Classifications

• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
  • A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
  • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
  • A61K8/35—Ketones, e.g. benzophenone
• • 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
  • A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
  • A61Q1/02—Preparations containing skin colorants, e.g. pigments
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
  • A61Q1/02—Preparations containing skin colorants, e.g. pigments
  • A61Q1/10—Preparations containing skin colorants, e.g. pigments for eyes, e.g. eyeliner, mascara
• • 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
  • A61Q5/02—Preparations for cleaning the hair

Definitions

• the invention relates to a cosmetic or dermatological composition for topical use, in particular for the photoprotection of the skin and hair, characterized in that it comprises at least in a cosmetically acceptable carrier:
• the invention relates to a new method for improving the stability of at least one dibenzoylmethane derivative with respect to UV radiation, consisting in associating with said dibenzoylmethane derivative an effective amount of at least one dimer derived from ⁇ -special alkylstyrene
• UV-A rays with wavelengths between 320 and 400 nm, which cause browning of the skin, are capable of inducing an alteration of the latter, in particular in the case of skin. sensitive or skin continuously exposed to solar radiation.
• UV-A rays cause in particular a loss of elasticity in the skin and the appearance of wrinkles, leading to premature skin aging. They promote the triggering of the erythematous reaction or amplify this reaction in certain subjects and can even be the cause of phototoxic or photoallergic reactions.
• UV-A rays For aesthetic and cosmetic reasons such as the conservation of the natural elasticity of the skin for example, more and more people wish to control the effect of UV-A rays on their skin. It is therefore desirable to also filter UV-A radiation.
• UV-A filters a particularly interesting family of UV-A filters is currently constituted by dibenzoylmethane derivatives, and in particular 4- (ter.-butyl) 4'-methoxy dibenzoylmethane, which indeed have a strong intrinsic absorption power.
• dibenzoylmethane derivatives which are now products well known per se as active filters in UV-A, are described in particular in French patent applications FR-A-2326405 and FR-A-2440933, as well as in European patent application EP-A-0114607; 4- (ter.-butyl) 4'-methoxy dibenzoyl-methane is also currently offered for sale under the trade name "PARSOL 1789" by the company HOFFMANN LAROCHE.
• the dibenzoylmethane derivatives are products relatively sensitive to ultraviolet radiation (especially UV-A), that is to say, more precisely, that they have an annoying tendency to degrade more or less quickly. under the action of the latter.
• UV-A ultraviolet radiation
• this substantial lack of photochemical stability of the dibenzoylmethane derivatives in the face of the ultraviolet radiation to which they are by nature intended to be subjected does not make it possible to guarantee constant protection during prolonged sun exposure, so that applications repeated at intervals of time Regular and close together must be performed by the user to obtain effective protection of the skin against UV rays.
• the Applicant has now discovered, surprisingly, that by combining the above-mentioned dibenzoylmethane derivatives with a quantity effective of at least one dimer derived from a particular ⁇ -alkylstyrene which will be defined later, it was possible to substantially and remarkably improve the photochemical stability (or photostability) of these same dibenzoylmethane derivatives.
• a new cosmetic or dermatological composition for topical use, in particular for the photoprotection of the skin and hair, characterized in that it comprises at less in a cosmetically acceptable support:
• Another object of the invention is a new process for stabilizing dibenzoylmethane derivatives with respect to UV radiation (wavelengths between 280 nm and 400 nm approximately), in particular solar radiation, characterized by the fact that it consists in associating with said dibenzoylmethane derivatives an effective amount of at least one dimer derived from ⁇ -alkylstyrene of formula (I) defined below.
• effective amount of dimer derived from ⁇ -alkylstyrene is meant an amount sufficient to obtain a significant and significant improvement in the photostability of the dibenzoylmethane derivative (s) of the photoprotective cosmetic composition.
• This minimum quantity of photostabilizing agent to be used which can vary depending on the nature of the cosmetically acceptable support chosen for the composition, can be determined without any difficulty by means of a conventional test for measuring photostability, such as that given in the examples below.
• the present invention also finally relates to the use of a dimer derived from ⁇ -alkylstyrene of formula (I) defined below in the preparation of a cosmetic or dermatological composition comprising at least one derivative of dibenzoylmethane in order to improve the stability vis-à-vis UV rays of said dibenzoylmethane derivative contained.
