, Acta Histochem.
  • M representing: a hydrogen atom, an alkali metal or an ammonium group or an ammonium group substituted with one or more identical or different, linear or branched, Ci-Cio alkyl radicals optionally bearing at least one hydroxyl .
  • the direct dye comprising a disulphide function is a cationic dye comprising at least one quaternary ammonium radical and such that, in formula (I) with p and p' equal to 1;
  • Ar represents a 5- or 6-membered
  • T represents -N(R)-, preferably in the para-position on Ar relative to the azo function, and T' represents an -N(R)- or -N + (R) (R 0 )- group or an imidazolium.
  • the disulphide dye is a cationic fluorescent dye comprising at least one fluorescent chromophore and one quaternary ammonium radical as defined in formula (I) with p and p' equal to 1:
  • Ar represents a 5- or 6-membered (hetero)aryl radical of phenyl or pyridium type, or a (hetero) aromatic bicycle of naphthyl, benzopyridinium, indolinyl or benzo- indolinyl type, optionally substituted with one or more halogen atoms, preferably chlorine or fluorine; with one or more alkyl groups, preferably Ci-C 4 alkyl groups; with one or more hydroxyl groups; with one or more alkoxy groups; with one or more hydroxyalkyl groups; with one or more amino or (di) alkylamino groups,
  • the disulphide dye is a cationic fluorescent dye comprising at least one quaternary ammonium radical and such that, in formula (I) with p and p' equal to 1, A and/or A' represent a naphthalimidyl radical of formula:
  • R e , R f , R g and R h which may be identical or different, represent a hydrogen atom or an optionally substituted C 1 -C 6 alkyl group.
  • W is an imidazolium, pyridinium, benzimidazolium, pyrazolium, benzothiazolium or quinolinium, optionally substituted with one or more Ci-C 4 alkyl radicals which may be identical or different.
  • G and G' which may be identical or different, represent an -NR c R d group, an -NR' c R' d group or a C 1 -C 6 alkoxy group which is optionally substituted, preferably unsubstituted; preferably, G and G' represent an -NR c R d group and an -NR' c R' d group, respectively;
  • R 1 , R 2 , R 3 and R 4 which may be identical or different, represent a hydrogen atom or an alkyl Ci-C 6 alkyl group;
  • R a and R' a which may be identical or different, represent an aryl (C 1 -C 4 ) alkyl group or a Ci-C 6 alkyl group optionally substituted with a hydroxyl group or an amino, Ci-C 4 alkylamino or Ci-C 4 dialkylamino group, it being possible for said alkyl radicals to form, with the nitrogen atom which bears them, a heterocyle comprising from 5 to 7 ring members, optionally comprising another heteroatom identical to or different from nitrogen; preferably, R a and R' a represent a C1-C3 alkyl group optionally substituted with a hydroxyl group, or a benzyl group;
  • R b and R' b which may be identical or different, represent a hydrogen atom, or an aryl (C 1 -C 4 ) alkyl group or a Ci-C 6 alkyl group which is optionally substituted; preferably, R b and R' b represent a hydrogen atom or a C 1 -C 3 alkyl or benzyl group;
  • R 0 , R' c , R d and R' d which may be identical or different, represent a hydrogen atom, an aryl (C 1 -C 4 ) alkyl group, a Ci-C 6 alkoxy group or a Ci-C 6 alkyl group which is optionally substituted;
  • R 0 , R' c , R d and R' d preferably represent a hydrogen atom, a hydroxyl group, a C1-C3 alkoxy group, an amino group, a C1-C3 (di) alkylamino group, or a C 1 -C 3 alkyl group which is optionally substituted with i) a hydroxyl group, ii) an amino group, iii) a C1-C3 (di) alkylamino group, or iv) a quaternary ammonium group (R") (R'") (R"”)N -; or else two adjacent radicals R c and R d
