WO2004028483A2 - Cosmetic or dermatological composition containing an ascorbic acid derivative and a filter - Google Patents

Cosmetic or dermatological composition containing an ascorbic acid derivative and a filter Download PDF

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Publication number
WO2004028483A2
WO2004028483A2 PCT/FR2003/002626 FR0302626W WO2004028483A2 WO 2004028483 A2 WO2004028483 A2 WO 2004028483A2 FR 0302626 W FR0302626 W FR 0302626W WO 2004028483 A2 WO2004028483 A2 WO 2004028483A2
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WO
WIPO (PCT)
Prior art keywords
composition according
radical
skin
composition
carbon atoms
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Application number
PCT/FR2003/002626
Other languages
French (fr)
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WO2004028483A3 (en
Inventor
Valérie DE POILLY
Original Assignee
L'oreal
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Publication date
Application filed by L'oreal filed Critical L'oreal
Priority to AU2003278242A priority Critical patent/AU2003278242A1/en
Priority to EP03769553A priority patent/EP1558205A2/en
Priority to JP2004539107A priority patent/JP2006504699A/en
Publication of WO2004028483A2 publication Critical patent/WO2004028483A2/en
Publication of WO2004028483A3 publication Critical patent/WO2004028483A3/en

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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/67Vitamins
    • A61K8/676Ascorbic acid, i.e. vitamin C
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/46Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur
    • A61K8/466Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur containing sulfonic acid derivatives; Salts
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/494Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8164Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers, e.g. poly (methyl vinyl ether-co-maleic anhydride)
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00Preparations for care of the skin
    • A61Q19/02Preparations for care of the skin for chemically bleaching or whitening the skin
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00Preparations for care of the skin
    • A61Q19/08Anti-ageing preparations

Definitions

  • Cosmetic or dermatological composition containing an ascorbic acid derivative and a filter
  • the present invention relates to an aqueous composition
  • an aqueous composition comprising, in a physiologically acceptable medium, at least one metal salt of phosphorylated ascorbic acid, at least one UN filter. comprising a sulfonic function, and at least one polymer of maleic anhydride, and to its uses in the cosmetic and dermatological fields, in particular for depigmenting the skin, preventing and / or combating skin spots, wrinkles and / or fine lines the skin, to prevent and / or fight against the signs of skin aging.
  • the invention also relates to the use of a polymer of maleic anhydride to obtain a homogeneous aqueous mixture of metal salt of phosphorylated ascorbic acid and of filter UN. sulfonic acid.
  • ascorbic acid stimulates the synthesis of connective tissue and in particular collagen, strengthens the defenses of the cutaneous tissue against external aggressions such as ultraviolet radiation and pollution, compensates for the vitamin E deficiency in the skin, depigments the skin. and has an anti-free radical function.
  • ascorbic acid is very sensitive to certain environmental parameters and in particular to oxidation phenomena.
  • ascorbic acid derivatives mention may be made, for example, of the metal salts of phosphorylated ascorbic acid and in particular magnesium ascorbylphosphate.
  • sunscreens are water-soluble compounds having a sulfonic function, and it has been observed that it is very difficult to obtain a stable and homogeneous composition when the composition contains such a filter and a metal salt of phosphorylated ascorbic acid. .
  • the Applicant has surprisingly discovered that, while the usual chelating agents such as EDTA (ethylenediaminetetraacetic acid) and its salts were ineffective in solving the problem of the invention, the use of a particular polymer in a composition containing metallic salts of phosphorylated ascorbic acid and filters comprising a sulfonic function, made it possible to solve the problem of incompatibility of these compounds, and to obtain homogeneous compositions.
  • the subject of the present invention is an aqueous composition comprising, in a physiologically acceptable medium, at least one metal salt of phosphorylated ascorbic acid, at least one UN filter. water-soluble comprising at least one sulphonic function, and at least one polymer of maleic anhydride.
  • topically acceptable medium means a medium compatible with skin tissues such as the skin, scalp, eyelashes, eyebrows, hair, nails and mucous membranes.
  • the composition of the invention is intended for topical application and it can in particular constitute a cosmetic or dermatological composition.
  • the polymer used makes it possible to obtain a homogeneous aqueous composition of metal salt of phosphorylated ascorbic acid and of a UN filter. water-soluble comprising at least one sulphonic function.
  • the subject of the invention is also the use of a polymer of maleic anhydride, in order to obtain a homogeneous aqueous composition containing at least one metal salt of phosphorylated ascorbic acid and at least one UN filter. water-soluble comprising at least one sulphonic function.
  • homogeneous is understood to mean a composition not comprising crystals and having a smooth appearance with the naked eye.
  • maleic anhydride polymer means both homopolymers and copolymers of maleic anhydride, and, in general, any polymer obtained by polymerization or copolymerization of one or more several maleic anhydride units, the latter being optionally hydrolysed, partially or totally.
  • hydrophilic polymers are used, that is to say polymers having a solubility in water, greater than or equal to 2 g / 1.
  • Polymers which are more particularly suitable for implementing the invention are polymers obtained by polymerization or copolymerization of one or more maleic anhydride units and whose maleic anhydride units are in hydrolyzed form, and preferably in the form of alkaline salts, by example in the form of sodium, potassium or lithium salts, sodium salts being preferred.
  • the polymers are in the form of copolymers comprising maleic anhydride monomers and co-monomers chosen from vinyl acetate, vinyl alcohol, vinylpyrrolidone, olefins comprising from 2 to 20 carbon atoms such as octadecene, ethylene, isobutylene, diisobutylene, isooctylene, and alkylvinyl ethers, in particular methyl vinyl ether or stearyl vinyl ether, styrene, and their mixtures.
  • the polymer used according to the invention has a molar fraction in maleic anhydride unit of between 0.1 and 1, and more preferably between 0.4 and 0.9.
  • the molar mass by weight of the maleic anhydride polymers used according to the invention can advantageously range from 1000 to 500,000 and preferably from 1000 to 50,000.
  • the polymer used is a copolymer of styrene and maleic anhydride, and in particular a copolymer of styrene and maleic anhydride in a 50/50 ratio.
  • the styrene / maleic anhydride copolymer 50/50
  • CTFA name Sodium tyrene / maleic acid copolymer
  • SMA1000HNa ® 40% sodium salt in water
  • SMA1000HNa ® sold under the reference SMA1000HNa ® by the company ATOFINA.
  • the polymer is present in the composition according to the invention in an amount sufficient to obtain the desired effect, that is to say in an amount sufficient for the mixture of metallic salt of phosphorylated ascorbic acid and filter with sulfonic function to be stable and homogeneous.
  • the molar ratio between the quantity of maleic anhydride units and the metal salt of phosphorylated ascorbic acid varies from 0.005 to 10 and preferably from 0.01 to 1.
  • the amount of polymer (in active material) ranges from 0.05 to 30% by weight, and more particularly from 0.1 to 10% by weight relative to the total weight of the composition.
  • the metallic salt of phosphorylated ascorbic acid can be chosen from alkali metal ascorbyl phosphates, alkaline earth metal ascorbyl phosphates, transition metal ascorbyl phosphates, and mixtures thereof. Mention may in particular be made of ascorbyl phosphates of magnesium, sodium, potassium, calcium, zinc and their mixtures. According to a preferred embodiment of the invention, it is magnesium ascorbyl phosphate.