• a dimer derived from ⁇ -alkylstyrene of formula (I) defined below in the preparation of a cosmetic or dermatological composition comprising at least one derivative of dibenzoylmethane in order to improve the stability vis-à-vis UV rays of said dibenzoylmethane derivative contained.
• dimeric compounds derived from ⁇ -alkylstyrene in accordance with the invention correspond to the following formula (I):
• - R 1 and R 2 identical or different, denote hydrogen, OH, NH 2 , a C 1 -C 1 2 alkyl radical, linear or branched; alkoxy C1-C 12, linear or branched; a linear or branched CrC 12 monoalkylamino radical; a linear or branched C 1 -C 12 dialkylamino radical or a water-solubilizing substituent chosen from a carboxylate group, a sulfonate group or an ammonium residue; - R 3 and R 4 , identical or different, denote a group COOR 6 , COR 6 , CONR 6 R 7 or CN;
• R 5 denotes a linear or branched C-1-C12 alkyl radical
• R 6 and R 7 identical or different denote hydrogen, a linear or branched C1-C12 alkyl radical; a linear or branched C2-C10 alkenyl radical; a C3-C10 cycloalkyl radical branched or not; a branched or unbranched C 3 -C 10 cycloalkenyl; C6-C18 aryl, C 4 -C heteroaryl; said cycloalkyl, cycloalkenyl or aryl groups which may contain one or more substituents chosen from halogens, a cyano group, a nitro group, an amino group, a Cr C4 monoalkylamino radical, a C ⁇ -C -dialkylamino radical, a hydroxy group, a radical C- ⁇ -C-4-alkyl, a C ⁇ -C alkoxy radical; said cycloalkyl groups, cycloalkenyl possibly comprising one or more heteroatoms (for example O, N,
• - A denotes O, S or a group NR 8 ;
• R 8 denotes hydrogen or a C 1 -C 12 alkyl radical, linear or branched;
• B denotes a linear or branched C 1 -C 12 alkylene radical which may contain one or more substituents chosen from hydroxy, OC-i-C ⁇ -acyl, NH 2 ,
• NH-Ci-Ce-alkyl NH-C ⁇ -C 6 .acyl, CN, COOH, COO-C ⁇ -C 6 -acyl; a C -C ⁇ 2 cycloalkylene radical, branched or not; a C 8 -C 22 aralkylene radical; a C9-C21 monooxoaralkylene radical; a group [X] n -Y-;
• At least two of the radicals R 1 , R 2 and R 8 can together form a 5 or 6-membered ring with the benzene ring to which they are linked.
• - X denotes a group -CH 2 -CH 2 -Z-, -CH 2 CH 2 CH 2 Z-, -CH (CH 3 ) -CH 2 -Z-,
• -CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -Z- -CH 2 -CH (CH 2 CH 3 ) -Z-
• - Y denotes a group -CH 2 -CH 2 -, -CH2CH2CH2-, -CH (CH 3 ) -CH 2 -, -CH 2 -CH 2 -CH 2 -CH2-, -CH -CH (CH 2 CH 3 ) -;
• - Z denotes O or S
• - n varies from 1 to 150.
• C 1 to C 2 alkyl radicals for the radicals R 1 , R 2 , R 6 , R 8 and B, there may be mentioned for example: methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2 -methylpropyl, 1, 1-dimethylethyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1, 1- dimethylpropyl, 1, 2-dimethylpropyl , 1-methylpentyle, 2-methylpentyle, 3-methylpentyle, 4-methylpentyle, 1,1-dimethylbutyl, 1,2-dimethylbutyie, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3 -dimethylbutyl, 1- eth
• alkenyl groups C2-C 10 for R 6 and R 7, there may be mentioned for example: ethenyl, n-propenyl, 1-methylethenyl, n-butenyl, 1-methyl-propenyl, 2-methyl propenyl, 1!
• Cycloalkyl radicals such as C 3 -C 10 for R 6 and R 7, there may be mentioned for example: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, 1-methylcyclopropyl, 1-ethylcyclopropyl, 1-propylcyclopropyle, 1-butyl-cyclopropyl , 1-pentylcyclopropyle, 1-methyl-1-butylcyclopropyle, 1, 2-dimethyl-cyclypropyl, 1-methyl-2-ethylcyclopropyle, cyclooctyle, cyclononyl or cyclodecyl.