  • R e and R' e which may be identical or different, represent a linear or branched, optionally unsaturated, divalent, C 1 -C 6 alkylenyl hydrocarbon- based chain;
  • Rf and R' f which may be identical or different, represent a quaternary ammonium group
  • R" (R'") (R"")N + - represents an optionally substituted cationic heteroaryl group, preferably an imidazolinium group optionally substituted with a C1-C3 alkyl group;
  • R g , R' g , R" g , R'"g, R h , R'h, R"h and R"' h which may be identical or different, represent a hydrogen atom, a halogen atom, an amino, Ci-C 4 alkylamino, Ci-C 4 dialkylamino, cyano, carboxyl, hydroxyl or trifluoromethyl group, an acylamino, Ci-C 4 alkoxy, (poly) hydroxy (C2-C4) alkoxy, alkylcarbonyloxy, alkoxycarbonyl or alkylcarbonylamino radical, an acylamino, carbamoyl or alkylsulphonylamino radical, an aminosulphonyl radical, or a C1-C16 alkyl radical optionally substituted with a group chosen from C1-C12 alkoxy, hydroxyl, cyano, carboxyl, amino, Ci-C 4 alkylamino and Ci-C 4
  • R g and R' g ; R" g and R''' g ; R h , and R'h/ R"h and R'"h borne by two adjacent carbon atoms, together form a benzo or indeno ring or a fused heterocycloalkyl or fused heteroaryl group; the benzo, indeno, heterocycloalkyl or heteroaryl ring being optionally substituted with a halogen atom, an amino, Ci-C 4 alkylamino, Ci-C 4 dialkyl- amino, nitro, cyano, carboxyl, hydroxyl or trifluoromethyl group, an acylamino, Ci-C 4 alkoxy, (poly) hydroxy (C 2 -C 4 ) alkoxy, alkylcarbonyloxy, alkoxycarbonyl or alkylcarbonylamino radical, an acylamino, carbamoyl or alkylsulphonylamino radical, an aminosul
  • G represents -NR c R d and G' represents -NR' c R' d
  • two groups R c and R' g ; R' c and R" g ; R d and R g ; R' d and R'" g together form a saturated heteroaryl or heterocycle optionally substituted with one or more Ci-C 6 alkyl groups, preferably a heterocycle containing one or two heteroatoms chosen from nitrogen and oxygen and comprising between 5 and 7 ring members; more preferably, the heterocycle is chosen from morpholinyl, piperazinyl, piperidinyl and pyrrolidinyl groups;
  • R 1 , R' x , R" ⁇ and R"' ir which may be identical or different, represent a hydrogen atom or a Ci-C 4 alkyl group
  • Ri, R 2 , R 3 , R 4 , R'i, R' 2 , R' 3 and R' 4 which may be identical or different, represent a hydrogen atom or a Ci-C 4 alkyl, Ci-Ci 2 alkoxy, hydroxyl, cyano, carboxyl, amino, Ci-C 4 alkylamino or Ci-C 4 dialkylamino group, it being possible for said alkyl radicals to form, with the nitrogen atom which bears them, a heterocycle comprising from 5 to 7 ring members, optionally comprising another heteroatom identical to or different from nitrogen; preferably, Ri, R 2 , R 3 , R 4 , R'i, R' 2 , R' 3 and R' 4 are hydrogen atoms or an amino group; more preferably, R 1 , R 2 , R 3
  • T a and T b which may be identical or different, represent i) either a covalent ⁇ bond, ii) or one or more radicals or combinations thereof chosen from -SO 2 -, -0-, -S-, -N(R)-, -N + (R) (R 0 )- and -CO-, with R and R°, which may be identical or different, representing a hydrogen atom, a Ci-C 4 alkyl or Ci-C 4 hydroxyalkyl radical, or an aryl- (C 1 -C 4 ) alkyl; preferably, T a is identical to T 13 and they represent a covalent ⁇ bond or a group chosen from -N(R)-, -C(O)-N(R)-, -N(R)-C(O)-, -O-C(O)-, -C(O)-O- and -N + (R) (R 0 )-, with R and R°, which may be identical
  • heterocycles which may be identical or different, represent an optionally substituted heterocyclic group; preferably, the heterocycles are identical, monocyclic and saturated, and comprise in total two nitrogen atoms and from 5 to 8 ring members;
  • M' representing an anionic counterion derived from a salt of an organic or inorganic acid, or of an organic or inorganic base, providing the electroneutrality of the molecule.
