WO2012069476A1 - Nouveaux colorants directs contenant une unité à base d'acide ascorbique, composition de colorant comprenant ces derniers et procédé de coloration d'éléments humains à base de kératine à l'aide de ces colorants - Google Patents

Nouveaux colorants directs contenant une unité à base d'acide ascorbique, composition de colorant comprenant ces derniers et procédé de coloration d'éléments humains à base de kératine à l'aide de ces colorants Download PDF

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WO2012069476A1
WO2012069476A1 PCT/EP2011/070686 EP2011070686W WO2012069476A1 WO 2012069476 A1 WO2012069476 A1 WO 2012069476A1 EP 2011070686 W EP2011070686 W EP 2011070686W WO 2012069476 A1 WO2012069476 A1 WO 2012069476A1
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alkyl
group
radical
hydrogen atom
crc
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PCT/EP2011/070686
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Andrew Greaves
Nicolas Daubresse
Frédéric Guerin
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L'oreal
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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
    • 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
    • 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
    • A61K8/4973—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
    • 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
    • C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
    • C09B1/16—Amino-anthraquinones
    • C09B1/20—Preparation from starting materials already containing the anthracene nucleus
    • C09B1/26—Dyes with amino groups substituted by hydrocarbon radicals
    • C09B1/28—Dyes with amino groups substituted by hydrocarbon radicals substituted by alkyl, aralkyl or cyclo alkyl 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
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/02—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups
    • C09B23/04—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups one >CH- group, e.g. cyanines, isocyanines, pseudocyanines
    • 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
    • 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
    • C09B26/00—Hydrazone dyes; Triazene dyes
    • C09B26/02—Hydrazone dyes
    • C09B26/04—Hydrazone dyes cationic
    • 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
    • C09B62/80—Anthracene dyes
    • 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
    • C09B62/825—Monoazo 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

Definitions

  • the invention relates to the dyeing of keratin materials using dyes bearing an ascorbic acid-based unit of formula (I), particularly bearing 3,4-dihydroxyfuran-2(5H)- one and 2,3,4(5H)-furantrione units.
  • the direct dyes that are conventionally used are, for example, dyes of the nitrobenzene type, anthraquinone dyes, nitropyridines and dyes of the azo, xanthene, acridine, azine or triarylmethane type.
  • the colorations that result from the use of direct dyes are temporary or semi-permanent colorations, since the nature of the interactions that bind the direct dyes to the keratin fibre, and their desorption from the surface and/or the core of the fibre, are responsible for their poor dyeing power and their poor fastness with respect to washing or to perspiration.
  • Oxidation bases which are colourless before oxidation such as ortho- or para-phenylenediamines, ortho- or para-aminophenols and heterocyclic compounds; and which, in the presence of oxidizing agents, colour the hair.
  • Oxidation bases may be mixed with couplers to obtain varied shades.
  • This oxidation dyeing process consists in applying to the keratin fibres bases or a mixture of bases and couplers with aqueous hydrogen peroxide solution, as oxidizing agent, in leaving it to diffuse, and then in rinsing the fibres. Oxidation dyeing systems make it possible to obtain base colorations that are relatively shampoo-fast, but do not make it possible to obtain chromatic shades.
  • a chemical bleaching process is performed. This process consists in treating the keratin fibres, such as the hair, with a strong oxidizing system, generally constituted by hydrogen peroxide optionally combined with persalts, usually in an alkaline medium.
  • This bleaching system has the drawback of degrading keratin fibres and of impairing their cosmetic properties. Specifically, the fibres have a tendency to become coarse, more difficult to disentangle and more brittle. Finally, the lightening or bleaching of keratin fibres with oxidizing agents is incompatible with treatments for changing the shape of said fibres, particularly relaxing treatments.
  • Another lightening technique consists in applying to dark hair fluorescent direct dyes. This technique, described especially in documents WO 03/028 685 and WO 2004/091 473, makes it possible to respect the quality of the keratin fibre during the treatment. However, these fluorescent direct dyes do not have sufficient fastness with respect to external agents.
  • Vitamins are compounds that are essential for the body, one of which, vitamin C, also known as ascorbic acid [50-81-7], l-ascorbic acid, l-xylo-ascorbic acid or l-threo- hex-2-enoic acid ⁇ -lactone, is known for its anti-scurvy virtues.
  • Ascorbic acid is also known as an antioxidant (see, for example, Ullmann's Encylopedia of Industrial Chemistry; "Vitamins", 2005 Wley-VCH Verlag GmbH & Co. KGaA, Weinheim 10.1002/14356007.a27 443 (pp. 110-122), or US 2006/0 039 937), an antithrombotic protective agent (see, for example, US 4 329 290), or an anticancer agent (see, for example, EP 0 875 246).
  • ascorbic acid derivatives have been used for functionalizing matrices such as ultraviolet screening agents (WO 2008/017346).
  • the aim of the present invention is to provide novel systems for the direct dyeing of keratin materials and for especially lightening dark keratin materials, in particular human keratin fibres such as the hair, which are powerful, remanent and easy to use.
  • one name of the invention is to provide direct dyeing systems for obtaining lightening effects especially on keratin materials such as naturally or artificially dark keratin fibres, which are fast with respect to successive shampooing, which do not degrade the keratin fibres and which do not impair their cosmetic properties.
  • Another aim of the invention is to dye keratin materials, especially keratin fibres such as the hair, in a manner that is intense, strong, chromatic and/or remanent with respect to external attacking factors.
  • the invention is also directed towards providing compounds for dyeing keratin fibres such as the hair with little coloration selectivity between the root and the end, whether it is performed on natural or permanent-waved fibres.
  • organic or mineral acid salts such as hydrates, thereof;
  • A represents a coloured chromophore
  • Asc represents a radical derived from ascorbic acid chosen from ascorbyl and dehydroascorbyl radicals, chosen from formulae (11-1 ) to (II-4), and which is linked to the rest of the molecule via one of the substituents R 5 , Re, R 7 , Re or Rg, or alternatively the said radical is linked to the rest of the molecule directly via one of the carbon atoms bearing the substituents R 5 , R 6 , R , Rs or R 9 , in which case one of these substituents is absent:
  • R 5 , R 6 , R 7 , Re, R9 and R 0 which may be identical or different, represent a hydrogen atom or a group chosen from i) (d-C 8 )alkyl, N) hydroxyl, iii) carboxyl, iv) and -O-protected with a protecting group;
  • R 5 and R 9 together form a divalent group -0-(CR a Rb) n -0- with R a and R , which may be identical or different, representing a hydrogen atom or a group (C C 8 ) alkyl such as methyl or t-butyl, (C C 8 )alkoxy, allyl, (poly)halo(CrC 8 )alkyl such as trifluoromethyl, and n is equal to 1 , 2 or 3, and in particular R 5 and R 9 together form a divalent group -0-CH 2 -CH 2 -0- or -0-C(CH 3 ) 2 -0-;
  • Rn and R 2 which may be identical or different, a hydrogen atom, an alkali metal, an alkaline-earth metal or a protecting group,
  • Rn and R 2 together form a divalent group -(CR a Rb) n - with R a and R , and n as defined previously;
  • ⁇ Y represents an oxygen or sulfur atom
  • X and X' which may be identical or different, represent:
  • the divalent group(s) or combinations thereof are chosen from -0-; -N(R)-; -C(O)- with R chosen from a hydrogen atom and a C C 4 alkyl radical; > p and p', which may be identical or different, represent an integer equal to 0 or 1 ; and
  • C S at represents a linear or branched, optionally cyclic C Ci 8 alkylene chain.
  • Another subject of the invention concerns a process for dyeing and/or lightening keratin materials, particularly keratin fibres, especially dark fibres, in which a suitable dye composition comprising one or more direct dyes bearing a group derived from ascorbic acid of formula (I) as defined previously is applied to the said materials.
  • Another subject of the invention is a dye composition
  • a dye composition comprising, in a cosmetically suitable medium, at least one direct dye bearing a unit derived from ascorbic acid of formula (I) as defined previously.
  • Another subject of the invention concerns a direct dye bearing a unit derived from ascorbic acid of formula (I) as defined previously.
  • the direct dyes of formula (I) afford fast coloration on keratin fibres.
  • the coloration, especially using the compounds of formula (I) with A representing a fluorescent coloured chromophore, is also visible on keratin materials that are even dark, in particular human keratin fibres, especially the hair, without degrading the said material, remanent with respect to shampooing, common attacking factors (sunlight or perspiration), and other hair treatments, even in the absence of a reducing agent.
  • the direct dyes of formula (I) afford lightening of keratin materials such as keratin fibres, particularly dark keratin fibres and more particularly dark hair, in general with a tone depth of less than or equal to 6, preferably less than or equal to 4.
  • the dyes of formula (I) according to the invention are moreover stable with respect to oxidizing agents, and show satisfactory solubility cosmetic dyeing media. These dyes especially broaden the colour range from yellow to blue.
  • the dyes of formula (I) colour keratin materials after application to keratin fibres in a manner that is strong, intense, chromatic and/or remanent with respect to external attacking factors, with low coloration selectivity between the root, and on different types of fibre, do not necessarily oblige a reductive treatment of the fibres or any chemical oxidizing agent, and which are visible on the said materials, even dark materials.
  • the term "dark keratin fibres", particularly naturally or artificially dark hair, means hair whose tone depth is less than or equal to 6 (dark blond) and preferably less than or equal to 4 (chestnut-brown).
  • the lightening of the hair is evaluated by the "tone depth” variation before and after application of the compound of formula (I).
  • tone is based on the classification of natural shades, one tone separating each shade from the shade immediately following or preceding it. This definition and the classification of natural shades are well known to hairstyling professionals and are published in the book Sciences des.s capillaires [Hair treatment sciences] by Charles Zviak, 1988, published by Masson, pp. 215 and 278.
  • the tone depths range from 1 (black) to 10 (very light blond), one unit corresponding to one tone; the higher the figure, the lighter the shade.
  • the term "bleached hair” means hair whose tone depth is greater than 4 (chestnut-brown) and preferably greater than 6 (dark blond).
  • 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 reflectance of the hair.
  • the curve corresponding to the treated hair should show a reflectance in the wavelength range from 500 to 700 nanometers higher than the curve corresponding to the untreated hair.