• cyclobutenyl As C 3 -C 10 cycloalkylene radicals having one or more double bonds, for the radicals R 6 and R 7 , there may be mentioned: cyclobutenyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl, 1, 3-cyclohexadienyl, 1, 4-cyclohexadienyl, cycloheptenyl , cycloheptatrienyl, cyclooctenyl, 1,5-cyclooctadienyl, cyclooctetraenyl, cyclononenyl or cyclodecenyl.
• C 1 -C 12 alkoxy radicals for the radicals R 1 and R 2 there may be mentioned: methoxy, n-propoxy, 1-methylpropoxy, n-pentoxy, 3-methylbutoxy, 2,2-dimethylpropoxy, 1-methyl-1 -ethylpropoxy, octoxy, ethoxy, n-propoxy, n-butoxy, 2-methylpropoxy, 1, 1-dimethylpropoxy, hexoxy, heptoxy, 2-ethylhexoxy.
• the aryl groups for the radicals R 6 and R 7 are more particularly phenyl, methoxyphenyl or naphthyl.
• the water-soluble groups designated by the radicals R 1 and R 2 are, for example, carboxylate groups, sulfonates and more particularly their salts with physiologically acceptable cations such as the alkali metal salts or the trialkylammonium salts such as the tri (hydroxyalkyl) salts ammonium or 2-methylpropan-1-ol-2-ammonium. Mention may also be made of ammonium groups such as alkylammoniums and their salified forms with physiologically acceptable anions.
• R 1 and R 2 identical or different, denote hydrogen, a C1-Cs alkyl radical, a C1-Cs alkoxy radical, a water-solubilizing substituent chosen from a carboxylate group, a sulfonate group or an ammonium residue;
• R 3 and R 4 identical or different, denote a COOR 6 or CN group;
• R 5 denotes a C1-C6 alkyl radical
• R 6 denotes a C- ⁇ -C 2 alkyl radical
• - A denotes O
• - B denotes a C- ⁇ -C ⁇ 2 alkylene radical, a C 4 -C- ⁇ 2 cycloalkylene radical, a Cs-C-22 aralkylene radical, a group [X] n -Y-;
• - X denotes a group -CH 2 -CH 2 -0-, -CH 2 CH 2 CH 2 0-, -CH (CH 3 ) -CH 2 -0-,
• - Y denotes a group -CH 2 -CH 2 -, -CH2CH 2 CH 2 -, -CH (CH 3 ) -CH 2 -, -CH2-CH2-CH2-, -CH2-CH (CH2CH 3 ) - ;
• - n varies from 1 to 20.
• R 1 and R 2 identical or different, denote hydrogen, an alkyl radical in
• C4-C8 a C 4 -C 6 alkoxy radical, a water-solubilizing substituent chosen from a carboxylate group, a sulfonate group or an ammonium residue;
• R 3 and R 4 denote a CN group
• R 5 an alkyl radical in CrC 6 ;
• - A denotes O;
• - B denotes a C1-C12 alkylene radical, a group [X] n -Y-;
• R 8 denotes hydrogen or a C 1 -C 1 2 alkyl radical
• - X denotes a group -CH 2 -CH 2 -O- or -CH (CH 3 ) -CH 2 -O-,
• - Y denotes a group -CH 2 -CH 2 - or -CH (CH 3 ) -CH 2
• - n varies from 1 to 20.
• R 5 is a CC 6 alkyl radical and more particularly methyl
• B denotes a C C 2 alkylene radical.
• the compounds of formula (I) are generally present in the composition of the invention in proportions of between 0.1% and 20% by weight, preferably between 0.5% and 10% by weight, relative to the total weight of composition.
• the dibenzoylmethane derivatives intended to be photostabilized in the context of the present invention are products already well known per se and described in particular in the aforementioned documents FR2326405, FR2440933 and EP01 14607, documents whose teachings are, as far as touches the very definition of these products, fully included for reference in this description.
• Another preferred dibenzoylmethane derivative according to the present invention is 4-isopropyl-dibenzoylmethane, a filter sold under the name of "EUSOLEX 8020" by the company MERCK, and corresponding to the following developed formula: o o
• the dibenzoylmethane derivative (s) may be present in the compositions in accordance with the invention, or in the compositions intended to be stabilized in accordance with the process of the invention, at contents which are generally between 0.1% and 20% by weight, and preferably at contents of between 0.5% and 10% by weight, relative to the total weight of the composition.