  • anionic counterions which may be identical or different, preferably identical, representing anionic counterions. More particularly, the anionic counterion is chosen from halides such as chloride or bromide, and mesylate.
  • the dye composition that is of use in the invention contains, in a suitable cosmetic medium, an amount of dye(s) comprising a thiol, disulphide or protected-thiol function or functions as defined above of generally between 0.001% and 30% relative to the total weight of the composition. Preferably, this amount is between 0.01% and 5% by weight relative to the total weight of the composition.
  • the dye(s) is (are) present in an amount of between 0.01% and 2%.
  • siliceous compound (s) comprising a thiol function or functions according to the invention and the disulphide or protected-thiol dye(s) can generate the dye(s) by reductive cleavage of the disulphide function (s) -S-S- to -SH.
  • the direct dye according to the invention is a dye comprising a disulphide function or functions .
  • a "salt of an organic or inorganic acid” is more particularly chosen from a salt derived i) from hydrochloric acid HCl, ii) from hydrobromic acid HBr, i ⁇ ) from sulphuric acid H 2 SO 4 , iv) from alkyl- sulphonic acids: AIk-S(O) 2 OH, such as methylsulphonic acid and ethylsulphonic acid; v) from arylsulphonic acids: Ar-S(O) 2 OH, such as benzenesulphonic acid and toluenesulphonic acid; vi) from citric acid; vii) from succinic acid; viii) from tartaric acid; ix) from lactic acid; x) from alkoxysulphinic acids: AIk-O-S(O)OH, such as methoxysulphinic acid and ethoxysulphinic acid; xi) from aryloxysulphinic acids, such as tol
  • an "anionic counterion" is an anion or an anionic group associated with the cationic charge of the dye; more particularly, the anionic counterion is chosen from i) halides such as chloride or bromide; ii) nitrates; iii) sulphonates, among which are C 1 -C 6 alkyl sulphonates: AIk-S (O) 2 ⁇ ⁇ , such as methyl sulphonate or mesylate and ethyl sulphonate; iv) arylsulphonates : Ar-S(O)2 ⁇ ⁇ , such as benzene- sulphonate and toluenesulphonate or tosylate; v) citrate; vi) succinate; vii) tartrate; viii) lactate; ix) alkyl sulphates: AIk-O-S(O)O " , such as methyl sulphate and ethyl sulphate;
  • addition salts that can be used in the context of the invention are in particular chosen from addition salts with a cosmetically acceptable base, such as alkali metal hydroxides, for instance sodium hydroxide or potassium hydroxide, aqueous ammonia, amines or alkanolamines .
  • a cosmetically acceptable base such as alkali metal hydroxides, for instance sodium hydroxide or potassium hydroxide, aqueous ammonia, amines or alkanolamines .
  • the siliceous compound comprising a thiol function is an organic compound comprising one or more silicon atoms and one or more "free" thiol functions SH.
  • the siliceous compound according to the invention may be nonpolymeric siliceous compounds comprising a thiol function or functions or siliceous oligomers comprising a thiol function or functions, linear siliceous polymers comprising a thiol function or functions such as ⁇ , ⁇ -SH, nonlinear siliceous polymers comprising a thiol function or functions, including branched polymers comprising a thiol function or functions, hyperbranched polymers comprising a thiol function or functions, siliceous dendrimers comprising a thiol function or functions and crosslinked siliceous polymers comprising a thiol function or functions.
  • these compounds have in particular a molecular molar mass (MM) of greater than or equal to 200, and preferably ranging from 200 to 1000.
  • MM molecular molar mass
  • One particular embodiment of the invention concerns nonpolymeric siliceous compounds comprising a thiol function or functions.
  • the siliceous compounds comprising a thiol function or functions according to the invention contain from 1 to 15 silicon atom(s) per molecule, and preferably 1 silicon atom per molecule.