  • the wavelength at which the difference is maximal between the reflectance curve for the treated hair and that for the untreated hair is in the wavelength range from 500 to 650 nanometers and preferably in the wavelength range 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 borne by a carbon atom, chosen from:
  • a C1-C16 and preferably C C C 8 alkyl radical optionally substituted with one or more radicals chosen from hydroxyl, C C 2 alkoxy, C 2 -C 4 (poly)hydroxyalkoxy, acylamino, amino substituted with two C 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 saturated or unsaturated, optionally substituted 5- to 7-membered and preferably 5- or 6- membered heterocycle optionally comprising another heteroatom identical to or different from nitrogen;
  • halogen atom such as chlorine, fluorine or bromine
  • an optionally cationic 5- or 6-membered heteroaryl radical preferentially imidazolium, optionally substituted with a (C C 4 )alkyl radical, preferentially methyl;
  • an optionally cationic 5- or 6-membered heteroaryl radical preferentially imidazolium, optionally substituted with a (C C 4 )alkyl radical, preferentially methyl;
  • an acylamino radical (-NR-COR') in which the radical R is a hydrogen atom or a Ci-C 4 alkyl radical optionally bearing at least one hydroxyl group and the radical R' is a C C 2 alkyl radical;
  • the carboxylic radical possibly being in acid or salified form (preferably with an alkali metal or a substituted or unsubstituted ammonium);
  • an alkylsulfonylamino radical (R'S0 2 -NR-) in which the radical R represents a hydrogen atom or a C C 4 alkyl radical optionally bearing at least one hydroxyl group and the radical R' represents a C C 4 alkyl radical or a phenyl radical;
  • ⁇ an aminosulfonyl radical ((R) 2 N-S0 2 -) in which the radicals R, which may be identical or different, represent a hydrogen atom or a C C 4 alkyl radical optionally bearing at least one hydroxyl group;
  • cyclic or heterocyclic part of a non-aromatic radical may be substituted with at least one substituent borne by a carbon atom, chosen from the groups:
  • alkylcarbonylamino ((RCO-NR'-) in which the radical R' is a hydrogen atom or a Ci-C 4 alkyl radical optionally bearing at least one hydroxyl group, and the radical R is a C C 2 alkyl radical or an amino radical substituted with two C C 4 alkyl groups, which may be identical or different, optionally bearing at least one hydroxyl group, the said alkyl radicals possibly forming, with the nitrogen atom to which they are attached a saturated or unsaturated, optionally substituted 5- to 7-membered heterocycle optionally comprising at least one other nitrogen or non-nitrogen heteroatom;
  • alkylcarbonyloxy in which the radical R is a C C 4 alkyl radical or an amino radical substituted with one or two identical or different C C 4 alkyl groups optionally bearing at least one hydroxyl group, the said alkyl radicals possibly forming with the nitrogen atom to which they are attached a saturated or unsaturated, optionally substituted 5- to 7-membered heterocycle, optionally comprising at least one other heteroatom identical to or different from nitrogen;
  • alkylcarbonyloxy in which the radical R is a C C 4 alkyl radical or an amino radical substituted with one or two identical or different C C 4 alkyl groups optionally bearing at least one hydroxyl group, the said alkyl radicals possibly forming with the nitrogen atom to which they are attached a saturated or unsaturated, optionally substituted 5- to 7-membered heterocycle, optionally comprising at least one other heteroatom identical to or different from nitrogen; a cyclic or heterocyclic radical, or a non-aromatic portion 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 fused or non-fused monocyclic or polycyclic group containing from 6 to 22 carbon atoms, and in which at least one ring is aromatic; preferentially, the aryl radical is a phenyl radical or an amino radical substitute
  • the charge when the charge is endocyclic, it is included in the electron derealization via the mesomeric effect, for example it is a pyridinium, imidazolium or indolinium
  • R and R' being a heteroaryl substituent as defined previously and particularly a (hydroxy)(CrC 8 )alkyl group such as methyl;
  • G represents a covalent ⁇ bond, or a divalent group or the combination chosen from: -N(R)-; -N + (R')(R")-, Q " ; -0-; -S-; -C(O)-; -S(0) 2 - with R' and R", which may be identical or different, representing a hydrogen atom or a group (hydroxy)(CrC 6 )alkyl and Q " represents an anionic counterion;
  • alk represents an alkylene group
  • G represents -N(R')- with R' chosen from a hydrogen atom and a C C 4 alkyl radical;
  • cationic aryl bearing an exocyclic charge means an aralkyi ring whose cationic group is outside the said ring: it is especially an ammonium or phosphonium substituent R + such as trimethylammonium outside the aryl such as phenyl or naphthyl:
  • a "cyclic radical” is a non-aromatic, monocyclic or polycyclic, fused or non-fused cycloalkyl radical, containing from 5 to 22 carbon atoms, which may comprise one or more unsaturations;
  • a "heterocyclic radical” is a non-aromatic, monocyclic or polycyclic, fused or non- fused 5- to 22-membered radical, comprising from 1 to 6 heteroatoms chosen from nitrogen, oxygen, sulfur and selenium atoms, morpholinyl, thiomorpholinyl, piperidyl, piperazinyl, pyrrolidinyl, tetrahydrofuryl, tetrahydr
  • the said "protecting group” is chosen from:
  • aryl for instance halophenyl such as para-chlorophenyl,
  • heteroaryl such as optionally /V-oxidized pyridine, for instance /V-oxido-3- methyl-2-picolyl or anthryl,
  • tetrahydropyranyl THP tetrahydropyranyl
  • THTP tetrahydrothiopyranyl
  • S- mono or S,S- dioxide tetrahydropyranyl
  • 4-methoxyTHP 4-methoxyTHTP
  • tetrahydrofuryl THF
  • aryl-heteroaryl such as 9-(9-phenyl)xanthenyl, 9-(9-phenyl-10-oxo)anthryl (tritylone),
  • n) mono/di/tri(CrC 8 )alkylsilyl such as trimethylsilyl (TMS), triethylsilyl, isopropyldimethylsilyl, methyldiisopropylsilyl, t-butyldimethylsilyl or triisopropylsilyl,
  • triarylsilyl such as triphenylsilyl
  • triaryl(CrC 8 )alkyl such as tribenzylsilyl, (triphenyl)dimethylsilyl, tri-para- xylylsilyl;
  • R-C(Y)- with o R representing 1) a hydrogen atom, or 2) a group (d-C 8 )alkyl such as methyl, 3) (poly)halo(aryl)(CrC 8 )alkyl such as chloromethyl, dichloromethyl, trichloromethyl or trifluoromethyl or chlorodiphenylmethyl, 4) (C C 8 )alkoxy such as methoxy, ethoxy, isobutoxy, 5) (aryl)(C 2 -C 8 )alkenyloxy such as vinyloxy, allyloxy, or cinnamyloxy, 6) (poly)halo(CrC 8 )alkoxy such as trichloroethoxy, 7) (C 2 - C 8 )alkenyl, 6) (Ci-C 8 )alkoxy(CrC 8 )alkyl such as methoxymethyl, 8) (poly)aryl(Ci-C 8 )alkyl such
  • o Y representing an oxygen or sulfur atom or a group R'N or R'R"N + , Q " with R' and R", which may be identical or different, representing a hydrogen atom or a group (CrC 8 )alkyl and Q " representing an organic or mineral anionic counterion;
  • R' and R which may be identical or different, representing 1) a hydrogen atom, or 2) a hydroxyl group, 3) (CrC 8 )alkoxy, 4) (C 2 - C 8 )alkenyloxy such as vinyloxy, 6) aryl such as 2,4,6- trimethylphenyl or mesityl, 7) aryl(CrC 8 )alkyl, the aryl group being optionally substituted with one or more groups (CrC 8 )alkyl such as benzyl or 2,4,6- trimethylbenzyl, 8) aryloxy such as phenoxy, 9) aryloxy(CrC 8 )alkyl such as phenoxymethyl, 10) cycloalkyl such as adamantyl, 11) heterocycloalkyl, 12) heteroaryl, or 13) (di)(CrC 8 )(alkyl)amino such as dimethylamino;
  • alkyl radical is a linear or branched C Ci 6 and preferably C C 8 hydrocarbon-based radical; particularly C C 4 such as methyl or ethyl;
  • the expression "optionally substituted” attributed to the alkyl radical means that the said alkyl radical may be substituted with one or more radicals chosen from the following radicals: i) hydroxyl, ii) C C 4 alkoxy, iii) acylamino, iv) amino optionally substituted with one or two identical or different C C 4 alkyl radicals, the said alkyl radicals possibly forming with the nitrogen atom that bears them a 5- to 7-membered heterocycle, optionally comprising another heteroatom identical to or different from nitrogen; v) or a quaternary ammonium group -N + R'R"R"', M " for which R', R" and R'", which may be identical or different, represent a hydrogen atom or a C C 4 alkyl group, or else -N + R'R"R"', forms a heteroaryl such as imidazolium optionally substituted with a C C 4 alkyl group, and M " represents the organic or mineral
  • the compounds of formula (I) according to the invention may be cationic, anionic or neutral;
  • one or more groups in the compound can ensure the electrical neutrality, for example if the rest of the compound is cationic, with groups -O " (oxalate), -COO " (carboxylate), R 3 N + - (ammonium), or R 3 P + - (phosphonium); - when the compound is anionic, then the organic or mineral counterion(s) are cationic, preferentially chosen from mineral cations such as alkali metals or alkaline-earth metals such as Na, Mg, K and Ca, and organic cations such as ammonium NH 4 + or (di/tri)(CrC 8 )alkylammonium,
  • the counterion(s) are anionic species, preferentially chosen from i) halides such as chloride or bromide; ii) nitrates; iii) sulfonates, including C C 6 alkylsulfonates; Alk-S(0) 2 0 " such as methanesulfonate or mesylate, and ethanesulfonate; iv) arylsulfonates: Ar- S(0) 2 0 " such as benzenesulfonate and toluenesulfonate or tosylate; v) citrate; vi) succinate; vii) tartrate; viii) lactate; ix) alkyl sulfites: Alk-0-S(0)0 " such as methyl sulfite and ethyl sulfite; x) aryl sulfites: Ar-0-S(0)0 " such as benzene s
  • an "organic or mineral acid salt” is more particularly chosen from a salt derived from i) hydrochloric acid HCI, ii) hydrobromic acid HBr, iii) sulfuric acid H 2 S0 4 , iv) alkylsulfonic acids: Alk-S(0) 2 OH such as methanesulfonic acid and ethanesulfonic acid; v) arylsulfonic acids: Ar-S(0) 2 OH such as benzenesulfonic acid and toluenesulfonic acid; vi) citric acid; vii) succinic acid; viii) tartaric acid; ix) lactic acid; x) alkoxysulfinic acids: Alk-0-S(0)OH such as methoxysulfinic acid and ethoxysulfinic acid; xi) aryloxysulfinic acids such as tolueneoxysulfinic acid and phenoxysulfinic acid; xii)
  • coloured chromophore means a radical derived from a dye, i.e. which has the capacity of colouring and which is in the form of a coloured compound that may be observed with the naked eye (absorbing light at a wavelength in the UV and visible radiation range, i.e. at a wavelength ab s of between 250 and 800 nm, particularly in the visible spectrum between 400 and 700 nm).