• compositions in accordance with the invention may also comprise other complementary organic UV filters active in UVA and / or UVB (absorbers), water-soluble or liposoluble or else insoluble in the cosmetic solvents commonly used.
• the additional organic UV filters are chosen in particular from anthranilates; salicylic derivatives, camphor derivatives; benzophenone derivatives; triazine derivatives such as those described in patent applications US4367390, US4,724,137, EP863145, EP517104, EP570838, EP796851, EP775698, EP878469 and EP933376, EP507691, EP507692, EP790243, EP944624; derivatives of ⁇ , ⁇ '-diphenylacrylate; benzotriazole derivatives; benzalmalonate derivatives; benzimidazole derivatives; imadazolines; bis-benzoazolyl derivatives as described in patents EP669323 and US 2,463,264; p-aminobenzoic acid derivatives (PABA); the derivatives of methylene bis- (hydroxyphenyl benzotriazole) as described in applications US 5,237,071, US 5,166,355, GB2303549, DE 19726184 and EP89
• Salicylic derivatives - Homosalate sold under the name "EUSOLEX HMS” by RONA / EM INDUSTRIES,
• Dipropyleneglycol Salicylate sold under the name "DIPSAL” by SCHER
• - TEA Salicylate sold under the name "NEO HELIOPAN TS” by HAARMANN and REIMER
• UVINUL 400 Benzophenone-1 sold under the trade name "UVINUL 400" by BASF
• UVINUL D50 Benzophenone-2 sold under the trade name "UVINUL D50" by BASF
• UVINUL M40 Benzophenone-3 or Oxybenzone, sold under the trade name "UVINUL M40" by BASF,
• UVINUL MS40 Benzophenone-4 sold under the trade name "UVINUL MS40" by BASF
• UVINUL DS-49 Benzophenone-9 sold under the trade name UVINUL DS-49 "by BASF,
• UVINUL T150 - Diethylhexyl Butamido Triazone sold under the trade name "UVASORB HEB” by SIGMA 3V
• UVASORB HEB Diethylhexyl Butamido Triazone sold under the trade name "UVASORB HEB” by SIGMA 3V
• Anthranilic derivatives - Menthyl anthranilate sold under the commercial name “NEO HELIOPAN MA” by HAARMANN and REIMER,
• the more particularly preferred complementary organic UV filters are chosen from the following compounds:
• the cosmetic compositions according to the invention may also contain pigments or else nanopigments (average size of the primary particles: generally between 5 nm and 100 nm, preferably between 10 nm and 50 nm) of metal oxides coated or not as for example of titanium oxide nanopigments (amorphous or crystallized in rutile form and / or anatase), iron, zinc, zirconium or cerium which are all UV photoprotective agents well known per se. Conventional coating agents are moreover alumina and / or aluminum stearate. Such metallic oxide nanopigments, coated or uncoated, are in particular described in patent applications EP-A-0518772 and EP-A-0518773.
• compositions according to the invention may also contain artificial tanning and / or browning agents for the skin (self-tanning agents), such as for example dihydroxyacetone (DHA).
• artificial tanning and / or browning agents for the skin such as for example dihydroxyacetone (DHA).
• DHA dihydroxyacetone
• compositions of the invention may also comprise conventional cosmetic adjuvants in particular chosen from fatty substances, organic solvents, ionic or nonionic thickeners, softeners, antioxidants, anti-free radical agents, opacifiers, stabilizers , the emollients, silicones, ⁇ -hydroxy acids, defoamers, moisturizers, vitamins, insect repellents, perfumes, preservatives, surfactants, anti-inflammatories, substance P antagonists, fillers , polymers, propellants, basifying or acidifying agents, dyes or any other ingredient usually used in cosmetics, in particular for the manufacture of sunscreen compositions in the form of emulsions.
• conventional cosmetic adjuvants in particular chosen from fatty substances, organic solvents, ionic or nonionic thickeners, softeners, antioxidants, anti-free radical agents, opacifiers, stabilizers , the emollients, silicones, ⁇ -hydroxy acids, defoamers, moisturizers, vitamins, insect repel
• the fatty substances can consist of an oil or a wax or their mixtures, and they also include fatty acids, fatty alcohols and fatty acid esters, linear or cyclic such as derivatives of benzoic acid, trimellitic and hydroxy benzoic acid.