  • siliceous compounds comprising a thiol function or functions according to the invention contain in particular 1 to 12 -SH thiol group (s) per molecule, and preferably 1 to 2 -SH groups per molecule .
  • siliceous compounds comprising a thiol function or functions according to the invention
  • Ri, R2 and R3, which may be identical or different, represent: i) a hydrogen atom, or a group chosen from ⁇ ) hydroxyl, (C1-C20) alkyl, iv ) (C1-C20) alkenylene, v ) (C1-C20) alkoxy, vi ) (C3-C9) cycloalkyloxy, vi i ) optionally substituted aryl such as phenyl or naphthyl, vi i i ] aryloxy such as phenoxy, ix ) cycloalkyl such as cyclopentyl or cyclohexyl, cycloalkyloxy such as cyclopentyloxy or cyclohexyloxy,
  • substituents Ri, R2 and R3 form, together with the silicon atom which bears them, a fused bicyclic, optionally substituted, heterocycle comprising from 4 to 8 ring members, and bearing, particularly in the ⁇ -position with respect to the silicon, 1, 2 or 3 heteroatoms, preferably oxygen, said heterocycle being more particularly optionally substituted with a (C 1 -C 4 ) alkyl group;
  • X represents: i) a ⁇ bond, 11. a heteroatom such as oxygen or an NR group with R representing a hydrogen atom or a (C 1 -C 4 ) alkyl group, or else
  • X forms, with one of the substituents Ri, R2 or R 3 and the silicon atom which bears it, a heterocycle, particularly comprising 4-7 ring members, more particularly saturated and comprising 5 ring members, optionally substituted in particular with a carboxyl group;
  • ALK represents a C1-C20 alkylene chain
  • - which is optionally interrupted and/or terminated, in the ⁇ -position with respect to X, when X is other than a bond or a heteroatom, with: i) a heteroatom such as oxygen or sulphur; ii) a group chosen from -C(O)-, -N(R)-,
  • R and R' which may be identical or different, representing a hydrogen atom or a (C 1 -C 4 ) alkyl group; or iii) a monocyclic heterocycle comprising from 1 to
  • heteroatoms chosen from oxygen, sulphur or nitrogen, optionally substituted and comprising from 5 to 7 ring members, such as piperazine or piperidine;
  • x is an integer between 1 and 20, limits included, in particular between 1 and 10;
  • n is an integer between 1 and 3;
  • R'i, R' 2, R' 3, R' 4 and R' 5 which may be identical or different, represent: i) the same groups as Ri, R2 and R3 as defined above, ii) or a trisubstituted siloxane group R a R b R c Si-O- with R a , R b and R c , which may be identical or different, representing the same groups as Ri, R2 and R3 as defined above, iii) or a group R' a R' b R' c Si-O-Si (R' d ) (R' e ) -ALK"-, with ALK" being as defined for ALK above, and R' a , R' b , R' c , R' d and R' e , which may be identical or different, representing:
  • R" a R" b R" c Si-O- with R" a , R" b and R" c , which may be identical or different, representing a hydrogen atom or a (C 1 -C 4 )alkyl group;
  • ALK and ALK' which may be identical or different, represent a group as defined for ALK above;
  • X and X' which may be identical or different, represent : i ) a ⁇ bond, ii ) a heteroatom such as oxygen, or an NR group with R representing a hydrogen atom or a (C 1 -C 4 ) alkyl group;
  • ⁇ X, X' and X which may be identical or different, preferably identical, represent the same atoms or groups as X or X' defined above; in particular, X, X' and X" are identical, and more particularly X, X' and X" represent an oxygen atom;
  • R'i to R' 4 , and R"i to R" 4 which may be identical or different, are as R' i to R' 4 defined above, more particularly, R' to R' and R' to R" 4 , represent a (C 1 -C 4 ) alkyl, (C 1 -C 4 ) alkoxy, (C 5 -C 7 )- cycloalkyl, (C 5 -C 7 ) cycloalkyloxy, HS- (C1-C20) alkyl or HS- (C1-C20) alkoxy group, an aryl group such as phenyl, an aryloxy group such as phenoxy, or a group R a R b R c Si-O- with R a , R b and R 0 , which may be identical or different, representing a hydrogen atom or a (C 1 -C 4 ) alkyl group;
  • At least one SH function is on one of the groups R' 1 to R' 4 , and R"i to R" 4 .