  • the amount of metal salt of phosphorylated ascorbic acid can vary to a large extent depending on the purpose. This amount can range, for example, from 0.1 to 20% by weight relative to the total weight of the composition, more particularly from 0.05 to 10% by weight and better still from 0.05 to 5% by weight relative to the weight. total of the composition.
  • the filters used in the composition of the invention have at least one sulfonic function and are water-soluble. They can be chosen from sulfonated filters and / or water-soluble sulfonates. These filters can be partially neutralized with an organic base such as triethanolamine and ethylene diamine.
  • the filters used can in particular be chosen from sulfone or sulfonate derivatives of benzylidene camphor, benzophenone or phenylbenzimidazole, and mixtures thereof.
  • the sulfone or sulfonate filters used in the invention are derivatives of benzylidene camphor.
  • benzylidene camphor derivatives which can be used in the invention have the following general formula (a):
  • B represents -H or -SO3H
  • D represents one or more alkyl or alkoxy radicals, identical or different when n> 2, linear or branched containing from 1 to 18 carbon atoms approximately, a halo radical, a hydroxyl radical.
  • A preferably in meta or para, represents:
  • Y represents H or SO3H
  • R 11 denotes a hydrogen atom, an alkyl or alkoxy radical, linear or branched containing from 1 to 6 carbon atoms approximately or the radical -SO3H, Ru being -
  • R ⁇ 2 denotes a hydrogen atom, an alkyl or alkoxy radical, linear or branched, containing from 1 to 6 carbon atoms approximately,
  • X is an oxygen or sulfur atom or a group -NR-, R being a hydrogen atom or an alkyl radical, linear or branched, containing from 1 to 6 carbon atoms approximately,
  • - n is equal to 0 or is a number ranging from 1 to 4 (0 ⁇ n ⁇ 4)
  • - Ri represents one or more alkyl or alkoxy radicals, identical or different, linear or branched, preferably containing approximately from 1 to 4 carbon atoms.
  • - R 2 denotes a hydrogen atom or a radical -SO3H
  • R 3 , R 4 , R 5 and R 6 identical or different, represent a hydroxyl group, an alkyl radical having from 1 to 4 carbon atoms approximately, linear or branched, an alkenyl radical having from 2 to 4 carbon atoms approximately, linear or branched, an alkoxy radical having from 1 to 4 carbon atoms, linear or branched, an alkenyloxy radical having from 2 to 4 carbon atoms, linear or branched, a halo radical; moreover, a radical R 3 to R ⁇ only can be a radical -SO3H, at least one of the radicals R 3 to R denoting the radical -SO3H when R 2 is a hydrogen atom. One or more -SO3H functions can also be neutralized.
  • R 4 denotes the radical -SO 3 H in the para position of the benzylidenecamphor and R 2 , R 3 , R 5 and R 6 each denote a hydrogen atom, that is to say the 4'-sulfo 3-benzylidenecamphor acid (CTFA name: Benzylidene Camphor Sulfonic Acid), manufactured under the name "MEXORYL SL" by the company CHIMEX,
  • R 3 , R 4 , R 5 and R 6 each denote a hydrogen atom and R 2 denotes a radical -SO 3 H, that is to say 3-benzylidene camphor-10 sulfonic acid.
  • R4 denotes a methyl radical in the para position of the benzylidenecamphor
  • R5 a radical -SO3H and R 2
  • R 3 and R @ represent a hydrogen atom, that is to say 4'-methyl 3'- acid sulfo 3-benzylidenecamphor
  • R 4 denotes a chlorine atom in the para position of the benzylidenecamphor
  • R 5 a radical -SO3H and R 2 , R 3 and R ⁇ represent a hydrogen atom, that is to say 4'-chloro 3 acid '-sulfo 3-benzylidenecamphor.
  • R 4 denotes a methyl radical in the para position of the benzylidenecamphor
  • R 3 , R 5 and R ⁇ denote a hydrogen atom
  • R 2 denotes a radical -SO3H, that is to say 4'-methyl 3 acid -benzylidene camphor 10-sulfonic.
  • R 2 represents a radical -SO3H
  • R 3 is a methyl radical
  • R 4 a hydrogen atom
  • R5 a tert-butyl radical
  • R ⁇ a hydroxyl radical, that is to say (3-t-butyl acid 2-hydroxy 5-methyl) 3-benzylidene camphor-10-sulfonic.
  • R 2 represents a radical -SO3H
  • R 3 is a methoxy radical
  • R 4 a hydrogen atom
  • R 5 a tert-butyl radical
  • R 6 a hydroxyl radical, that is to say the acid (3-t -butyl 2-hydroxy 5-methoxy) 3-benzylidene camphor-10-sulfonic.
  • R 2 represents a radical -SO3H
  • R 3 and R 5 each denote a tert-butyl radical
  • R 4 a hydroxyl radical
  • RQ a hydrogen atom, that is to say acid (3,5-diterbutyl 4 -hydroxy) 3-benzylidene camphor-10-sulfonic.
  • R 4 represents a methoxy radical in para
  • R 5 represents -SO3H
  • R 2 , R 3 and R 6 represent H, that is to say 4'-methoxy 3'-sulfo-3-benzylidene camphor acid.
  • R 2 denotes a radical -SO3H
  • R 3 and R ⁇ represent H
  • R ⁇ and R 5 forming a methylenedioxy radical, that is to say 3- (4,5-methylenedioxy) benzylidene campho-10-sulfonic acid .
  • R2 represents a radical -SO3H
  • R 4 a methoxy radical
  • the radicals R 3 , R 5 and R 6 represent H, that is to say 3- (4-methoxy) benzylidene campho-10-sulfonic acid
  • R 2 represents a radical -SO3H
  • j and R 5 are both a methoxy radical and the radicals R 3 and R 6 represent H, that is to say 3- (4,5-dimethoxy) benzylidene acid camphor-10-sulfonic acid.
  • R 2 represents a radical -SO3H
  • R 4 is an n-butoxy radical and the radicals R 3 ,
  • R 5 and Re represent a hydrogen atom, that is to say 3- (4-n.butoxy) benzylidene campho-10-sulfonic acid.
  • R 2 represents a radical -SO3H
  • i is an n-butoxy radical
  • R 5 is a methoxy radical
  • R 3 and R ⁇ both denote a hydrogen atom, that is to say 3- ( 4-n.butoxy 5-methoxy) benzylidene campho-10-sulfonic.
  • Ru denotes a hydrogen atom, an alkyl or alkoxy radical, linear or branched, containing from 1 to 6 carbon atoms approximately or a radical -SO3H,
  • R 12 denotes a hydrogen atom, an alkyl or alkoxy radical, linear or branched, containing from 1 to 6 carbon atoms approximately,
  • R 13 denotes a hydrogen atom or a radical -SO3H
  • - X is an oxygen or sulfur atom or a group -NR-, R being a hydrogen atom or an alkyl radical, linear or branched, preferably containing from 1 to 6 carbon atoms.
  • R 12 and R 13 both denote a hydrogen atom, that is to say 2- [4- (camphomethylidene) phenyl] benzimidazole-5-sulfonic acid.
  • R 9 denotes a divalent radical: - (CH2) ⁇ r o ⁇ _CH 2 -CHOH-CH2-, m being an integer ranging from 1 to 10 (1 ⁇ m ⁇ 10),
  • - R1 0 denotes a hydrogen atom, an alkoxy radical containing from 1 to 4 carbon atoms approximately or a divalent radical - O - linked to the radical Rg when the latter is also divalent
  • phenylbenzimidazole sulfonic acid (CTFA name: Phenylbenzimidazole Sulfonic Acid), sold under the trade name EUSOLEX 232 by the company MERCK.