• the oils can be chosen from animal, vegetable, mineral or synthetic oils and in particular from vaseline oil, paraffin oil, silicone oils, volatile or not, isoparaffins, polyolefins, fluorinated oils and perfluorinated.
• the waxes can be chosen from animal, fossil, vegetable, mineral or synthetic waxes known per se.
• organic solvents mention may be made of lower alcohols and polyols.
• compositions of the invention can be prepared according to techniques well known to those skilled in the art, in particular those intended for the preparation of emulsions of the oil-in-water or water-in-oil type.
• compositions can be in particular in the form of an emulsion, simple or complex (O / W, W / O, O / W / O or W / O / W) such as a cream, a milk, a gel or a cream gel, powder, solid stick and optionally be packaged as an aerosol and be in the form of a foam or spray.
• the aqueous phase thereof may comprise a nonionic vesicular dispersion prepared according to known methods (Bangham, Standish and Watkins. J. Mol. Biol. 13, 238 (1965), FR2315991 and FR2416008).
• the cosmetic composition of the invention can be used as a composition for protecting the human epidermis or the hair against ultraviolet rays, as a sunscreen composition or as a make-up product.
• the cosmetic composition according to the invention when used for the protection of the human epidermis against UV rays, or as an antisun composition, it may be in the form of a suspension or of dispersion in solvents or fatty substances, in the form of nonionic vesicular dispersion or alternatively in the form of an emulsion, preferably of the oil-in-water type, such as a cream or a milk, in the form of an ointment, gel, cream gel, solid stick, powder, stick, aerosol foam or spray.
• the cosmetic composition according to the invention when used for protecting the hair against UV rays, it can be in the form of a shampoo, lotion, gel, emulsion, nonionic vesicular dispersion and constitute, for example, a composition to rinse, apply before or after shampooing, before or after coloring or bleaching, before, during or after permanent or straightening, a styling or treating lotion or gel, a lotion or gel for brushing or setting, composition for perming or straightening, coloring or bleaching the hair.
• a shampoo, lotion, gel, emulsion, nonionic vesicular dispersion constitute, for example, a composition to rinse, apply before or after shampooing, before or after coloring or bleaching, before, during or after permanent or straightening, a styling or treating lotion or gel, a lotion or gel for brushing or setting, composition for perming or straightening, coloring or bleaching the hair.
• composition When the composition is used as an eyelash, eyebrow or skin makeup product, such as epidermis treatment cream, foundation, lipstick stick, eyeshadow, blush, mascara or liner also called “eyeliner", it can be in solid or pasty form, anhydrous or aqueous, such as oil-in-water or water-in-oil emulsions, nonionic vesicular dispersions or even suspensions.
• the aqueous phase (comprising in particular hydrophilic filters) generally represents from 50 to 95% by weight, preferably from 70 at 90% by weight, relative to the whole of the formulation
• the oily phase (comprising in particular the lipophilic filters) from 5 to 50% by weight, preferably from 10 to 30% by weight, relative to the whole of the formulation
• the (co) emulsifier (s) from 0.5 to 20% by weight, preferably from 2 to 10% by weight, relative to the whole of the formulation.
• an object of the invention is the use of a composition as defined above for the manufacture of a cosmetic or dermatological composition intended for the protection of the skin and / or the hair against radiation ultraviolet, especially solar radiation.
• Another object of the present invention resides in a method for improving the stability of at least one dibenzoylmethane derivative with respect to UV radiation, consisting in associating with said dibenzoylmethane derivative an effective amount of at least one UV filter of the dimer type derived from ⁇ -alkylstyrene of formula (I) as defined above.
• Another object of the present invention consists in the use of a UV filter of the dimer type derived from ⁇ -alkylstyrene of formula (I) as defined above in the preparation of a cosmetic or dermatological composition comprising at least a UV filter of the type derived from dibenzoylmethane with the aim of improving the stability with respect to UV rays of said derivative of dibenzoylmethane.

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• 2000
  • 2000-12-21 FR FR0016791A patent/FR2813527B1/fr not_active Expired - Fee Related
• 2001
  • 2001-08-23 JP JP2002524464A patent/JP2004526665A/ja active Pending
  • 2001-08-23 EP EP01963119A patent/EP1367986A2/de not_active Withdrawn
  • 2001-08-23 US US10/129,483 patent/US20030165443A1/en not_active Abandoned
  • 2001-08-23 WO PCT/FR2001/002655 patent/WO2002019979A2/fr not_active Ceased

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