  • the dye absorbs in the yellow, orange, red, violet or blue range (see, for example, Ullmann's Encyclopedia of Industrial chemistry "Dyes, General Survey", 2005 Wiley-VCH Verlag GmbH & Co. KgaA, Weinheim10.1002/14356007.a09_073 and Color Chemistry, Synthesis, Properties, and Applications of Organic Dyes and Pigments, H. Zollinger, 2003, 3rd Ed. Verlag Helvetica Chimica Acta, Wiley-VCH, chap. 1.1 and 2.1).
  • the term "fluorescent chromophore” means a radical derived from a fluorescent dye as defined previously, which, besides being a dye, i.e.
  • a fluorescent dye is especially a compound that is capable of absorbing UV or visible radiation at a wavelength ab s of between 400 and 700 nm and capable of re-emitting in the visible range at an emission wavelength em of between 410 and 800 nm.
  • fluorescent compounds are dyes that are capable of absorbing in the visible range ab s between 400 and 800 nm and of re-emitting in the visible range em between 410 and 810 nm. More preferentially, fluorescent dyes are dyes that are capable of absorbing at a ab s of between 420 and 550 nm and of re-emitting in the visible range em between 470 and 600 nm.
  • the radical A of formula (I) may contain one or more chromophores, which may be identical or different, it being understood that at least one chromophore is coloured.
  • coloured chromophores that are useful, mention may be made of those derived from the following dyes: acridines; acridones; anthrapyrimidines; anthraquinones; azines; (poly)azos, hydrazono or hydrazones, in particular arylhydrazones; azomethines; benzanthrones; benzimidazoles; benzimidazolones; benzindoles; benzoxazoles; benzopyrans; benzothiazoles; benzoquinones; bisazines; bis-isoindolines; carboxanilides; coumarins; cyanins such as zerocyanins, azacarbocyanins, diazacarbocyanins, diazahemicyanins, hemicyanin, or tetraazacarbocyanins; diazines; diketopyrrolopyrroles; dioxazines; diphenylamines;
  • polymethines such as dimethines of stilbene or styryl type; naphthalimides; naphthanilides; naphtholactams; naphthoquinones; nitro, especially nitro(hetero)aromatics; oxadiazoles; oxazines; perilones; perinones; perylenes; phenazines; phenoxazine; phenothiazines; phthalocyanin; polyenes/carotenoids; porphyrins; pyranthrones; pyrazolanthrones; pyrazolones; pyrimidinoanthrones; pyronines; quinacridones; quinolines; quinophthalones; squaranes; tetrazoliums; thiazines, thioindigo; thiopyronines; triarylmethanes, or xanthenes.
  • chromophore A is chosen from those derived from (poly)azo dyes such as (di)azo, hydrazono dyes and (poly)methine dyes such as styryls and anthraquinones.
  • the coloured chromophore A is chosen from cationic chromophores, preferentially those known as
  • Het + represents a cationic heteroaryl radical, preferably bearing an endocyclic cationic charge, such as imidazolium, indolium or pyridinium, optionally substituted with one or more (C C 8 ) alkyl groups such as methyl;
  • Ar + represents an aralkyi radical, such as phenyl or naphthyl, bearing an exocyclic cationic charge, particularly tri(CrC 8 )alkylammonium such as trimethylammonium;
  • Ar represents an aryl group, especially phenyl, optionally substituted, preferentially with one or more electron-donating groups such as i) optionally substituted (C C 8 )alkyl, ii) optionally substituted (C C 8 )alkoxy, iii) (di)(CrC 8 )(alkyl)amino optionally substituted on the alkyl group(s) with a hydroxyl group, iv) aryl(CrC 8 )alkylamino, v) optionally substituted A/-(Ci-C 8 )alkyl-A/-aryl(CrC 8 )alkylamino or alternatively Ar represents a julolidine group;
  • - Ar is an optionally substituted divalent (hetero)alkylene group such as phenylene, particularly para-phenylene, or naphthalene, which are optionally substituted, preferentially with one or more groups (CrC 8 )alkyl, hydroxyl or (CrC 8 )alkoxy;
  • - Ar" is an optionally substituted (hetero)aryl group such as phenyl or pyrazolyl, which are optionally substituted, preferentially with one or more groups (CrC 8 )alkyl, hydroxyl, (di)(CrC 8 )(alkyl)amino, (CrC 8 )alkoxy or phenyl;
  • R a and R b which may be identical or different, represent a hydrogen atom or a group (d-Cs)alkyl, which is optionally substituted, preferentially with a hydroxyl group;
  • R a with a substituent of Het + and/or R b with a substituent of Ar form, together with the atoms that bear them, a (hetero)cycloalkyl; particularly, R a and R b represent a hydrogen atom or a group (CrC 4 )alkyl, which is optionally substituted with a hydroxyl group;
  • - Q " represents an anionic counterion such as a halide or an alkyl sulfate
  • chromophore (III), ( ⁇ ), (IV), (IV) or (V) is linked to the rest of the molecule of formula (I) via Het + , Ar + , Ar or Ar".
  • R 1 representing a group (C C 4 )alkyl such as methyl
  • R 2 and R 3 which may be identical or different, representing a hydrogen atom or a group (Ci-C 4 )alkyl such as methyl;
  • R 4 representing a hydrogen atom or an electron-donating group such as optionally substituted (CrC 8 )alkyl, optionally substituted (C C 8 )alkoxy, or (di)(C
  • R 4 is a hydrogen atom
  • - Z represents a group CH or a nitrogen atom, preferentially CH,
  • the chromophores (111-1 ) and (IV-1 ) are chosen from Basic Red 51 ,
  • the chromophore A is chosen from anionic chromophores, especially those derived from direct dyes known as "Acid dyes". More particularly, the anionic chromophore A is chosen from (poly)azo dyes such as anionic (di)azo, anthraquinone, naphthoquinone, triaryl methane and nitro dyes, xanthene derivatives, quinoline derivatives and indoles.
  • R 7 , R 8 , R9, R10, R'7, R'e, R'9 and R' 0 which may be identical or different, represent a hydrogen atom or a group chosen from:
  • R"-S(0) 2 - with R" representing a hydrogen atom, an alkyl group, an aryl group, (di)(CrC 8 )(alkyl)amino, aryl(C C 8 ) (alkyl)amino; preferentially a phenylamino or phenyl group;
  • aryl(CrC 8 )(alkyl)amino optionally substituted with one or more groups chosen from i) nitro; ii) nitroso; iii) (0) 2 S(0 " )-, M + and iv) alkoxy with M + as defined previously;
  • cycloalkyi especially cyclohexyl
  • Ar-N N- with Ar representing an optionally substituted aryl group, preferentially a phenyl optionally substituted with one or more groups (C C 8 )alkyl, (0) 2 S(0 , M + or phenylamino;
  • W represents a sigma bond ⁇ , an oxygen or sulfur atom, or a divalent radical i)
  • R -NR- with R as defined previously, or ii) methylene -C(R a )(Rb)- with R a and R , which may be identical or different, representing a hydrogen atom or an aryl group, or alternatively R a and R form, with the carbon atom that bears them, a spiro cycloalkyi; preferentially W represents a sulfur atom or R a and R together form a cyclohexyl;
  • the chromophore (VI) or (VII) comprises at least one sulfonate radical (0) 2 S(0 " )-, M + or a carboxylate radical (O)CO " -, M + on one of the rings A, B, or C; preferentially sodium sulfate;
  • chromophores of formula (VI) derived from dyes, mention may be made of: Acid Red 1 , Acid Red 4, Acid Red 13, Acid Red 14, Acid Red 18, Acid Red 27, Acid Red 32, Acid Red 33, Acid Red 35, Acid Red 37, Acid Red 40, Acid Red 41 , Acid Red 42, Acid Red 44, Acid Red 68, Acid Red 73, Acid Red 135, Acid Red 138, Acid Red 184, Food Red 1 , Food Red 13, Acid Orange 6, Acid Orange 7, Acid Orange 10, Acid Orange 19, Acid Orange 20, Acid Orange 24, Acid Yellow 9, Acid Yellow 36, Acid Yellow 199, Food Yellow 3; Acid Violet 7, Acid Violet 14, Acid Blue 113, Acid Blue 117, Acid Black 1 , Acid Brown 4, Acid Brown 20, Acid Black 26, Acid Black 52, Food Black 1 , Food Black 2;
  • chromophores of formula (VII) derived from dyes mention may be made of: Acid Red 11 1 , Acid Red 134, Acid yellow 38. b) the anionic pyrazolone azo chromophores of formula (VIII) or (IX):
  • Rii, Ri2 and R 3 which may be identical or different, represent a hydrogen or halogen atom, an alkyl group or -(0) 2 S(0 " ), M + with M + as defined previously;
  • ⁇ Ri4 represents a hydrogen atom, a group (d-C 8 )alkyl or a group -C(0)0 " , M + with M + as defined previously;
  • ⁇ Ri5 represents a hydrogen atom
  • Ri 6 represents an oxo group, in which case R' 16 is absent, or alternatively R 5 with Ri 6 together form a double bond;
  • R 7 and R 8 which may be identical or different, represent a hydrogen atom, or a group chosen from:
  • Ar-0-S(0) 2 - with Ar representing an optionally substituted aryl group, preferentially a phenyl optionally substituted with one or more groups (C C 8 )alkyl;
  • Ri 9 and R 2 o together form either a double bond, or a benzo group D, which is optionally substituted;
  • R'i6, R'i9 and R' 2 o which may be identical or different, represent a hydrogen atom or a group (CrC 8 )alkyl, or hydroxyl;
  • R 2 i represents a hydrogen atom or a group (CrC 8 )alkyl or (CrC 8 )alkoxy;
  • R a and R a which may be identical or different, are as defined previously, preferentially R a represents a hydrogen atom and R represents an aryl group;
  • ⁇ Y represents either a hydroxyl group or an oxo group
  • ⁇ represents a single bond when Y is an oxo group; and represents a double bond when Y represents a hydroxyl group; it being understood that:
  • the chromophore (VIII) or (IX) comprises at least one sulfonate radical (0) 2 S(0 " )-, M + or a carboxylate radical -C(0)0 " , M + on one of the rings D or E; preferentially sodium sulfonate;
  • chromophores of formula (VIII) derived from dyes mention may be made of: Acid Red 195, Acid Yellow 23, Acid Yellow 27, Acid Yellow 76, and as examples of chromophores of formula (IX) derived from dyes, mention may be made of: Acid Yellow 17.