  • the quantity of UN filter (s). with a sulfonic function can vary to a large extent depending on the sun protection sought and the SPF desired for the composition.
  • This amount (in active material) can range, for example, from 0.01 to 10% by weight relative to the total weight of the composition, more particularly from 0.02 to 5% by weight of active material relative to the total weight of the composition. .
  • the physiologically acceptable medium of the aqueous composition according to the invention comprises water. It may more particularly consist of water and optionally a physiologically acceptable organic solvent chosen, for example, from lower alcohols having from 1 to 8 carbon atoms and in particular from 1 to 6 carbon atoms, such as ethanol, l isopropanol, propanol, butanol; polyethylene glycols having from 6 to 80 ethylene oxide units; polyols such as propylene glycol, isoprene glycol, butylene glycol, glycerin, sorbitol; and their mixtures.
  • a physiologically acceptable organic solvent chosen, for example, from lower alcohols having from 1 to 8 carbon atoms and in particular from 1 to 6 carbon atoms, such as ethanol, l isopropanol, propanol, butanol; polyethylene glycols having from 6 to 80 ethylene oxide units; polyols such as propylene glycol, isoprene glycol, butylene glycol, g
  • composition according to the invention generally has a pH compatible with the skin, preferably ranging from 2 to 7, and better still from 3 to 6, this pH varying according to the acid active agents contained in the composition.
  • the compositions according to the invention can be presented in all the galenical forms conventionally used for a topical application and in particular in the form of aqueous or hydroalcoholic solutions, or aqueous gels, or, when an oily phase is added, in the form of oil emulsions.
  • compositions are prepared according to the usual methods.
  • compositions used according to the invention can be more or less fluid and have the appearance of a white or colored cream, an ointment, a milk, a lotion, a serum, 'a paste, a foam. They can optionally be applied to the skin in the form of an aerosol. They can also be in solid form, and for example in the form of a stick.
  • composition used according to the invention comprises an oily phase
  • it preferably contains at least one oil, in particular a cosmetic oil. It may also contain other fatty substances.
  • oils which can be used in the composition of the invention there may be mentioned, for example: - hydrocarbon oils of animal origin, such as perhydrosqualene; - hydrocarbon-based oils of vegetable origin, such as liquid triglycerides of fatty acids comprising from 4 to 10 carbon atoms such as triglycerides of heptanoic or octanoic acids or also, for example sunflower, corn, soybean oils, squash, grapeseed, sesame, hazelnut, apricot, macadamia, macaw, sunflower, castor, avocado, caprylic / capric acid triglycerides like those sold by Stearineries Dubois or those sold under the names Miglyol 810, 812 and 818 by the company Dynamit Nobel, jojoba oil, shea butter oil; - synthetic esters and ethers, in particular of fatty acids, such as oils of formulas R 1 COOR 2 and R 1 OR 2 in which R 1 represents the remainder of a fatty acid
  • linear or branched hydrocarbons of mineral or synthetic origin, such as paraffin oils, volatile or not, and their derivatives, branched chain hydrocarbon oils containing from 10 to 20 carbon atoms such as isohexadecane, l 'isododecane, isoparaffins and their mixtures, petrolatum, polydecenes, hydrogenated polyisobutene such as Parléam® oil; - natural or synthetic essential oils such as, for example, eucalyptus, lavandin, lavender, vetiver, litsea cubeba, lemon, sandalwood, rosemary, chamomile, savory, walnut oils nutmeg, cinnamon, hyssop, caraway, orange, geraniol, cade and bergamot;
  • alcohols and fatty acids having 8 to 26 carbon atoms such as alcohol or cetylic acid, stearyl alcohol, stearic acid, the mixture of cetyl alcohol and stearyl alcohol (cetylstearyl alcohol) , octyl dodecanol, 2-butyloctanol, 2-hexyldecanol, 2-undecylpentadecanol, oleic alcohol or linoleic alcohol;
  • silicone oils such as polymethylsiloxanes (PDMS) volatile or not with a linear or cyclic silicone chain, liquid or pasty at room temperature, in particular cyclopolydimethylsiloxanes (cyclomethicones) such as cyclohexasiloxane; polydimethylsiloxanes comprising groups alkyl, alkoxy or phenyl, during or at the end of the silicone chain, groups having from 2 to 24 carbon atoms; phenylated silicones such as phenyltrimethicones, phenyldimethicones, phenyltrimethylsiloxydiphenyl-siloxanes, diphenyl-dimethicones, diphenylmethyldiphenyl trisiloxanes, 2-phenylethyltrimethyl-siloxysilicates, and polymethylphenyls; - their mixtures.
  • PDMS polymethylsiloxanes
  • cyclomethicones such as cyclohex
  • Hydrocarbon oil is understood to mean, in the list of oils mentioned above, any oil mainly comprising carbon and hydrogen atoms, and optionally ester, ether, fluorinated, carboxylic acid and / or alcohol groups.
  • the other fatty substances which may be present in the oily phase are, for example, fatty acids containing from 8 to 30 carbon atoms, such as stearic acid, lauric acid, palmitic acid and oleic acid; waxes such as lanolin, beeswax, carnauba or candellila wax, paraffin, lignite or microcrystalline waxes, ceresin or ozokerite, synthetic waxes such as polyethylene waxes, waxes from Fischer-Tropsch; silicone resins such as trifluoromethyl-C1-4-alkyldimethicone and trifluoropropyldimethicone; and silicone elastomers such as the products marketed under the names "KSG” by the company Shin-Etsu, under the names "Trefil", "BY29” or "EPSX” by the company Dow Corning or under the names "Gransil” by the Grant Industries.
  • fatty acids containing from 8 to 30 carbon atoms such as stearic acid
  • fatty substances can be chosen in a variety of ways by a person skilled in the art in order to prepare a composition having the properties, for example of consistency or texture, desired.
  • the proportion of the oily phase of the emulsion can range from 5 to 80% by weight, and preferably from 5 to 50% by weight relative to the total weight of the composition.
  • the emulsions generally contain at least one emulsifier chosen from amphoteric, anionic, cationic or nonionic emulsifiers, used alone or as a mixture, and optionally a co-emulsifier.
  • the emulsifiers are appropriately selected as follows. emulsion to be obtained (W / O or O / W).
  • the emulsifier and the co-emulsifier are generally present in the composition, in a proportion which can range, for example, from 0.3 to 30% by weight, and preferably from 0.5 to 20% by weight relative to the total weight of the composition.
  • dimethicone copolyols such as the mixture of cyclomethicone and dimethicone copolyol, sold under the name "DC 5225 C” by the company Dow Corning, and alkyl dimethicone copolyols, for example, may be mentioned as emulsifiers.
  • One or more co-emulsifiers can also be added.
  • the co-emulsifier can be chosen from the group comprising alkylated polyol esters.
  • alkylated polyol esters mention may in particular be made of glycerol and / or sorbitan esters and for example polyglycerol isostearate, such as the product sold under the name Isolan Gl 34 by the company Goldschmidt, sorbitan isostearate, such as the product sold under the name Ariacel 987 by the company ICI, sorbitan and glycerol isostearate, such as the product sold under the name Ariacel 986 by the company ICI, and their mixtures.