  • the siliceous compounds comprising a thiol function or functions according to the invention are those of formula (A) .
  • siliceous compounds comprising a thiol function or functions that can be used according to the invention, mention may be made of the following compounds :
  • the siliceous compounds comprising a thiol function or functions according to the invention is 1-propanethiol, 3- (triethoxysilyl) - .
  • the concentration of siliceous compounds comprising a thiol function or functions is between 0.001% and 40% of the composition, preferably between 0.1% and 15%, preferably between 0.4% and 10%, this percentage being expressed as weight per weight. 3 .
  • the medi um The medi um :
  • the medium suitable for dyeing is a cosmetic medium generally constituted of water or of a mixture of water and one or more organic solvent (s) or of a mixture of organic solvents.
  • organic solvent is intended to mean an organic substance capable of dissolving another substance without chemically modifying it.
  • 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 phenoxy- ethanol, 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 phenoxy- ethanol, and mixtures thereof.
  • the solvents 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
  • the dye composition in accordance with the invention may also contain various adjuvants conventionally used in compositions for dyeing the hair, such as anionic, cationic, nonionic, amphoteric or zwitterionic surfactants, or mixtures thereof, anionic, cationic, nonionic, amphoteric or zwitterionic non-thiolated and siliceous polymers or blends thereof, inorganic or organic thickeners, and in particular anionic, cationic, nonionic and amphoteric polymeric associative thickeners, antioxidants, penetrating agents, sequestering agents, fragrances, buffers, dispersing agents, conditioning agents such as, for example, volatile or non-volatile and modified or non- modified silicones, film-forming agents, ceramides, preservatives or opacifiers.
  • adjuvants conventionally used in compositions for dyeing the hair, such as anionic, cationic, nonionic, amphoteric or zwitterionic surfactants, or mixtures
  • the above adjuvants are in general present in an amount of between, for each of them, 0.01% and 20% by weight relative to the weight of the composition.
  • the dye composition may, in addition, contain one or more additional direct dyes other than the disulphide or protected-thiol direct dyes.
  • These direct dyes are, for example, chosen from those conventionally used in direct dyeing, and among which mention may be made of all aromatic and/or nonaromatic dyes commonly used, such as neutral, acidic or cationic nitrobenzene direct dyes, neutral, acidic or cationic azo direct dyes, natural direct dyes, neutral, acidic or cationic quinone, and in particular anthraquinone, direct dyes, azine, triarylmethane and indoamine direct dyes, methines, styryls, porphyrins, metalloporphyrins, phthalocyanins, methine cyanins, and fluorescent dyes.
  • the additional direct dye(s) used according to the invention preferably represent (s) from 0.001% to 10% by weight, approximately, of the total weight of the dye composition, and even more preferably from 0.05% to 5% by weight approximately.
  • the dye composition may also contain one or more oxidation bases and/or one or more couplers conventionally used for dyeing keratin fibres.
  • oxidation bases mention may be made of para-phenylenediamines, bisphenylalkylenediamines, para-aminophenols, bis-para-aminophenols, ortho-amino- phenols and heterocyclic bases, and addition salts thereof.
  • couplers mention may in particular be made of meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalene couplers and 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
  • the 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 the addition salts with an acid, such as hydrochlorides, hydrobromides, sulphates, citrates, succinates, tartrates, lactates, tosylates, benzene- sulphonates, phosphates and acetates, and the addition salts with a base, such as alkali metal hydroxides, for instance sodium hydroxide or potassium hydroxide, aqueous ammonia, amines or alkanolamines .
  • an acid such as hydrochlorides, hydrobromides, sulphates, citrates, succinates, tartrates, lactates, tosylates, benzene- sulphonates, phosphates and acetates
  • a base such as alkali metal hydroxides, for instance sodium hydroxide or potassium hydroxide, aqueous ammonia, amines or al
  • the composition of the present invention contains at least one oxidation base and, optionally, at least one coupler, as defined above.