  • R22, R23, R24, R25, R ⁇ 6 and R27 which may be identical or different, represent a hydrogen or halogen atom, or a group chosen from:
  • aryloxy or arylthio optionally substituted, preferentially substituted with one or more groups chosen from alkyl and (0) 2 S(0 " )-, M + with M + as defined previously;
  • aryl(CrC 8 )(alkyl)amino optionally substituted with one or more groups chosen from alkyl and (0) 2 S(0 " )-, M + with M + as defined previously; - (di) (C C 8 )(alkyl)amino;
  • ⁇ Z' represents a hydrogen atom or a group NR 28 R29 with R 28 and R 29 , which may be identical or different, representing a hydrogen atom or a group chosen from: - (C C 8 )alkyl; polyhydroxy(CrC 8 )alkyl such as hydroxyethyl;
  • aryl optionally substituted with one or more groups, particularly i) (d-C 8 )alkyl such as methyl, n-dodecyl, n-butyl; ii) (0) 2 S(0 , M + with M + as defined previously; iii) R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X"- with R°, X, X' and X" as defined previously, preferentially R° represents a group (CrC 8 )alkyl; cycloakyl; especially cyclohexyl;
  • ⁇ Z represents a group chosen from hydroxyl and NR' 2 8R'29 with R' 28 and R' 29 , which may be identical or different, representing the same atoms or groups as R 28 and R 29 as defined previously;
  • the chromophore (X) or (XI) comprises at least one sulfonate radical (0) 2 S(0 , M + or a carboxylate radical -C(0)0 " , M + ; preferentially sodium sulfonate;
  • chromophores of formula (X) derived from dyes mention may be made of: Acid Blue 25, Acid Blue 43, Acid Blue 62, Acid Blue 78, Acid Blue 129, Acid Blue 138, Acid Blue 140, Acid Blue 251 , Acid Green 25, Acid Green 41 , Acid Violet 42, Acid Violet 43, Mordant Red 3;
  • chromophores of formula (XI) derived from dyes mention may be made of: Acid Black 48; d) nitro chromophores of formula (XII) or (XIII):
  • R 30 , R 3 1 and R 32 which may be identical or different, represent a hydrogen or halogen atom, or a group chosen from:
  • heterocycloalkyl such as piperidino, piperazino or morpholino
  • R30, R31 and R32 represent a hydrogen atom
  • R c and R d which may be identical or different, represent a hydrogen atom or an alkyl group
  • ⁇ W is as defined previously; W particularly represents a group -NH-;
  • ALK represents a linear or branched divalent C C 8 alkylene group; in particular, ALK represents a group -CH 2 -CH 2 -;
  • ⁇ n 1 or 2;
  • ⁇ p represents an integer between 1 and 5 inclusive
  • ⁇ q represents an integer between 1 and 4 inclusive
  • ⁇ u is 0 or 1 ;
  • J represents a nitro or nitroso group; particularly nitro; ⁇ when n is 2, J represents an oxygen or sulfur atom, or a divalent radical -S(0) m - with m representing an integer 1 or 2; preferentially J represents a radical -S0 2 -;
  • ⁇ M' represents a hydrogen atom or an organic or mineral cationic counterion
  • ⁇ may be present or absent, represents a benzo group optionally
  • the chromophore (XII) or (XIII) comprises at least one sulfonate radical (0) 2 S(0 " )-, M + or a carboxylate radical -C(0)0 " , M + ; preferentially sodium sulfonate;
  • chromophores of formula (XII) derived from dyes mention may be made of: Acid Brown 13; Acid Orange 3; as examples of chromophores of formula (XIII) derived from dyes, mention may be made of: Acid Yellow 1 , sodium salt of 2,4- dinitro-1-naphthol-7-sulfonic acid, 2-piperidino 5-nitrobenzenesulfonic acid, 2(4'-N,N(2"- hydroxyethyl)amino-2'-nitro)anilineethanesulfonic acid, 4-P-hydroxyethylamino-3- nitrobenzenesulfonic acid; e) the triarylmethane chromophores of formula (XIV):
  • R33, R34, R35 and R 36 which may be identical or different, represent a hydrogen atom or a group chosen from (d-C 8 )alkyl, optionally substituted aryl and optionally substituted aryl(CrC 8 )alkyl; particularly a group (CrC 8 )alkyl and benzyl optionally substituted with a group (0) m S(0 , M + with M + and m as defined previously;
  • R37, R38, R39, R40, R41 , R42, R43 and R 44 which may be identical or different, represent a hydrogen atom or a group chosen from:
  • X, X' and X" which may be identical or different, representing an oxygen or sulfur atom, or NR with R representing a hydrogen atom or a group (CrC 8 )alkyl;
  • R 44 together form a fused benzo group: ⁇ ; with ⁇ optionally substituted with one or more groups chosen from i) nitro; ii) nitroso; iii) (0) 2 S(0 " )-, M + ; iv) hydroxyl; v) mercapto; vi) (di)(C C 8 )(alkyl)amino; vii) R°-C(X)-X'-; viii) R°-X'- C(X)-; ix) R°-X'-C(X)-X"-; with M + , R°, X, X', X" as defined previously;
  • R 37 to R 40 represent a hydrogen atom
  • R 41 to R 44 which may be identical or different, represent a hydroxyl group or (0) 2 S(0 " )-, M + ; and when R 43 with R 44 together form a benzo group, it is preferentially substituted with a group (0) 2 S(0 " )-; it being understood that:
  • the chromophore (XIV) comprises at least one of the rings G', H', or ⁇ containing at least one sulfonate radical (0) 2 S(0 or a carboxylate radical -C(0)0 " ; preferentially sulfonate;
  • chromophores of formula (XIV) derived from dyes
  • R 45 , R 46 , R47 and R 48 which may be identical or different, represent a hydrogen atom or a group chosen from:
  • R 49 , R 50 , R51 and R 52 which may be identical or different, represent a hydrogen atom or a group chosen from:
  • R54, R55 and R 48 represent a hydrogen or halogen atom
  • ⁇ G represents an oxygen or sulfur atom or a group NR e with R e as defined previously; particularly G represents an oxygen atom; ⁇ L represents an alkoxide O " , M + ; a thioalkoxide S " , M + or a group NR f , with R f representing a hydrogen atom or a group (d-C 8 )alkyl, and M + as defined previously; M + is particularly sodium or potassium;
  • ⁇ L' represents an oxygen or sulfur atom or an ammonium group: N + R f R g , with R f and R g , which may be identical or different, representing a hydrogen atom, a group (CrC 8 )alkyl, optionally substituted aryl; U represents particularly an oxygen atom or a phenylamino group optionally substituted with one or more groups (CrC 8 )alkyl or (0) m S(0 , M + with m and M + as defined previously;
  • ⁇ Q and Q' which may be identical or different, represent an oxygen or sulfur atom; particularly Q and Q' represent an oxygen atom;
  • ⁇ M + is as defined previously;
  • chromophores of formula (XV) derived from dyes
  • R53, R54, R55, R56, R57, R58, R59 and R 60 which may be identical or different, represent a hydrogen atom or a group chosen from:
  • ⁇ G represents an oxygen or sulfur atom or a group NR e with R e as defined previously; particularly G represents an oxygen atom;
  • Rj and R h which may be identical or different, represent a hydrogen atom or a group (C C 8 )alkyl;
  • the chromophore (XVI) comprises at least one sulfonate radical (0) 2 S(0 " )-, M + or a carboxylate radical -C(0)0 " , M + ; preferentially sodium sulfonate;
  • dyes of formula (XVI) mention may be made of: Acid Blue 74. h) the anionic quinoline-
  • R 6 i represents a hydrogen or halogen atom or a group (CrC 8 )alkyl
  • R62, R63, and R 6 4 which may be identical or different, represent a hydrogen atom or a group (0) 2 S(0 " )-, M + with M + representing a hydrogen atom or an organic or mineral cationic counterion; ⁇ or alternatively R 6 i with R 6 2, or R 6 i with R 6 4, together form a benzo group optionally substituted with one or more groups (0) 2 S(0 " )-, M + with M + representing a hydrogen atom or an organic or mineral cationic counterion; it being understood that:
  • the chromophore (XVII) comprises at least one sulfonate radical (0) 2 S(0 " )-, M + preferentially sodium sulfonate;
  • chromophores of formula (XVII) derived from dyes mention may be made of: Acid Yellow 2, Acid Yellow 3 and Acid Yellow 5.
  • the anionic dyes that are most particularly preferred are the dyes designated in the Color Index under the code C.I. 58005 (monosodium salt of 1 ,2-dihydroxy-9, 10- anthraquinone-3-sulfonic acid), C.I. 60730 (monosodium salt of 2-[(9,10-dihydro-4- hydroxy-9,10-dioxo-1-anthracenyl)amino]-5-methylbenzenesulfonic acid), C.I. 15510 (monosodium salt of 4-[(2-hydroxy-1-naphthyl)azo]benzenesulfonic acid), C.I.
  • the anionic chromophore A is chosen from anionic (poly)azo dyes such as (di)azo dyes, anthraquinones, naphthoquinones, triarylmethanes, nitro dyes, and quinoline and indole derivatives, i.e. it does not contain any xanthene derivatives.
  • A is not an anionic fluorescein-based chromophore, more particularly A is not an anionic chromophore obtained from a xanthene derivative of formula (XV) as defined previously.