  • polyglycerol isostearate such as the product sold under the name Isolan Gl 34 by the company Goldschmidt
  • sorbitan isostearate such as the product sold under the name Ariacel 987 by the company ICI
  • sorbitan and glycerol isostearate such as the product sold under the name Ariacel 986 by the company ICI, and their mixtures.
  • non-ionic surfactants may be mentioned, for example, as emulsifiers, and in particular esters of polyols and of fatty acids with saturated or unsaturated chain comprising for example from 8 to 24 carbon atoms and better still from 12 with 22 carbon atoms, and their oxyalkylenated derivatives, that is to say comprising oxyethylenated and / or oxypropylenated units, such as the glyceryl esters of C 8 -C 24 fatty acid, and their oxyalkylenated derivatives; polyethylene glycol and Cs-C 24 fatty acid esters, and their oxyalkylenated derivatives; esters of sorbitol and of C 8 -C 24 fatty acid, and their oxyalkylenated derivatives; esters of sugar (sucrose, glucose, alkylglucose) and of C 8 -C 24 fatty acid, and their oxyalkylenated derivatives;
  • glyceryl ester of fatty acid there may be mentioned in particular glyceryl stearate (mono-, di- and or glyceryl tri-stearate) (CTFA name: glyceryl stearate) or glyceryl ricinoleate, and mixtures thereof.
  • CFA name glyceryl stearate
  • glyceryl ricinoleate glyceryl ricinoleate
  • polyethylene glycol and fatty acid esters mention may in particular be made of polyethylene glycol stearate (polyethylene glycol mono-, di- and / or tri-stearate), and more especially polyethylene glycol 50 OE monostearate (CTFA name). : PEG-50 stearate), polyethylene glycol 100 OE monostearate (CTFA name: PEG-100 stearate and mixtures thereof.
  • surfactants such as for example the product containing Glyceryl stearate and PEG-100 stearate, sold under the name ARLACEL 165 by the company Uniqema, and the product containing Glyceryl stearate (glyceryl mono-distearate ) and potassium stearate, sold under the name TEGIN by the company Goldschmidt (name CTFA: glyceryl stearate SE).
  • fatty acid and glucose or alkylglucose ester mention may in particular be made of glucose palmitate, alkylglucose sesquistearates such as methylglucose sesquistearate, alkylglucose palmitates such as methylglucose or ethylglucose palmitate, fatty esters of methylglucoside and more especially the diester of methylglucoside and oleic acid (CTFA name: Methyl glucose dioleate); the mixed ester of methylglucoside and of the oleic acid / hydroxystearic acid mixture (CTFA name: Methyl glucose dioleate / hydroxystearate); the ester of methylglucoside and isostearic acid (CTFA name: Methyl glucose isos tearate); the ester of methylglucoside and of lauric acid (CTFA name: Methyl glucose laurate); the mixture of monoester and diester of methylglucoside and
  • oxyethylenated ethers of fatty acid and of glucose or of alkylglucose mention may, for example, be made of oxyethylenated ethers of fatty acid and of methylglucose, and in particular the polyethylene glycol ether of methyl glucose diester and of stearic acid.
  • CTFA name PEG-20 methyl glucose distearate
  • Glucam E-20 distearate the product sold under the name Glucam E-20 distearate by the company AMERCHOL
  • CTFA name PEG-20 methyl glucose sesquistearate
  • Glucamate SSE-20 the product sold under the name Glucamate SSE-20 by the company AMERCHOL and that sold under the name Grillocose PSE-20 by the company GOLDSCHMIDT, and their mixtures.
  • sucrose esters mention may, for example, be made of sucrose palmito-stearate, sucrose stearate and sucrose mono laurate.
  • fatty alcohol ethers mention may be made, for example, of polyethylene glycol and fatty alcohol ethers containing from 8 to 30 carbon atoms, and in particular from 10 to 22 carbon atoms, such as polyethylene glycol ethers and cetyl, stearyl, tearyl alcohol (mixture of cetyl and stearyl alcohol). Mention may be made, for example, of ethers comprising from 1 to 200 and preferably from 2 to 100 oxyethylenated groups, such as those of CTFA name Ce teareth-20, Ceteareth-30, and their mixtures.
  • alkylpolyglucosides such as the product sold under the name MYDOL 10 by the company Kao Chemicals, the product sold under the name PLANTAREN 2000 by the company Henkel, and the product sold under the name ORAMIX NS 10 by the company Seppic; caprylyl / capryl glucoside such as the product sold under the name ORAMIX CG 110 by the company Seppic or under the name LUTENSOL GD 70 by the company BASF; laurylgiucoside such as the products marketed under the names PLANTAREN 1200 N and PLANTACARE 1200 by the company Henkel; coco-glucoside such as the product sold under the name PLANTACARE 818 / UP by the company Henkel; ketostearyl glucoside optionally mixed with cetostearyl alcohol, marketed for example under the name MONTANOV 68 by the company Seppic, under the name TEGO-CARE
  • the composition is in the form of O / W emulsions.
  • the cosmetic or dermatological composition of the invention may also contain one or more adjuvants customary in the cosmetic or dermatological field.
  • adjuvants are used in the usual proportions in the cosmetic field, and for example from 0.01 to 30% of the total weight of the composition, and they are, depending on their nature, introduced into the aqueous phase of the composition or into a phase oily when it is present, or in vesicles or any other type of vector. These adjuvants and their concentrations must be such that they do not modify the property sought for the emulsion of the invention.
  • one or more gelling agents in particular hydrophilic, that is to say soluble or dispersible in water, can be incorporated into the composition.
  • hydrophilic gelling agents mention may, for example, be made of carboxyvinyl polymers, modified or not, such as the products sold under the names Carbopol (name CTFA: carbomer) and Pemulen (name CTFA: Acrylates / C 10-30 akyl acrylate crosspolymer) by the company Goodrich; polyacrylamides; polymers and copolymers of 2-acrylamido 2-methylpropane sulfonic acid, optionally crosslinked and / or neutralized, such as the poly (2-acrylamido 2-methylpropane sulfonic acid) sold by the company Hoechst under the name "Hostacerin AMPS" (name GTFA : ammonium polyacr yldime.hyltaur amide); crosslinked anionic copoly
  • the fillers which can be used in the composition of the invention include, for example, in addition to pigments, silica powder; talc; polyamide particles and in particular those sold under the name ORGASOL by the company Atochem; polyethylene powders; microspheres based on acrylic copolymers, such as those in ethylene glycol dimethacrylate / lauryl methacrylate copolymer sold by the company Dow Corning under the name of POLYTRAP; expanded powders such as hollow microspheres and in particular, microspheres marketed under the name EXPANCEL by the company Kemanord Plast or under the name MICROPEARL F 80 ED by the company Matsumoto; silicone resin microbeads such as those sold under the name TOSPEARL by the company Toshiba Silicone; and their mixtures. These fillers can be present in amounts ranging from 0 to 20% by weight and preferably from 1 to 10% by weight relative to the total weight of the composition.