  • compositions may also comprise one or more oxidant (s) .
  • the oxidant may be chosen, for example, from hydrogen peroxide, urea peroxide, alkali metal bromates such as sodium bromate, persalts such as perborates and persulphates, and enzymes such as peroxidises and two- electron or four-electron oxidoreductases such as uricases, and 4-electron oxidases such as laccases.
  • hydrogen peroxide is particularly preferred.
  • the content of oxidant is in general between 1% and 40% by weight, relative to the weight of the composition, preferably between 1% and 20% by weight, relative to the weight of the composition.
  • the pH of the dye composition comprising the dye(s) is generally between 2 and 12 approximately, and preferably between 3 and 11 approximately. It can be adjusted to the desired value by means of acidifying or basifying agents customarily used in the dyeing of keratin fibres, or else using conventional buffer systems .
  • the pH of the composition according to the invention is preferably between 6 and 9.
  • inorganic or organic acids such as hydrochloric acid, orthophosphoric acid, sulphuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid or lactic acid, and sulphonic acids.
  • basifying agents mention may be made, by way of example, of aqueous ammonia, alkali metal carbonates, alkanolamines such as mono-, di- and triethanolamines, and also derivatives thereof, sodium hydroxide, 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 contains alkaline agents including at least monoethanolamine .
  • the dye composition may be in various galenical forms, such as in the form of a liquid, lotion, cream or gel, or in any other form suitable for dyeing keratin fibres. It may also be packaged under pressure in an aerosol bottle in the presence of a propellant and may form a foam. 4 The dyeing method
  • a subject of the invention is also a method of direct dyeing which comprises the application to keratin materials, in particular keratin fibres such as dark hair, of a dye composition containing one or more direct dye(s) comprising a disulphide function or functions and one or more siliceous compound (s) comprising a protected-thiol function or functions. After a leave-in time, the keratin fibres are rinsed, allowing coloured fibres to appear.
  • the leave-in time after application of the composition containing one or more direct dye(s) comprising a disulphide function or functions and one or more siliceous compound (s) comprising a thiol function or functions is fixed for between 5 minutes and 1 hour, preferably between 15 minutes and 1 hour.
  • composition may be obtained by extemporaneously mixing at least two compositions, one of which comprises one or more disulphide or thiol dye(s) comprising a protected-thiol function or functions, and the other of which comprises one or more siliceous compound (s) comprising a protected-thiol function or functions.
  • the dyeing method according to the invention comprises applying, with or without intermediate rinsing, to keratin materials, in particular keratin fibres such as dark hair, i) a dye composition comprising, in a cosmetic medium, one or more disulphide or protected-thiol dye(s) , in particular disulphide or protected-thiol fluorescent dye(s) , and ii) a composition comprising one or more siliceous compound (s) comprising a thiol function or functions.
  • the application may be carried out in any order.
  • the composition with the siliceous thiol is applied as a post-treatment.
  • the duration of the post-treatment with a siliceous compound comprising a protected-thiol function or functions may be short, for example from 1 second to 30 minutes, preferably from 1 minute to 15 minutes.
  • a dye comprising a protected-thiol function or functions of formula (I) comprises a group Y protecting the thiol function
  • the method of the invention may be preceded by a deprotection step aimed at restoring the SH function in situ.
  • the deprotection step may also be carried out during a step of pretreatment of the hair, for instance a reducing pretreatment of the hair.
  • a treatment with an oxidant may optionally be combined as a post-treatment.
  • Any type of oxidant that is 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 persulphates, 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 optional post-treatment with an oxidant is between 1 second and 40 minutes, 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 80 0 C, preferably between 20 and 60 0 C.
  • composition may be applied to dry hair, or the application may be preceded by wetting of the hair.