  • the radical A of formula (I) may contain one or more identical or different fluorescent coloured chromophores.
  • A is is a coloured and fluorescent chromophore.
  • coloured and fluorescent chromophore does not mean “optical brightener” chromophores, or any other fluorescent but colourless compounds, i.e. which do not absorb in the visible spectrum (see Ullmann's Encyclopedia of Industrial Chemistry, in the chapters “Fluorescent Dyes” and “Optical Brighteners”, 2005, Wiley- VCH Verlag GmbH & Co. KGaA, Weinheim 10.1002/143560007.a18_153; and 2005, Wiley-VCH Verlag GmbH & co. KGaA, Weinheim 10.1002/143560007.a1 1_279).
  • fluorescent coloured chromophores that are useful in the present invention, mention may be made of radicals derived from the following dyes: acridines, acridones, azlactones, benzanthrones, benzimidazoles, benzimidazolones, benzindoles, benzoxazoles, benzopyrans, benzothiazoles, coumarins, difluoro ⁇ 2-[(2/-/-pyrrol-2- ylidene-kN)methyl]-1 H-pyrrolato-kN ⁇ bores (BODIPY ®), dipyrinones, diketopyrrolopyrroles, fluorindines, (poly)methines (especially cyanins and styryls/hemicyanins), naphthalimides, naphthanilides, naphthylamine (such as dansyls), naphtholactams, oxadiazoles, oxazines, perilones
  • the chromophores are chosen from those derived from dyes of coumarin type, of (poly)methine type, especially cyanins and styryl/hemicyanin dyes, and of naphthalimide type.
  • radical A of formula (I) contains at least one cationic radical borne by, or included in, at least one of the chromophores.
  • the cationic radical is a quaternary ammonium; more preferentially, the cationic charge is endocyclic.
  • cationic radicals are, for example, a cationic (di/tri)(CrC 8 )alkylammonium radical bearing an exocyclic charge, or a cationic acridinium, benzimidazolium, benzobistriazolium, benzopyrazolium, benzopyridazinium, benzoquinolium, benzothiazolium, benzotriazolium, benzoxazolium, bipyridinium, bis-tetrazolium, dihydrothiazolium, imidazopyridinium, imidazolium, indolium, isoquinolium, naphthoimidazolium, naphthooxazolium, naphthopyrazolium, oxadiazolium, oxazolium, oxazolopyridinium, oxonium, phenazinium, phenooxazolium, pyrazinium, pyrazolium, pyrazoyltriazol
  • W + representing a cationic heterocyclic or heteroaryl group, particularly comprising a quaternary ammonium optionally substituted with one or more groups (d-C 8 )alkyl optionally substituted especially with one or more hydroxyl groups;
  • W' + representing a divalent heterocyclic or heteroaryl radical as defined for W + ;
  • Ar representing an aryl group such as phenyl or naphthyl, optionally substituted preferentially with i) one or more halogen atoms such as chlorine or fluorine; ii) one or more groups (CrC 8 )alkyl, preferably of C C 4 such as methyl; iii) one or more groups hydroxyl; iv) one or more groups (C C 8 )alkoxy such as methoxy; v) one or more groups hydroxy(CrC 8 )alkyl such as hydroxyethyl, vi) one or more groups amino or (di)(CrC 8 )alkylamino, preferably with the C C 4 alkyl part optionally substituted with one or more hydroxyl groups, such as (di)hydroxyethylamino, vii) with one or more acylamino groups; viii) one or more heterocycloalkyl groups such as piperazinyl, piperidyl or 5- or 6-membered heteroary
  • Ar' is a divalent aryl radical as defined for Ar
  • m' represents an integer between 1 and 4 inclusive, particularly m is 1 or 2; more preferentially 1 ;
  • R c and R d which may be identical or different, represent a hydrogen atom or an optionally substituted group (CrC 8 )alkyl, preferentially of C C 4 , or alternatively R c contiguous with W or W and/or R d contiguous with Ar or Ar' form, with the atoms that bear them, a (hetero)cycloalkyl, particularly R c is contiguous with W + or W' + and forms a (hetero)cycloalkyl such as cyclohexyl;
  • the dyes of formula (I) contain a chromophore A that is not an anionic fluorescein-based chromophore, and more particularly A is not an anionic chromophore based on a xanthene derivative of formula (XV) as defined previously.
  • the dye of formula (I) is a quaternized or quaternizable fluorescent dye such that, in formula (I), A represents a naphthalimidyl radical optionally bearing an exocyclic cationic charge, of formula (XX) or (XXI):
  • G' represents an amino group -NR f R e or ammonium group -N + R f R e R h , M " ;
  • G represents a divalent amino group -N(R h )- or ammonium group -N + (R h )(R j )-, M " ;
  • R e , R f , R 9 , R h and R j which may be identical or different, represent a hydrogen atom or a C C 6 alkyl group optionally substituted preferentially with a hydroxyl, amino, di(CrC 6 )alkylamino or tri(CrC 6 )alkylammonium group, such as trimethylammonium, M " ; with M " with M " representing an organic or mineral counterion,
  • R 1 which may be identical or different, represents a hydrogen atom, a halogen atom, a (di)(CrC 4 )(alkyl)amino, cyano, carboxyl, hydroxyl or trifluoromethyl group, an acylamino, (C C 4 )alkoxy, (poly)hydroxy(C 2 -C 6 )alkoxy, (C C 4 )alkylcarbonyloxy, (C C 4 )alkoxycarbonyl or (Ci-C 4 )alkylcarbonylamino radical, an acylamino, carbamoyl or (Ci-C 4 )alkylsulfonylamino radical, an aminosulfonyl radical, or a radical (CrCi 6 )alkyl optionally substituted with a group chosen from (CrC 6 )alkoxy, hydroxyl, cyano, carboxyl and (di)(C C 4 )(alkyl)a
  • G' represents an amino group -NR f R e and G" represents a divalent amino group -N(R h )-
  • R 1 represents a hydrogen atom
  • R e and R 9 represent a Ci-C 6 alkyl group substituted with a group di(CrC 6 )alkylamino or tri(C C 6 )alkylammonium, M "
  • R f , R h represent a hydrogen atom or a C C 6 alkyl group
  • the amino group R f R e N- or -N(R h )- is in position 4 or 5 of the naphthalimidyl radical.
  • W + or W' + is an imidazolium, pyridinium, benzimidazolium, pyrazolium, benzothiazolium or quinolinium optionally substituted with one or more identical or different C C 4 alkyl radicals.
  • C sat represents a linear or branched, optionally substituted, optionally cyclic divalent C Ci 8 alkylene chain.
  • Substituents that may be mentioned include amino, (C C 4 )alkylamino and di(C C 4 )alkylamino groups, or the group R a -Z a -C(Z b )- (in which Z a , Z b , which may be identical or different, represent an oxygen or sulfur atom, or a group NR a ', and R a represents an alkali metal, a hydrogen atom or a group C C 4 alkyl and R a ' represents a hydrogen atom or a group Ci-C 4 alkyl) preferably present in the beta or gamma position of the ascorbic acid- based radical of formula (11-1 ) to (M-4) as defined previously or of formula ( ⁇ -1 ) to ( ⁇ -4) as defined in point 1.4 below.
  • C sat represents a chain -(CR 1 R 2 ) k - with k representing an integer between 1 and 10 inclusive
  • R 1 and R 2 which may be identical or different, representing a hydrogen atom or a group (C C 4 )alkyl, (C Ci 2 )alkoxy, hydroxyl, cyano, carboxyl or (di)(C C 4 )(alkyl)amino, the said alkyl radicals possibly forming, with the nitrogen atom that bears them, a 5- to 7-membered heterocycle, optionally comprising another heteroatom identical to or different from nitrogen; preferentially, and R 2 , are hydrogen atoms or an amino group; more preferentially, and R 2 represent a hydrogen atom, thus forming an alkylene chain -(CH 2 ) k — with k' being an integer between 1 and 8 inclusive. More particularly, k' is 1 , 2 or 3.
  • radical(s) X and X' which may be identical or different, represent the following sequence:
  • T and T' which may be identical or different, represent one or more radicals or combinations thereof chosen from: -S(0) 2 -; -0-; -S-; -N(R)-; -N + (R)(R°)-, Q " ;
  • R, R° which may be identical or different, representing a hydrogen atom, a C C 4 alkyl, C C 4 hydroxyalkyl or aryl(C C 4 )alkyl radical and Q " representing an organic or mineral anionic counterion; and a cationic or non- cationic, preferentially monocyclic heterocycloalkyl or heteroaryl radical, preferentially containing two heteroatoms (more preferentially two nitrogen atoms) and preferentially being 5- to 7-membered, more preferentially imidazolium, piperazinyl or piperidyl;
  • T and T represent one or more radicals or combinations thereof chosen from -0-, -N(R)-, -C(O)-, with R chosen from a hydrogen atom and a (C C 4 )alkyl radical;
  • indices t and t' which may be identical or different, are equal to 0 or 1 ;
  • R 2 which may be identical or different, represent a hydrogen atom or a group (C C 4 )alkyl, (C C 4 )alkoxy, hydroxyl, cyano, carboxyl or (di)(C C 4 )(alkyl)amino, the said alkyl radicals possibly forming, with the nitrogen atom that bears them, a 5- to 7-membered heterocycle, optionally comprising another heteroatom identical to or different from nitrogen, such as morpholino or piperidino; and R 2 particularly represent a hydrogen atom;
  • Z represents divalent group chosen from:
  • the ascorbic acid-based radical Asc of the dye of formula (I) represents an ascorbyl or dehydroascorbyl radical chosen from formulae (11-1 ) to (M-4) as defined previously.