  • active agents which can be used in the composition of the invention, mention may, for example, be made of enzymes (for example lactoperoxidase, lipase, protease, phospholipase, cellulases); flavonoids; moisturizers such as protein hydrolysates; sodium hyaluronate; polyols such as glycerin, glycols such as polyethylene glycols, and sugar derivatives; anti-inflammatory drugs; procyannidolic oligomers; vitamins such as vitamin A (retinol), vitamin E (tocopherol), vitamin C (ascorbic acid), vitamin B5 (panthenol), vitamin B3 (niacinamide), derivatives of these vitamins (especially esters) and their mixtures; urea; caffeine; depigmentants such as kojic acid, hydroquinone and caffeic acid; salicylic acid and its derivatives; alpha-hydroxy acids such as lactic acid and glycolic acid and their derivatives; retinoids such as caroten
  • steroids examples include dehydroepiandrosterone (or DHEA), as well as (1) its precursors and biological derivatives, in particular the salts and esters of DHEA, such as DHEA sulfate and salicylate, 7-hydroxy DHEA , 7-keto DHEA, esters of 7-hydroxy and 7-keto DHEA, in particular 3-beta-acetoxy-7-oxo DHEA, and (2) its precursors and chemical derivatives, in particular sapogenins such as diosgenin or hecogenin, and / or their derivatives such as hecogenin acetate, and / or natural extracts containing it and in particular extracts of Dioscorea, such as wild yam (Wild Yam).
  • DHEA dehydroepiandrosterone
  • DHEA its precursors and biological derivatives
  • DHEA such as DHEA sulfate and salicylate
  • 7-hydroxy DHEA 7-keto DHEA
  • the organic UV filters other than those with a sulfonic function described above can be present in an amount of active material ranging from 0.01 to 20% by weight of active material, preferably from 0.1 to 15% by weight, and better 0.2 to 10% by weight relative to the total weight of the composition.
  • organic filters active in UV-A and / or UV-B, which can be added to the composition of the invention
  • salicylic derivatives such as ethyl hexyl salicylate sold under the trade name NEO HELIOPAN OS by Haarmann and Reimer
  • dibenzoylmethane derivatives such as Butyl Methoxydibenzoylmethane sold in particular under the trade name PARSOL 1789 by Hoffmann La Roche
  • cinnamic derivatives such as ethylhexyl Methoxycinnamate sold in particular under the trade name PARSOL MCX by Hoffmann La Roche
  • derivatives of ⁇ , ⁇ '-diphenylacrylate such as octocrylene (2-ethylhexyl ⁇ -cyano- ⁇ , ⁇ -diphenylacrylate) sold under the trade name UVINUL N539 by the company BASF
  • the composition according to the invention can constitute a cosmetic or dermatological composition and it can be used in all the usual applications of vitamin C and its derivatives. It can be used in particular to depigment and / or whiten the skin, prevent and / or fight against skin spots, wrinkles and / or fine lines of the skin, to prevent and / or fight against the signs of skin aging and / or against the harmful effects of UV radiation. It can also make it possible to tone, regenerate and / or smooth the fine lines of the skin, and / or to strengthen the skin tissues against environmental aggressions. It can also be used to treat age spots that appear on the skin with age.
  • the subject of the invention is also the cosmetic use of the composition as defined above for depigmenting and / or bleaching the skin, preventing and / or combating skin spots, wrinkles and / or fine lines on the skin. skin, to prevent and / or fight against the signs of skin aging and / or against the harmful effects of UN radiation.
  • the subject of the invention is also a cosmetic treatment process intended for depigmenting and / or bleaching the skin, preventing and / or combating skin spots, wrinkles and / or fine lines on the skin, preventing and / or combating signs of skin aging and / or against the harmful effects of UV radiation, comprising the application to the skin of a composition as defined above. It also relates to the use of the composition as defined above for the manufacture of an ointment intended for treating aging spots.
  • compositions according to the invention are given by way of illustration and without limitation.
  • the names are given in CTFA names or in chemical names.
  • the quantities are given in% by weight, unless otherwise stated.
  • the pH of the solution is 2.0. A clear solution is obtained.
  • the pH of the solution is 2.0.
  • a precipitate forms in the solution.
  • EDTA known as chelating does not solve the problem of incompatibility between magnesium ascorbyl phosphate and the sulfonic filter.
  • the pH of the solution is 1.5. A precipitate forms in the solution.
  • This example shows the incompatibility between the magnesium ascorbyl phosphate and the sulfonic filter.
  • the procedure is as follows: The magnesium ascorbyl phosphate is placed in water, or the polymer or EDTA is added, then the UN filter.
  • Cetearyl alcohol (and) Ceteareth-30 (Emulgator E-2209 from Goldschmidt) 1%
  • Procedure successively mixing phases A to F, introducing one after the other.
  • composition obtained is not homogeneous and contains many crystals.
  • EDTA known as chelating does not solve the problem of incompatibility between magnesium ascorbyl phosphate and the sulfonic filter.
  • Example 5 according to the invention. O / W emulsion
  • Phase B 0.2% xanthan gum
  • the composition obtained is fluid, smooth and homogeneous to the naked eye. It can be used as a photoprotective composition for treating and combating the signs of skin aging (anti-aging).
  • Example 6 according to the invention (O / W emulsion)
  • Cetearyl alcohol (and) Ceteareth-30 (Emulgator E-2209 from Goldschmidt) 1%
  • the composition obtained is fluid, smooth and homogeneous to the naked eye. It can be used as a depigmenting and photoprotective composition, making it possible to combat the appearance of spots.

Abstract

The invention relates to an aqueous composition which contains, in a physiologically-acceptable medium, at least one phosphorylated ascorbic acid metal salt, at least one water-soluble U.V. filter comprising at least one sulphonic function, and at least one maleic anhydride polymer. In particular, a maleic anhydride/styrene copolymer can be used as a polymer. The inventive composition is intended, in particular, to be used to depigment the skin, to prevent and/or combat skin blemishes, wrinkles and/or fine lines in the skin and to prevent and/or combat the signs of cutaneous ageing.

Description

Composition cosmétique ou dermatologique contenant un dérivé d'acide ascorbique et un filtre Cosmetic or dermatological composition containing an ascorbic acid derivative and a filter
La présente invention se rapporte à une composition aqueuse comprenant dans un milieu physiologiquement acceptable, au moins un sel métallique d'acide ascorbique phosphorylé, au moins un filtre UN. comportant une fonction sulfonique, et au moins un polymère d'anhydride maléique, et à ses utilisations dans les domaines cosmétique et dermatologique, notamment pour dépigmenter la peau, prévenir et/ou lutter contre les taches cutanées, les rides et/ou les ridules de la peau, pour prévenir et/ou lutter contre les signes du vieillissement cutané.The present invention relates to an aqueous composition comprising, in a physiologically acceptable medium, at least one metal salt of phosphorylated ascorbic acid, at least one UN filter. comprising a sulfonic function, and at least one polymer of maleic anhydride, and to its uses in the cosmetic and dermatological fields, in particular for depigmenting the skin, preventing and / or combating skin spots, wrinkles and / or fine lines the skin, to prevent and / or fight against the signs of skin aging.
L'invention se rapporte aussi à l'utilisation d'un polymère d'anhydride maléique pour obtenir un mélange aqueux homogène de sel métallique d'acide ascorbique phosphorylé et de filtre UN. sulfonique.The invention also relates to the use of a polymer of maleic anhydride to obtain a homogeneous aqueous mixture of metal salt of phosphorylated ascorbic acid and of filter UN. sulfonic acid.