  • a subject of the invention is also a multicompartment dyeing device or dyeing "kit” in which a first compartment contains a dye composition comprising one or more disulphide or protected-thiol dye(s) , and a second compartment contains one or more siliceous compound (s) comprising a thiol function or functions. Said device may contain a third compartment comprising one or more oxidant (s) .
  • the disulphide direct dyes that are of use in the present invention are known compounds and can be prepared according to methods known to those skilled in the art, in particular using the methods described in application EP 1 647 580. DYEING EXAMPLE
  • Example 1 Synthesis of 2, 2' - ⁇ disulphanediylbis- [ethane-2, l-diylimino-4 , 1-phenylenediazene- 2, 1-diyl] ⁇ bis (1, 3-dimethyl-lH-imidazol-3- ium) dichloride [1]
  • the cystamine base (552.2 mg; 3.62 mmol) obtained from cystamine dihydrochloride by addition of sodium hydroxide and extraction with ethyl acetate, is solubilized in 2 ml of pentanol.
  • 2- [ (4-Methoxy- phenyl) diazenyl] -1, 3-dimethyl-lH-imidazol-3-ium chloride (2.42 mg; 9.1 mmol) in suspension in 80 ml of dichloromethane, is added. The mixture is brought to 50 0 C and stirred for 1 hour. It is concentrated under vacuum (elimination of dichloromethane) , 20 ml of water are added, and the reaction mixture is kept at 50 0 C for a further hour.
  • NW natural white
  • PW permanent-waved white
  • Compositions 1 and 2 are applied to the NW or PW hair, followed by a leave-in time of 25 minutes at ambient temperature (22.6°C) . The locks are then rinsed and then dried.
  • the colour of the locks after dyeing was evaluated in the L*a*b* system by means of a MINOLTA® CM2600D spectrophotometer .
  • the three parameters denote, respectively, the intensity (L*) , the shade (a*) and the saturation (b*) .
  • L* intensity
  • a* shade
  • b* saturation

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Abstract

La présente invention concerne une composition comprenant i) un ou plusieurs colorant(s) direct(s) comprenant une fonction ou des fonctions disulfure ou comprenant une fonction ou des fonctions thiol protégée(s), et ii) un ou plusieurs composés siliceux comprenant une fonction ou des fonctions thiol, utilisée pour colorer des fibres de kératine, en particulier des fibres de kératine humaines telles que les cheveux. Elle concerne en outre un procédé de coloration de fibres de kératine utilisant ladite composition et l’utilisation de colorants directs comprenant une fonction disulfure ou thiol protégée associée aux composés siliceux comprenant des fonctions thiol, dans la coloration et l'éclaircissement de fibres de kératine. Cette composition permet de produire de nouveaux systèmes pour une coloration très intense et homogène des cheveux, qui sont résistants à des agents externes et qui n’altèrent pas les propriétés cosmétiques de fibres de kératine.
PCT/EP2009/051786 2008-02-29 2009-02-16 Composition pour colorer des fibres de kératine comprenant au moins un colorant direct comprenant une fonction disulfure/thiol protégée et au moins un composé siliceux comprenant une fonction thiol et procédé utilisant la composition Ceased WO2009109457A2 (fr)

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EP09716887A EP2259766A2 (fr) 2008-02-29 2009-02-16 Composition pour colorer des fibres de kératine comprenant au moins un colorant direct comprenant une fonction disulfure/thiol protégée et au moins un composé siliceux comprenant une fonction thiol et procédé utilisant la composition

Applications Claiming Priority (4)

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FR0851338A FR2928087B1 (fr) 2008-02-29 2008-02-29 Composition pour la coloration de fibres keratiniques comprenant au moins un colorant direct a fonction disulfure/thiol protege et au moins un compose silicie a fonction thiol et procede utilisant la composition.