  • the ascorbic acid-based radical is chosen from formulae (11-1 ) to (II- 3) such that:
  • R 5 is absent and Asc is linked to the rest of the molecule via the carbon atom bearing R 6 and R 7 ; - R 6 , R 7 and R 8 represent a hydrogen atom
  • R1 0 represents a hydrogen atom or a (C C 4 )alkyl, particularly hydrogen
  • R 9 represents a hydroxyl group or the same -O-protected with a protecting group as defined previously; preferentially:
  • aryl for instance halophenyl such as para-chlorophenyl,
  • aryl(CrC 8 )alkyl such as benzyl, s) R-C(O)-, with R representing 1) a hydrogen atom, or 2) a group (CrC 8 )alkyl such as methyl, 3) (poly)halo(aryl)(CrC 8 )alkyl such as chloromethyl, dichloromethyl, trichloromethyl, trifluoromethyl or chlorodiphenylmethyl, 4) (CrC 8 )alkoxy such as methoxy, ethoxy or isobutoxy, 5) (aryl)(C 2 -C 8 )alkenyloxy such as vinyloxy, allyloxy or cinnamyloxy, 6) (poly)halo(CrC 8 )alkoxy such as trichloroethoxy, 7) (C 2 -C 8 )alkenyl, 6) (C C 8 )alkoxy(CrC 8 )alkyl such as meth
  • R 9 represents a hydroxyl group or the same -O-protected with a protecting group chosen from:
  • R-C(O)- with R representing 1) a hydrogen atom, or 2) a group (C C 8 )alkyl such as methyl.
  • the dye of formula (I) comprises a group Asc of formula (11-1 ) to (M-3) as defined previously with R 9 absent and Asc linked to the rest of the molecule via the carbon atom bearing R 8 ;
  • R 6 , R 7 and R 9 represent a hydrogen atom
  • R-io represents a hydrogen atom or a (C C 4 )alkyl, particularly hydrogen
  • R 5 represents a hydroxyl group or the same -O-protected with a protecting group as defined previously.
  • Asc is chosen from the groups of formulae ( ⁇ -1 ) to ( ⁇ -3):
  • R' 9 representing a hydrogen atom or a protecting group as defined previously; preferentially, R' 9 represents a hydrogen atom, Rn and R 2 being as defined previously, and • ⁇ / ⁇ - representing the point of attachment of Asc to the rest of the molecule of formula (I).
  • the dye of formula (I) comprises a group Asc of formula (M-4) as defined previously with R 9 absent and Asc linked to the rest of the molecule via the carbon atom bearing Y and R 0 represents a hydrogen atom or a (C C 4 )alkyl, particularly hydrogen, in which case Asc is of formula (M'-4) below:
  • the dyes of formula (I) are such that they correspond to formula ( ⁇ '):
  • Asc' represents an ascorbic acid-based radical of formulae (11-1 ) to (M-4) as defined previously, particularly (M'-1 ) to (M'-4);
  • C sat represents a (d-C 8 )alkylene chain, such as -(CH 2 ) k - with k being an integer between 1 and 8 inclusive; preferentially, k is 1 , 2 or 3;
  • R 2 are as defined previously, particularly represent a hydrogen atom or a group (CrC 4 )alkyl
  • T a , T b , and T c which may be identical or different, represent one or more radicals or combinations thereof chosen from -S(0) 2 - -0-, -S-, -N(R)-, -N + (R)(R°)- M " and -C(O)-, with R, R°, which may be identical or different, representing a hydrogen atom or a radical (C C 4 )alkyl or hydroxy(C C 4 )alkyl; or an aryl(C C 4 )alkyl such as benzyl, and M " represents an organic or mineral anionic counterion such as a halide;
  • T a represents a group -N(R)- and T c represents a group chosen from a radical -0-, -C(O)- or -N(R)-, or a combination thereof with R, representing a hydrogen atom or a group (C C 4 )alkyl such as methyl; and
  • the radical Het + , W + , or W' + is a group chosen from imidazolium, pyridinium, benzopyridinium, benzimidazolium, quinolinium, indolinium and pyrazolium, optionally substituted preferentially with one or more identical or different C C 4 alkyl radicals. More particularly, Het + , W + or W' + , is chosen from pyridinium, imidazolium and indolinium groups optionally substituted with one or more identical or different (C C 4 )alkyl radicals, such as methyl.
  • Ar is an optionally substituted phenyl
  • Ar' is an optionally substituted phenylene
  • Ar + is an optionally substituted phenyl or naphthyl bearing an exocyclic tri(CrC 8 )alkylammonium cationic charge, M- with M- representing an organic or mineral anionic counterion, such as trimethylammonium.
  • the dye bearing an ascorbic acid-based group is a dye chosen from the compounds of formulae (l a ) to (l n ) below:
  • Asc' represents an ascorbic acid-based radical of formulae (11-1 ) to (M-4) as defined previously, particularly ( ⁇ -1 ) to ( ⁇ -4);
  • G represents a group -NR c R d , or (d-C 6 )alkoxy; preferentially G represents a group -NR c R d , which is preferentially in the para position relative to the styryl, azo or hydrazono group;
  • R a and R' a which may be identical or different, represent an optionally substituted group (CrC 6 )alkyl; preferentially, R a represents a group (CrC 3 )alkyl optionally substituted with a hydroxyl group, preferentially unsubstituted, such as methyl;
  • R b represents a hydrogen atom or an optionally substituted C C 6 alkyl group; preferentially unsubstituted, such as methyl;
  • R c and R d which may be identical or different, represent a hydrogen atom, a group aryl(CrC 4 )alkyl, (CrC 6 )alkoxy or an optionally substituted group (C
  • R c and R d preferentially represent a hydrogen atom or a group (C
  • heterocyclic or heteroaryl group or alternatively two adjacent radicals R c and R d , borne by the same nitrogen atom together form a heterocyclic or heteroaryl group; preferentially, the heterocycle or heteroaryl is monocyclic and 5- to 7-membered; more preferentially, the groups are chosen from imidazolyl and pyrrolidinyl;
  • R c and R d represent identical groups; preferentially R c and R d represent a (CrC 3 )alkyl optionally substituted with a hydroxyl group, such as methyl, hydroxyethyl and 2-hydroxypropyl;
  • R g , R' g , R h and R' h which may be identical or different, represent a hydrogen atom, a halogen atom, a group (di)(C C 4 )(alkyl)amino, cyano, carboxyl, hydroxyl, trifluoromethyl, an acylamino, (C C 4 )alkoxy, (poly)hydroxy(C 2 -
  • G represents -NR c R d two groups R c and R' g ; R d and R g ; together form a saturated heteroaryl or heterocyde, optionally substituted with one or more groups (CrC 6 )alkyl, preferentially a 5- to 7-membered heterocyde containing one or two heteroatoms chosen from nitrogen and oxygen; more preferentially the heterocyde is chosen from morpholinyl, piperazinyl, piperidyl and pyrrolidinyl groups;
  • Ri, R j , R' j and R'j which may be identical or different, represent a hydrogen atom, or a group C C 4 alkyl; more preferentially, R, R j , R' j and R'j represent a hydrogen atom;
  • R s represents a sulfonate radical (0) 2 S(0 " )-, M + or a carboxylate radical -C(0)0 " , M + with M + representing an organic or mineral cationic counterion; preferentially sulfonate such as sodium sulfonate;
  • Ri , R ⁇ , R3 and R 4 which may be identical or different, represent a hydrogen atom or a group (C C 4 )alkyl, (CrCi 2 )alkoxy, hydroxyl, cyano, carboxyl or (di)(Ci-C 4 )(alkyl)amino, the said alkyl radicals possibly forming, with the nitrogen atom that bears them, a 5- to 7-membered heterocyde, optionally comprising another heteroatom identical to or different from nitrogen;
  • R 2 , R 3 and R 4 are hydrogen atoms or an amino group; more preferentially, R ⁇ R 2 , R 3 and R 4 , represent a hydrogen atom;
  • R e , R f , R 9 , and R h which may be identical or different, represent a hydrogen atom or an alkyl C C 6 group optionally substituted preferentially with a group di(CrC 6 )alkylamino or tri(CrC 6 )alkylammonium, M " with M " representing an organic or mineral anionic counterion, such as trimethylammonium, M " ;
  • R e and R 9 represent an alkyl C C 6 group substituted with a group di(CrC 6 )alkylamino or tri(CrC 6 )alkylammonium, M " and R f , R h represent a hydrogen atom or a C C 6 alkyl group; and the amino group R f R e N- or -N(R h )- is in position 4 of the naphthalimidyl radical;
  • t and t' which may be identical or different, are equal to 0 or 1 ; preferentially, t' is 0:
  • T a , T b and T c which may be identical or different, represent one or more radicals or combinations thereof chosen from -S(0) 2 -, -0-, -S-, -N(R)-, -N + (R)(R°)- M " and -C(O)-, with R, R°, which may be identical or different, representing a hydrogen atom, a radical (C C 4 )alkyl or hydroxy(C C 4 )alkyl; or an aryl(Ci-C 4 )alkyl, and M " represents an organic or mineral anionic counterion such as halide, preferentially, t' is zero and T c represents a group chosen from a radical -0-, -C(O)-, -N(R)- or a combination thereof with R, representing a hydrogen atom or a group (C C 4 )alkyl such as methyl; more particularly, T c represents a group -C(0)-0-, -O
  • • """ ⁇ j represents an aryl or heteroaryl group fused to the phenyl ring; or alternatively is absent from the phenyl ring; when the ring is present, the ring is preferentially a benzo; more preferentially, the ring is absent;
  • the direct dyes are chosen from those of formulae (l a ), (l b ), (l c ), (l f ), (l g ), (1), (lj), (l k ), (L) and (l n ).
  • the dyes according to the invention are chosen from the direct dyes of formulae (I'.), (I' b ), (l' c ), (l' f ), (l' g ), ( ⁇ ',), (I' j ), (l' k ), (l' m ) and (l' n ) below:
  • R a , R j and R' j represent a group (d-C 4 )alkyl such as methyl;
  • R b represents a hydrogen atom or a group (C C 4 )alkyl such as methyl; preferentially, R is a hydrogen atom;
  • R g and R' g are as defined previously and preferentially represent a hydrogen atom
  • R s represents a sulfonate radical (0) 2 S(0 " )-, M + such as sodium sulfonate;
  • R s is ortho to the group R c R d N- of (I' j )
  • T c represents a group chosen from a radical -0-, -C(O)-, -N(R)- or a combination thereof with R, representing a hydrogen atom or a group (C
  • T c represents a group -C(0)-0- or -N(R)-C(0)-;
  • ⁇ m' is 1 , 2 or 3;
  • n' is an integer between 1 and 10 inclusive, and more particularly between 3 and 6 such as 5;
  • R c and R d represent identical groups (CrC 3 )alkyl optionally substituted with a hydroxyl group, such as methyl or hydroxyethyl;
  • R e and R 9 represent a C C 6 alkyl group substituted with a group di(C C 6 )alkylamino or tri(CrC 6 )alkylammonium, M " ;
  • R f and R h represent a hydrogen atom or a C C 6 alkyl group; preferably the amino group R f R e N- or -N(R h )- is in position 4 of the naphthalimidyl radical; and M' representing an organic or mineral anionic counterion;
  • the styryl, hydrozono or azo function is in position 2 (ortho) or 4 (para) relative to the phenyl, preferentially in position 4 and that the styryl or hydrazono function is in position 2' (ortho) or 4' (para) relative to the pyridinium, or 2' (ortho) or 4' (para) relative to the phenyl for (l' k ), preferentially in position 4'.