Il est connu d'introduire dans des compositions cosmétiques, divers actifs destinés à apporter des traitements spécifiques à la peau et/ou aux cheveux. Toutefois, certains de ces actifs présentent l'inconvénient d'être instables en milieu aqueux et de se dégrader facilement au contact de l'eau, en particulier à cause de phénomènes d'oxydation. Ils perdent ainsi rapidement leur activité au cours du temps et cette instabilité va à encontre de l'efficacité recherchée.It is known to introduce into cosmetic compositions, various active agents intended to provide specific treatments to the skin and / or the hair. However, some of these active agents have the drawback of being unstable in an aqueous medium and of degrading easily on contact with water, in particular due to oxidation phenomena. They quickly lose their activity over time and this instability goes against the desired efficiency.
On cherche ainsi depuis longtemps à formuler l'acide ascorbique ou vitamine C, du fait de ses nombreuses propriétés bénéfiques. En particulier, l'acide ascorbique stimule la synthèse du tissu conjonctif et notamment du collagène, renforce les défenses du tissu cutané contre les agressions extérieures telles que les rayonnements ultraviolets et la pollution, compense la déficience en vitamine E de la peau, dépigmente la peau et possède une fonction anti-radicaux libres. Ces deux dernières propriétés en font un excellent candidat comme actif cosmétique ou dermatologique pour lutter contre le vieillissement de la peau ou prévenir celui-ci. Malheureusement, en raison de sa structure chimique d'alpha- cétolactone, l'acide ascorbique est très sensible à certains paramètres de l'environnement et notamment aux phénomènes d'oxydation. Il s'ensuit donc une dégradation rapide de l'acide ascorbique formulé en présence de ces paramètres, et plus particulièrement en présence d'oxygène, de lumière, d'ions métalliques, en fonction de la température, ou encore dans certaines conditions de pH (Pharm. Acta. Helv., 1969, 44, 611-667 ; STP Pharma, 1985, 4, 281-286).It has thus been sought for a long time to formulate ascorbic acid or vitamin C, because of its numerous beneficial properties. In particular, ascorbic acid stimulates the synthesis of connective tissue and in particular collagen, strengthens the defenses of the cutaneous tissue against external aggressions such as ultraviolet radiation and pollution, compensates for the vitamin E deficiency in the skin, depigments the skin. and has an anti-free radical function. These last two properties make it an excellent candidate as a cosmetic or dermatological active ingredient to fight against or prevent aging of the skin. Unfortunately, due to its chemical structure of alpha-ketolactone, ascorbic acid is very sensitive to certain environmental parameters and in particular to oxidation phenomena. So there follows a rapid degradation of the ascorbic acid formulated in the presence of these parameters, and more particularly in the presence of oxygen, light, metal ions, depending on the temperature, or even under certain pH conditions (Pharm. Acta. Helv ., 1969, 44, 611-667; STP Pharma, 1985, 4, 281-286).
Plusieurs solutions ont donc été envisagées dans l'art antérieur pour diminuer et/ou retarder la dégradation de l'acide ascorbique. Une de ces solutions a consisté à utiliser des dérivés d'acide ascorbique. Comme dérivés d'acide ascorbique, on peut citer par exemple les sels métalliques d'acide ascorbique phosphorylé et notamment l'ascorbylphosphate de magnésium.Several solutions have therefore been envisaged in the prior art for reducing and / or delaying the degradation of ascorbic acid. One of these solutions consisted in using ascorbic acid derivatives. As ascorbic acid derivatives, mention may be made, for example, of the metal salts of phosphorylated ascorbic acid and in particular magnesium ascorbylphosphate.
Par ailleurs, on associe fréquemment à de tels actifs, des molécules capables d'aider les cellules à se défendre contre l'excès de radicaux libres photo-induits et notamment des filtres solaires (ou filtres UN.), qui sont aptes à protéger la peau des agressions contre la peau, provoquées par le soleil et la lumière ultraviolette. Certains de ces filtres solaires particulièrement efficaces sont des composés hydrosolubles ayant une fonction sulfonique, et on a observé qu'il est très difficile d'obtenir une composition stable et homogène quand la composition contient un tel filtre et un sel métallique d'acide ascorbique phosphorylé.In addition, such active ingredients are frequently associated with molecules capable of helping cells to defend themselves against excess photo-induced free radicals, and in particular sun filters (or UN filters), which are capable of protecting the skin aggressions against the skin, caused by the sun and ultraviolet light. Some of these particularly effective sunscreens are water-soluble compounds having a sulfonic function, and it has been observed that it is very difficult to obtain a stable and homogeneous composition when the composition contains such a filter and a metal salt of phosphorylated ascorbic acid. .
Aussi, il subsiste le besoin d'une composition cosmétique et/ou dermatologique ayant une bonne stabilité bien que contenant à la fois des sels métalliques d'acide ascorbique phosphorylé et des filtres UN. comportant une fonction sulfonique.Also, there remains the need for a cosmetic and / or dermatological composition having good stability although containing both metallic salts of phosphorylated ascorbic acid and UN filters. having a sulfonic function.
La demanderesse a découvert de façon surprenante que, alors que les chélatants habituels tels que l'EDTA (acide éthylènediamine tétracétique) et ses sels étaient inefficaces pour résoudre le problème de l'invention, l'utilisation d'un polymère particulier dans une composition contenant des sels métalliques d'acide ascorbique phosphorylé et des filtres comportant une fonction sulfonique, permettait de résoudre le problème d'incompatibilité de ces composés, et d'obtenir des compositions homogènes. Aussi, la présente invention a pour objet un composition aqueuse comprenant dans un milieu physiologiquement acceptable, au moins un sel métallique d'acide ascorbique phosphorylé, au moins un filtre UN. hydrosoluble comportant au moins une fonction sulfonique, et au moins un polymère d'anhydride maléique.The Applicant has surprisingly discovered that, while the usual chelating agents such as EDTA (ethylenediaminetetraacetic acid) and its salts were ineffective in solving the problem of the invention, the use of a particular polymer in a composition containing metallic salts of phosphorylated ascorbic acid and filters comprising a sulfonic function, made it possible to solve the problem of incompatibility of these compounds, and to obtain homogeneous compositions. Also, the subject of the present invention is an aqueous composition comprising, in a physiologically acceptable medium, at least one metal salt of phosphorylated ascorbic acid, at least one UN filter. water-soluble comprising at least one sulphonic function, and at least one polymer of maleic anhydride.
On entend par "milieu topiquement acceptable", un milieu compatible avec les tissus cutanés tels que la peau, le cuir chevelu, les cils, les sourcils, les cheveux, les ongles et les muqueuses. La composition de l'invention est destinée à une application topique et elle peut constituer notamment une composition cosmétique ou dermatologique.The term "topically acceptable medium" means a medium compatible with skin tissues such as the skin, scalp, eyelashes, eyebrows, hair, nails and mucous membranes. The composition of the invention is intended for topical application and it can in particular constitute a cosmetic or dermatological composition.
Le polymère utilisé permet l'obtention d'une composition aqueuse homogène de sel métallique d'acide ascorbique phosphorylé et d'un filtre UN. hydrosoluble comportant au moins une fonction sulfonique.The polymer used makes it possible to obtain a homogeneous aqueous composition of metal salt of phosphorylated ascorbic acid and of a UN filter. water-soluble comprising at least one sulphonic function.
Aussi, l'invention a encore pour objet l'utilisation d'un polymère d'anhydride maléique, pour obtenir une composition aqueuse homogène contenant au moins un sel métallique d'acide ascorbique phosphorylé et au moins un filtre UN. hydrosoluble comportant au moins une fonction sulfonique.Also, the subject of the invention is also the use of a polymer of maleic anhydride, in order to obtain a homogeneous aqueous composition containing at least one metal salt of phosphorylated ascorbic acid and at least one UN filter. water-soluble comprising at least one sulphonic function.