FR0851338 2008-02-29
US6445408P 2008-03-06 2008-03-06
US61/064,454 2008-03-06

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WO2012113720A3 (fr) * 2011-02-25 2012-12-13 L'oreal Composition de coloration de fibres kératiniques comprenant un colorant direct présentant un groupe fonctionnel disulfure/thiol, un polymère épaississant, un alcool gras éthoxylé et/ou un tensioactif non ionique, un agent alcalin et un agent réducteur
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WO2017036268A1 (fr) * 2015-08-29 2017-03-09 Si-Novation Ltd Silice modifiée avec des groupes fonctionnels polyorganiques, ses procédés de fabrication et son utilisation
CN110099669A (zh) * 2016-12-22 2019-08-06 莱雅公司 蒽醌染料和荧光染料用于染色角蛋白纤维的用途，染色方法及组合物
JP2020132772A (ja) * 2019-02-21 2020-08-31 三菱瓦斯化学株式会社 硫黄系有機材料、及び該硫黄系有機材料により表面修飾を施した無機材料
WO2023067170A1 (fr) * 2021-10-21 2023-04-27 Fundació Institut De Bioenginyeria De Catalunya Composés pour le traitement du paludisme
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Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62255413A (ja) * 1986-04-28 1987-11-07 Kao Corp 加温式毛髪変形用処理剤
DE69200991T2 (de) * 1991-04-04 1995-07-06 Dow Corning Grundierung für Nagellacke sowie dessen Verfahren.
US5776454A (en) * 1996-09-13 1998-07-07 Dow Corning Corporation Permanent waving with mercaptosilicones
EP1143916A2 (fr) * 1999-01-08 2001-10-17 The Procter & Gamble Company Compositions topiques comprenant des thiols fonctionnels proteges
MXPA06011502A (es) * 2004-04-08 2006-12-15 Ciba Sc Holding Ag Tintes de disulfuro, composicion que comprende los mismos y metodo para tenir el pelo.
FR2876576B1 (fr) * 2004-10-14 2006-12-08 Oreal Composition de teinture comprenant un colorant disulfure particulier et procede de coloration des fibres keratiniques humaines a partir de ce colorant

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FR2971939A1 (fr) * 2011-02-25 2012-08-31 Oreal Composition pour colorer les fibres keratiniques comprenant un colorant direct a fonction disulfure/thiol, un corps gras, un agent alcalin, et un agent reducteur
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WO2012113720A3 (fr) * 2011-02-25 2012-12-13 L'oreal Composition de coloration de fibres kératiniques comprenant un colorant direct présentant un groupe fonctionnel disulfure/thiol, un polymère épaississant, un alcool gras éthoxylé et/ou un tensioactif non ionique, un agent alcalin et un agent réducteur
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FR2971934A1 (fr) * 2011-02-25 2012-08-31 Oreal Composition pour colorer les fibres keratiniques comprenant un colorant direct a fonction disulfure/thiol, un polymere epaississant, un alcool gras ethoxyle, un agent alcalin, et un agent reducteur
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FR2971935A1 (fr) * 2011-02-25 2012-08-31 Oreal Composition pour colorer les fibres keratiniques comprenant un colorant direct a fonction disulfure/thiol, un polymere epaississant, un tensioactif non ionique, un agent alcalin, et un agent reducteur
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RU2680068C2 (ru) * 2013-09-02 2019-02-14 Л'Ореаль Способ окрашивания кератиновых волокон с применением катионных стириловых дисульфидных красителей и композиция, содержащая указанные красители
WO2015059368A1 (fr) * 2013-09-02 2015-04-30 L'oreal Procede de coloration des fibres keratiniques a partir de colorants cationiques styryles disulfures, et composition comprenant lesdits colorants
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KR20190094212A (ko) * 2016-12-22 2019-08-12 로레알 케라틴 섬유의 염색에 있어서의 안트라퀴논 염료 및 형광 염료의 용도, 염색 방법 및 조성물
US20230240954A1 (en) * 2016-12-22 2023-08-03 L'oreal Use of anthraquinone dyes and of fluorescent dyes for dyeing keratin fibres, dyeing process and composition
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JP7263826B2 (ja) 2019-02-21 2023-04-25 三菱瓦斯化学株式会社 硫黄系有機材料、及び該硫黄系有機材料により表面修飾を施した無機材料
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FR2928087A1 (fr) 2009-09-04
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EP2259766A2 (fr) 2010-12-15

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