  • the direct dyes are chosen from those of formulae (l b ), and (l m ) and more particularly (l' b ), and
  • dyes bearing an ascorbic acid-based group mention may be made especially of the following compounds:
  • the dyes of formula (l a ) may be synthesized via a condensation reaction between a compound (a1) and a compound (a2). This reaction is well known to those skilled in the art. It is known as the Knoevenagel reaction and consists in condensing an aldehyde with a nucleophile of activated methyl type. This reaction is described in the literature. Reference may be made, for example, to the book Advanced Organic Chemi -471-60180-2). This reaction is illustrated in the scheme below:
  • Compounds (a2) may be synthesized via a nucleophilic substitution reaction between a compound (a3) and a compound (a4).
  • This reaction is known to those skilled in the art and is described in the literature. By way of example, reference may be made to the book Advanced Organic Chemistry (ISBN 0-471-60180-2). This reaction is illus
  • R to R 4 R a , R b , G, m, n, Tb, t' Tc, R,, R',, R h , R' h as defined previously and Hal representing a halogen atom such as fluorine.
  • Compounds (a4) may be synthesized via a reaction between a compound (a5) and a compound (a6). This reaction is illustrated in the scheme below:
  • R ⁇ to R 4 , R , m, n, Tb, t' as defined previously; Nu representing a nucleophilic group; ⁇ representing an electrophilic group; and T c the bond generated after attack of the nucleophile on the electrophile.
  • Carbodiimides Carboxylic acids N-Acylureas or anhydrides
  • acyl halides may rearrange to give isocyanates. These reactions are known to those skilled in the art and are described in the literature. Reference may be made to the book Advanced Organic Chemistry (ISBN 0- 471 -60180-2).
  • compounds (a4) may be synthesized via a reaction between a compound (a7) and a compound (a8). This reaction is illustrated in the scheme below:
  • R to R 4 R a , R b , m, n, Tb, t' Tc, ⁇ , Nu as defined previously;
  • compounds (a2) may be synthesized via a reaction between a compound (a9) and a compound (a10). This reaction is illustrated in the scheme below:
  • T a the bond generated after attack of the nucleophile on the electrophile.
  • the covalent bonds T that may be generated are such as those listed in Table A for T c starting from the condensation of electrophiles with nucleophiles (see Table A above):
  • Hal represents a halogen atom such as fluorine
  • Another synthetic variant consists in reacting a compound (a12) with a heterocyclic compound (a8). This reaction is illustrated in the scheme below:
  • R ⁇ to R 4 R a , R b , m, n, Tb, t' Tc, ⁇ , Nu, R g , R' g , R h , R' h and M' as defined previously;
  • the dyes of formula (lb) may be synthesized via a condensation reaction between a compound (a1) and a compound (a2).
  • This reaction is well known to those skilled in the art, and is known as the Knoevenagel reaction, which consists in condensing an aldehyde with a nucleophile of activated methyl type. This reaction is illustrated in the scheme below:
  • Compounds (a23) are known to those skilled in the art and are described in the literature. Some of them are commercially available. Compounds (a24) may be synthesized via a quaternization reaction between an electrophilic compound (a25) and a pyridine compound (a26). This reaction is well known to those skilled in the art.
  • R to R 4 R a , R b , m, n, Tb, t' Tc, ⁇ , Nu, R,, R', and M' as defined previously;
  • the group Gp' represents a leaving group, which, once it has left, generates an anionic counterion. Mention may be made of halides such as iodide, bromide, chloride or the mesylate, sulfate, phosphate, triflate or tosylate group.
  • the compounds (a25) may be synthesized via a reaction between a compound (a26) and a compound (a6). This reaction is illustrated in the scheme below: Q ' (CRi3 ⁇ 4 m ScRjF -T-Asc 1
  • R to R 4 R a , R b , m, n, Tb, t' Tc, ⁇ , Nu as defined previously;
  • compounds (a28) may be synthesized via a reaction between a compound (a26) and a compound (a6). This reaction is illustrated in the scheme below:
  • R to R 4 R a , R b , m, n, Gp', Tb, t' Tc, ⁇ , Nu, as defined previously;
  • Compounds (a29) may be synthesized via a reaction between a compound (a30) and a compound (a23). This reaction is illustrated in the scheme below:
  • R-i to R 4 R a , R b , G, m, n, T a , £, 3Vu, R g , R' g , Ri, R'i, R h , R' h , M' as defined previously; compounds (a23) are as defined previously.
  • Compounds (a30) may be synthesized via a reaction between a compound (a27) and a pyridine derivative (a26). This reaction is illustrated by the scheme below: Gp'- (CR, R 2 ) m
  • Another synthetic variant consists in reacting a compound (a31) with compounds (a8)
  • Compounds (a31 ) may be synthesized via a reaction between a compound (a32) and a compound (a23). This reaction is illustrated in the scheme below:
  • the dyes of formula (lc) may be synthesized via the synthetic routes described previously for the dyes of formula (la).
  • the main difference is that compounds (a14), compounds bearing an indolinium unit, are used instead of compounds (a1 ), compounds bearing a pyridinium unit.
  • the reaction with compounds (a14) is illustrated in the scheme below:
  • R ⁇ to R 4 R a , Rb, m, n, Tb, t' Tc, ⁇ , Nu, R g , R' g , Ri, R'i, Rn, R'n, Rj, R'j, and M' as defined previously;
  • compounds (lb) may be synthesized via a condensation reaction between a compound (a15) and a compound (a8).
  • the reaction with compounds (a14) is illustrated in the scheme below:
  • R ⁇ to R 4 R a , R b , m, n, Tb, f Tc, ⁇ , Nu, R g , R' g , Ri, R'i, Rn, R'n, Rj, R'j and M' as defined previously;
  • compounds (l d ) may be synthesized via a reaction between a compound (a36) and a compound (a6). This reaction is illustrated by the scheme below:
  • Compounds (a36) may be synthesized via a reaction between a compound
  • Compounds (a39) may be synthesized via a reaction between a compound (a4
  • compounds (a39) may be synthesized via a reaction between a compound (a41 ) and a compound (a38). This reaction is illustrated in the scheme below:
  • Compounds (a41 ) may be synthesized via a reaction between a compound (a41 ) and a compound (a38). This reaction is illustrated in the scheme below:
  • R ⁇ to R 4 R a , R b , G, m, n, Tb, t' Tc, ⁇ , N ⁇ u, Ri, R'i, R j , R' j , M' as defined previously;
  • the group Gp' represents a leaving group, which, once it has been removed, generates an anionic counterion M'. Mention may be made of halides such as iodide, bromide, chloride or the triflate, sulfate, phosphate, mesylate or tosylate group.
  • compounds (1 g) may be synthesized via a reaction between a compound ( heme below:
  • Compounds (a45) may be synthesized via a reaction between a compound (a46) and a compound (a27). This reaction is illustrated in the scheme below:
  • compounds (l g ) may be synthesized via a reaction between a compound ( eme below:
  • Compounds (a45') may be synthesized via a reaction between a compound (a46) an
  • R 4 with to R 4 , R a , G, m, n, Tb, t' Tc, ⁇ , Nu, R g , R' g , R h , R' h and M' as defined previously;
  • the first step, to form compound (a49), is a reaction that is well known to those skilled in the art. It is known as a "diazotization" reaction. This reaction is described in the literature. It consists in diazotizing an aromatic amine (compounds (a48)) and in condensing it with an electron-rich aromatic molecule to form a diazo bond. Reference may be made, for example, to the book Advanced Organic Chemistry (ISBN 0-471- 60180-2). Compounds (a48) are known to those skilled in the art and are described in the literature.
  • the second step, to form compound (a46), is a reaction that is well known to those skilled in the art. It is known as a "quaternization" reaction. This reaction is described in the literature. Reference may be made, for example, to the book Advanced Organic Chemistry (ISBN 0-471 -60180-2).
  • R s represents a sulfonate group (S0 3 " M + ) with M + as defined previously, such as sodium or potassium.
  • Compounds (a8) are as described previously.
  • Compounds (l m ) may be synthesized via a reaction between a compound (a60) and a compound (a61 ), to give the intermediate ( ⁇ '), which may itself react with a nucleophilic group G'H to give (C).
  • the latter group is capable of reacting, for example via esterification, with a hydroxyl group of an ascorbic derivative Asc-OH. This reaction is illustrated in the scheme below:
  • Hal represents a halogen atom such as chlorine, bromine or iodine.
  • composition comprising the dye of formula (I) or (l')
  • Another subject of the invention is a dye composition
  • a dye composition comprising, in a cosmetically suitable medium, at least one fluorescent dye bearing a group derived from ascorbic acid of formula (I) or ( ⁇ ) as defined previously.
  • composition of the invention may also contain a reducing agent.
  • the composition does not contain any reducing agent.
  • the cosmetic composition comprising one or more dyes of formula (I) or ( ⁇ ) does not contain any chemical oxidizing agent.
  • chemical oxidizing agent means any chemical or enzymatic oxidizing agent other than atmospheric oxygen.
  • the dye composition that is useful in the invention generally contains an amount of dye of formula (I) or ( ⁇ ) 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 preferentially 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 chosen, for example, from neutral, acidic or cationic nitrobenzene direct dyes, neutral, acidic or cationic azo direct dyes, tetraazapentamethine dyes, neutral, acidic or cationic quinone and 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 the dyeing of keratin fibres.
  • oxidation bases mention may be made of para-phenylenediamines, bis(phenyl)alkylenediamines, para-aminophenols, bis-para-aminophenols, ortho- aminophenols and heterocyclic bases, and the addition salts thereof.
  • couplers mention may be made especially of meta- phenylenediamines, meta-aminophenols, meta-diphenols, naphthalene-based couplers and heterocyclic couplers, and the addition salts thereof.