On entend par "homogène" une composition ne comportant pas de cristaux et ayant un aspect lisse à l'œil nu.The term “homogeneous” is understood to mean a composition not comprising crystals and having a smooth appearance with the naked eye.
Polymères d'anhydride maléique Selon l'invention, on entend par "polymère d'anhydride maléique", aussi bien les homopolymères que les copolymères d'anhydride maléique, et, de manière générale, tout polymère obtenu par polymérisation ou copolymérisation d'une ou plusieurs unités anhydride maléique, ces dernières étant optionnellement hydrolysées, partiellement ou totalement. De préférence, on utilise dans la composition de l'invention, des polymères hydrophiles, c'est à dire des polymères ayant une solubilité dans l'eau, supérieure ou égale à 2 g/1. Des polymères convenant plus particulièrement à la mise en œuvre de l'invention sont des polymères obtenus par polymérisation ou copolymérisation d'une ou plusieurs unités anhydride maléique et dont les unités anhydride maléiques sont sous forme hydrolysée, et préférentiellement sous forme de sels alcalins, par exemple sous forme de sels de sodium, de potassium ou de lithium, les sels de sodium étant préférés.Maleic anhydride polymers According to the invention, the term "maleic anhydride polymer" means both homopolymers and copolymers of maleic anhydride, and, in general, any polymer obtained by polymerization or copolymerization of one or more several maleic anhydride units, the latter being optionally hydrolysed, partially or totally. Preferably, in the composition of the invention, hydrophilic polymers are used, that is to say polymers having a solubility in water, greater than or equal to 2 g / 1. Polymers which are more particularly suitable for implementing the invention are polymers obtained by polymerization or copolymerization of one or more maleic anhydride units and whose maleic anhydride units are in hydrolyzed form, and preferably in the form of alkaline salts, by example in the form of sodium, potassium or lithium salts, sodium salts being preferred.
Dans un aspect avantageux de l'invention, les polymères se présentent sous la forme de copolymères comportant des monomères anhydride maléique et des co- monomères choisis parmi l'acétate de vinyle, l'alcool vinylique, la vinylpyrrolidone, les oléfines comportant de 2 à 20 atomes de carbone comme l'octadécène, l'éthylène, l'isobutylène, le diisobutylène, l'isooctylène, et les alkylvinyléthers en particulier le méthylvinyl éther ou le stéarylvinyl éther, le styrène, et leurs mélanges.In an advantageous aspect of the invention, the polymers are in the form of copolymers comprising maleic anhydride monomers and co-monomers chosen from vinyl acetate, vinyl alcohol, vinylpyrrolidone, olefins comprising from 2 to 20 carbon atoms such as octadecene, ethylene, isobutylene, diisobutylene, isooctylene, and alkylvinyl ethers, in particular methyl vinyl ether or stearyl vinyl ether, styrene, and their mixtures.
Dans un aspect avantageux de l'invention, le polymère utilisé selon l'invention possède une fraction molaire en unité anhydride maléique comprise entre 0,1 et 1 , et plus préférentiellement entre 0,4 et 0,9.In an advantageous aspect of the invention, the polymer used according to the invention has a molar fraction in maleic anhydride unit of between 0.1 and 1, and more preferably between 0.4 and 0.9.
La masse molaire en poids des polymères d'anhydride maléique utilisés selon l'invention peut aller avantageusement de 1000 à 500 000 et de préférence de 1000 à 50 000.The molar mass by weight of the maleic anhydride polymers used according to the invention can advantageously range from 1000 to 500,000 and preferably from 1000 to 50,000.
Selon un mode particulier de réalisation de l'invention, le polymère utilisé est un copolymère de styrène et d'anhydride maléique, et notamment un copolymère de styrène et d'anhydride maléique dans un rapport 50/50.According to a particular embodiment of the invention, the polymer used is a copolymer of styrene and maleic anhydride, and in particular a copolymer of styrene and maleic anhydride in a 50/50 ratio.
Comme polymères particulièrement appropriés, on peut citer par exemple, le copolymère styrène/anhydride maléique (50/50) (nom CTFA : Sodium tyrene/maleic acid copolymer) sous forme de sel de sodium à 40% dans l'eau, commercialisé sous la référence SMA1000HNa® par la société ATOFINA. Le polymère est présent dans la composition selon l'invention en quantité suffisante pour obtenir l'effet recherché, c'est à dire en quantité suffisante pour que le mélange de sel métallique d'acide ascorbique phosphorylé et de filtre à fonction sulfonique soit stable et homogène. Selon un mode particulier de réalisation de l'invention, le rapport molaire entre la quantité d'unités anhydride maléique et le sel métallique d'acide ascorbique phosphorylé varie de 0,005 à 10 et préférentiellement de 0,01 à 1.As particularly suitable polymers, mention may be made, for example, of the styrene / maleic anhydride copolymer (50/50) (CTFA name: Sodium tyrene / maleic acid copolymer) in the form of a 40% sodium salt in water, sold under the reference SMA1000HNa ® by the company ATOFINA. The polymer is present in the composition according to the invention in an amount sufficient to obtain the desired effect, that is to say in an amount sufficient for the mixture of metallic salt of phosphorylated ascorbic acid and filter with sulfonic function to be stable and homogeneous. According to a particular embodiment of the invention, the molar ratio between the quantity of maleic anhydride units and the metal salt of phosphorylated ascorbic acid varies from 0.005 to 10 and preferably from 0.01 to 1.
De préférence, la quantité de polymère (en matière active) va de 0,05 à 30 % en poids, et plus particulièrement de 0,1 à 10 % en poids par rapport au poids total de la composition.Preferably, the amount of polymer (in active material) ranges from 0.05 to 30% by weight, and more particularly from 0.1 to 10% by weight relative to the total weight of the composition.
Sel métallique d'acide ascorbique phosphoryléMetal salt of phosphorylated ascorbic acid
Le sel métallique d'acide ascorbique phosphorylé peut être choisi parmi les ascorbyl phosphates de métal alcalin, les ascorbyl phosphates de métal alcalino- terreux, les ascorbyl phosphates de métal de transition, et leurs mélanges. On peut citer notamment les ascorbyl phosphates de magnésium, de sodium, de potassium, de calcium, de zinc et leurs mélanges. Selon un mode préféré de réalisation de l'invention, il s'agit de l'ascorbyl phosphate de magnésium.The metallic salt of phosphorylated ascorbic acid can be chosen from alkali metal ascorbyl phosphates, alkaline earth metal ascorbyl phosphates, transition metal ascorbyl phosphates, and mixtures thereof. Mention may in particular be made of ascorbyl phosphates of magnesium, sodium, potassium, calcium, zinc and their mixtures. According to a preferred embodiment of the invention, it is magnesium ascorbyl phosphate.
La quantité de sel métallique d'acide ascorbique phosphorylé peut varier dans une large mesure selon le but recherché. Cette quantité peut aller par exemple de 0,1 à 20 % en poids par rapport au poids total de la composition, plus particulièrement de 0,05 à 10 % en poids et mieux de 0,05 à 5 % en poids par rapport au poids total de la composition.The amount of metal salt of phosphorylated ascorbic acid can vary to a large extent depending on the purpose. This amount can range, for example, from 0.1 to 20% by weight relative to the total weight of the composition, more particularly from 0.05 to 10% by weight and better still from 0.05 to 5% by weight relative to the weight. total of the composition.