  • the coupler(s) are each generally present in an amount of between 0.001 % and 10% by weight and preferably between 0.005% and 6% by weight relative to the total weight of the dye composition.
  • the oxidation base(s) present in the dye composition is (are) each generally present in an amount of between 0.001 % and 10% by weight and preferably between 0.005% and 6% by weight relative to the total weight of the dye composition.
  • the addition salts of the oxidation bases and couplers used in the context of the invention are especially chosen from the salts of addition with an acid, such as the hydrochlorides, hydrobromides, sulfates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates, and the salts of addition with a base, such as alkali metal hydroxides, for instance sodium hydroxide, potassium hydroxide, ammonia, amines or alkanolamines.
  • an acid such as the hydrochlorides, hydrobromides, sulfates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates
  • a base such as alkali metal hydroxides, for instance sodium hydroxide, potassium hydroxide, ammonia, amines or alkanolamines.
  • the medium that is suitable for dyeing is a cosmetic medium generally formed from water or a mixture of water and of at least one organic solvent.
  • organic solvents include C C 4 lower alkanols, such as ethanol and isopropanol; polyols and polyol ethers, for instance 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and monomethyl ether, and also aromatic alcohols, for instance benzyl alcohol or phenoxyethanol, and mixtures thereof.
  • the composition contains an aromatic alcohol such as benzyl alcohol.
  • the solvents are preferably present in proportions preferably of between 1 % and 99% by weight approximately and even more preferentially between 5% and 95% by weight approximately relative to the total weight of the dye composition.
  • the dye composition may also contain various adjuvants conventionally used in hair dye compositions, such as anionic, cationic, nonionic, amphoteric or zwitterionic surfactants or mixtures thereof, anionic, cationic, nonionic, amphoteric or zwitterionic polymers or mixtures thereof, mineral or organic thickeners, and in particular anionic, cationic, nonionic and amphoteric polymeric associative thickeners, antioxidants, penetrants, sequestrants, fragrances, buffers, dispersants, conditioning agents, for instance volatile or non-volatile, modified or unmodified silicones such as amino silicones, film-forming agents, ceramides, preserving agents, opacifiers and conductive polymers.
  • adjuvants conventionally used in hair dye compositions, such as anionic, cationic, nonionic, amphoteric or zwitterionic surfactants or mixtures thereof, anionic, cationic, nonionic, amphoteric or zwitterionic
  • the above adjuvants are generally present in an amount for each of them of between 0.01 % and 20% by weight relative to the weight of the composition. Needless to say, a person skilled in the art will take care to select this or these optional additional compound(s) such that the advantageous properties intrinsically associated with the dye composition in accordance with the invention are not, or are not substantially, adversely affected by the envisaged addition(s).
  • the pH of the dye composition is generally between 3 and 14 approximately and preferably between 4 and 11 approximately, and more particularly the pH is such that 3 ⁇ pH ⁇ 9. It may be adjusted to the desired value by means of acidifying or basifying agents usually used in the dyeing of keratin fibres, or alternatively using standard buffer systems.
  • the pH of the composition comprising at least one dye of formula (I) is an acidic pH (i.e. 3 ⁇ pH ⁇ 7) and in particular the pH is 4.
  • the pH is basic (i.e. 7 ⁇ pH ⁇ 11), more particularly 7 ⁇ pH ⁇ 9.
  • acidifying agents that may be mentioned, for example, are mineral or organic acids, for instance hydrochloric acid, orthophosphoric acid or sulfuric acid, carboxylic acids, for instance acetic acid, tartaric acid, citric acid and lactic acid, and sulfonic acids.
  • basifying agents examples that may be mentioned include aqueous ammonia, alkali metal carbonates, alkanolamines such as monoethanolamine, diethanolamine and triethanolamine, and also derivatives thereof, sodium hydroxide, potassium hydroxide and the compounds of formula ( ⁇ ) below:
  • W a is a divalent group (d-C 6 )alkylene optionally interrupted with one or more heteroatoms such as O or N and/or optionally substituted with one or more hydroxyl groups or a C C 4 alkyl radical; particularly, W a represents a propylene group;
  • R a i , a2, Ra3 and R a4 which may be identical or different, represent a hydrogen atom or a C C 4 alkyl or C C 4 hydroxyalkyl radical.
  • the dye composition may be in various forms, such as in the form of a liquid, a cream or gel, or in any other form that is suitable for dyeing keratin fibres, and especially the hair. ///. Dyeing and/or lightening process using a dye of formula (I) or (l')
  • Another subject of the invention is a process for dyeing and/or lightening keratin material, especially dark keratin material, which consists in applying to the said materials a composition comprising at least one dye of formula (I) or ( ⁇ ') as defined previously.
  • the process of optical lightening of dark keratin materials such as keratin fibres with a tone depth of less than or equal to 6 and more particularly less than or equal to 4 involves fluorescent dyes of formula (I) or ( ⁇ '), i.e. dyes in which A represents a fluorescent coloured chromophore. Mention may be made particularly of those defined in point 1.2 above. More particularly, the chromophore A is chosen from those of formulae (XVIII), (XIX), (XX) and (XXI) as defined previously.
  • the fluorescent dyes are chosen from (l' a ), (I'b), (l' c ), (I'm) and (l' n ).
  • the fluorescent dyes used for lightening dark keratin materials such as keratin fibres with a tone depth of less than or equal to 6 and more particularly less than or equal to 4 are within the orange range.
  • a reducing agent may be applied before, at the same time as or after application of the composition containing at least one dye of formula (I).
  • no reducing agent is used in the process according to the invention.
  • the composition containing at least one dye of formula (I) has been applied to the keratin materials
  • the composition is left on for a certain time, and the keratin materials are then rinsed, and/or drained dry and/or undergo a heat treatment and/or are exposed to ultraviolet (UV) light.
  • UV ultraviolet
  • the fibres undergo a heat treatment, especially at a temperature of between 50 and 200°C and preferentially between 80 and 180°C.
  • the duration of the treatment after application of the composition containing may be short, for example from 0.1 second to 1 hour, particularly between 5 minutes and 50 minutes and more particularly between 10 and 45 minutes, and preferentially the leave-on time is 30 minutes.
  • the duration of the post-treatment with heat may be short, for example from 0.1 to 30 minutes.
  • the temperature is between 40°C and 250°C, more particularly between 50°C and 200°C and preferentially from 80°C to 180°C.
  • the heat treatment of the keratin fibres is performed using an iron for smoothing keratin fibres or using a hairstyling hood, a hairdryer or an infrared ray dispenser.
  • the dyeing and/or lightening process according to the invention consists in applying the composition according to the invention to keratin materials and then in draining them dry and/or subjecting them to a heat treatment particularly at a temperature of between 50 and 200°C and more preferentially between 80 and 180°C, with, for example, a smoothing iron.
  • a heat treatment particularly at a temperature of between 50 and 200°C and more preferentially between 80 and 180°C, with, for example, a smoothing iron.
  • the heat treatment is followed by rinsing.
  • the duration of the post-treatment with UV is between 1 second and 2 hours, preferentially 30 minutes.
  • One particular embodiment of the invention concerns a process in which the compound of formula (I) may be applied directly to the hair without reducing agents, free of pretreatment or post-treatment reducing agents.
  • a treatment with a chemical oxidizing agent may optionally be combined.
  • Any type of chemical oxidizing agent that is standard in the field may be used.
  • 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.
  • This oxidizing agent may be applied to the fibres before or after applying the composition containing at least one compound of formula (I).
  • the dyeing or optical lightening process does not involve any chemical oxidizing agent.
  • DMF A/,A/-dimethylformamide
  • Compound (D) is reacted in refluxing acetonitrile in the presence of a large excess of the dye to be grafted (5 equivalents) for at least 12 hours (step iv).
  • Compound (F) commercial compound sold by Sigma-Aldrich.
  • the expected product, dye 3 is thus obtained after purification on a column of silica gel.
  • Compound (J) is obtained by reacting the commercial compound (F) with one equivalent of the ethyl ester of bromobutyric acid in refluxing toluene (step viii), followed by saponification of the ester and purification on an ion-exchange column in water (step ix).

Abstract

La présente invention concerne la coloration d'éléments à base de kératine à l'aide des colorants portant une unité à base d'acide ascorbique de formule (I), en particulier portant des unités de 3,4-dihydroxyfuran-2(5H)-one et de 2,3,4(5H)-furane-trione. L'invention concerne une composition de colorant comprenant un colorant portant un groupe à base d'acide ascorbique, et un procédé de coloration, spécialement avec un effet éclaircissant, d'éléments à base de kératine tels que les cheveux, en utilisant ladite composition. De manière similaire, l'invention concerne de nouveaux colorants portant un groupe à base d'acide ascorbique et leurs utilisations dans l'éclaircissement d'éléments à base de kératine. Cette composition permet des colorations particulièrement rapides et visibles sur des fibres de kératine foncées, même en l'absence d'agent chimique oxydant.
PCT/EP2011/070686 2010-11-24 2011-11-22 Nouveaux colorants directs contenant une unité à base d'acide ascorbique, composition de colorant comprenant ces derniers et procédé de coloration d'éléments humains à base de kératine à l'aide de ces colorants WO2012069476A1 (fr)

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FR1059679A FR2967683B1 (fr) 2010-11-24 2010-11-24 Nouveaux colorants directs a motif derive de l'acide ascorbique, composition de teinture les comprenant et procede de coloration des matieres keratiniques humaines a partir de ces colorants
FR1059679 2010-11-24
US41849810P 2010-12-01 2010-12-01
US61/418,498 2010-12-01

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WO2014090364A1 (fr) 2012-12-13 2014-06-19 Merck Patent Gmbh Quinones substituées ou analogues utilisés comme colorants
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

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FR3028521B1 (fr) * 2014-11-17 2017-12-15 Oreal Nouveaux colorants directs a motif derive de l'acide ascorbique et a linker heterocyclique, composition de teinture les comprenant et procede de coloration des matieres keratiniques humaines a partir de ces colorants

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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
WO2014090364A1 (fr) 2012-12-13 2014-06-19 Merck Patent Gmbh Quinones substituées ou analogues utilisés comme colorants
US9458142B2 (en) 2012-12-13 2016-10-04 Merck Patent Gmbh Substituted quinones or analogues as colouring agents

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