Filtres UN.UN filters.
Les filtres utilisés dans la composition de l'invention ont au moins une fonction sulfonique et sont hydrosolubles. Ils peuvent être choisis parmi les filtres sulfonés et/ou sulfonates hydrosolubles. Ces filtres peuvent être partiellement neutralisés par une base organique comme la triéthanolamine et l'éthylène diamine. Les filtres utilisés peuvent être notamment choisis parmi les dérivés sulfones ou sulfonates du benzylidene camphre, de la benzophénone ou du phénylbenzimidazole, et leurs mélanges.The filters used in the composition of the invention have at least one sulfonic function and are water-soluble. They can be chosen from sulfonated filters and / or water-soluble sulfonates. These filters can be partially neutralized with an organic base such as triethanolamine and ethylene diamine. The filters used can in particular be chosen from sulfone or sulfonate derivatives of benzylidene camphor, benzophenone or phenylbenzimidazole, and mixtures thereof.
Selon un mode préféré de réalisation de l'invention, les filtres sulfones ou sulfonates utilisés dans l'invention sont des dérivés du benzylidene camphre.According to a preferred embodiment of the invention, the sulfone or sulfonate filters used in the invention are derivatives of benzylidene camphor.
En particulier, les dérivés de benzylidene camphre utilisables dans l'invention présente la formule générale (a) suivante :In particular, the benzylidene camphor derivatives which can be used in the invention have the following general formula (a):
Figure imgf000007_0001
Figure imgf000007_0001
dans laquelle :in which :
B représente -H ou -SO3H,B represents -H or -SO3H,
0 < p < 1 avec B = -SO3H quand p = 0,0 <p <1 with B = -SO3H when p = 0,
0 < n < 4,0 <n <4,
D représente un ou plusieurs radicaux alkyle ou alcoxy, identiques ou différents quand n > 2, linéaires ou ramifiés contenant de 1 à 18 atomes de carbone environ, un radical halogéno, un radical hydroxyle.D represents one or more alkyl or alkoxy radicals, identical or different when n> 2, linear or branched containing from 1 to 18 carbon atoms approximately, a halo radical, a hydroxyl radical.
A, de préférence en meta ou en para, représente :A, preferably in meta or para, represents:
soit un radical SO3H ;or an SO3H radical;
soit un groupement :
Figure imgf000008_0001
either a group:
Figure imgf000008_0001
dans lequel Y représente H ou SO3H ;wherein Y represents H or SO3H;
soit un groupementeither a group
Figure imgf000008_0002
Figure imgf000008_0002
dans lequel :in which :
R11 désigne un atome d'hydrogène, un radical alkyle ou alcoxy, linéaire ou ramifié contenant de 1 à 6 atomes de carbone environ ou le radical -SO3H, Ru étant -R 11 denotes a hydrogen atom, an alkyl or alkoxy radical, linear or branched containing from 1 to 6 carbon atoms approximately or the radical -SO3H, Ru being -
SO3H lorsque B = -H,SO3H when B = -H,
2 désigne un atome d'hydrogène, un radical alkyle ou alcoxy, linéaire ou ramifié, contenant de 1 à 6 atomes de carbone environ,2 denotes a hydrogen atom, an alkyl or alkoxy radical, linear or branched, containing from 1 to 6 carbon atoms approximately,
X est un atome d'oxygène, de soufre ou un groupement -NR-, R étant un atome d'hydrogène ou un radical alkyle, linéaire ou ramifié, contenant de 1 à 6 atomes de carbone environ,X is an oxygen or sulfur atom or a group -NR-, R being a hydrogen atom or an alkyl radical, linear or branched, containing from 1 to 6 carbon atoms approximately,
et dans laquelle au moins une fonction -SO3H est éventuellement neutralisée.and in which at least one -SO3H function is optionally neutralized.
On peut citer comme exemples particuliers de composés de formule (a) les dérivés de formules (I), (II), (III) suivantes :As particular examples of compounds of formula (a), the following derivatives of formulas (I), (II), (III) can be cited:
Formule (I)
Figure imgf000009_0001
dans laquelle
Formula (I)
Figure imgf000009_0001
in which
- Z, de préférence en position para ou meta, désigne un groupement- Z, preferably in the para or meta position, denotes a group
Figure imgf000009_0002
Figure imgf000009_0002
dans lequel Y représente -H ou -SO3H, éventuellement neutralisé,in which Y represents -H or -SO3H, possibly neutralized,
- n est égal à 0 ou est un nombre allant de 1 à 4 (0 <n< 4),- n is equal to 0 or is a number ranging from 1 to 4 (0 <n <4),
- Ri représente un ou plusieurs radicaux alkyle ou alkoxy, identiques ou différents, linéaires ou ramifiés, contenant de préférence environ de 1 à 4 atomes de carbone.- Ri represents one or more alkyl or alkoxy radicals, identical or different, linear or branched, preferably containing approximately from 1 to 4 carbon atoms.
Un composé de formule (I) particulièrement préféré est celui correspondant à n = 0, Z est en position para et Y = -SO3H : l'acide benzène 1 ,4 [di(3-méthylidène- campho 10-sulfonique)], appelé aussi ou acide téréphtalylidène - di- camphosulfonique ou (selon la nomenclature CTFA) "Terephthalylidene Dicamphor Sulfonic Acid", et fabriqué sous le nom « MEXORYL SX » par la société CHIMEX.A particularly preferred compound of formula (I) is that corresponding to n = 0, Z is in the para position and Y = -SO 3 H: benzene acid 1, 4 [di (3-methylidene-camphor 10-sulfonic)], called also or terephthalylidene - di-camphosulfonic acid or (according to the CTFA nomenclature) "Terephthalylidene Dicamphor Sulfonic Acid", and manufactured under the name "MEXORYL SX" by the company CHIMEX.
Formule (II) :
Figure imgf000010_0001
dans laquelle :
Formula (II):
Figure imgf000010_0001
in which :
- R2 désigne un atome d'hydrogène ou un radical -SO3H,- R 2 denotes a hydrogen atom or a radical -SO3H,
- R3, R4, R5 et R6, identiques ou différents, représentent un groupement hydroxyle, un radical alkyle ayant de 1 à 4 atomes de carbone environ, linéaire ou ramifié, un radical alcényle ayant de 2 à 4 atomes de carbone environ, linéaire ou ramifié, un radical alcoxy ayant de 1 à 4 atomes de carbone, linéaire ou ramifié, un radical alcényloxy ayant de 2 à 4 atomes de carbone, linéaire ou ramifié, un radical halogéno ; de plus un radical R3 à Rβ seulement peut être un radical -SO3H, au moins un des radicaux R3 à R désignant le radical -SO3H quand R2 est un atome d'hydrogène. Une ou plusieurs fonctions -SO3H peuvent aussi être neutralisées.- R 3 , R 4 , R 5 and R 6 , identical or different, represent a hydroxyl group, an alkyl radical having from 1 to 4 carbon atoms approximately, linear or branched, an alkenyl radical having from 2 to 4 carbon atoms approximately, linear or branched, an alkoxy radical having from 1 to 4 carbon atoms, linear or branched, an alkenyloxy radical having from 2 to 4 carbon atoms, linear or branched, a halo radical; moreover, a radical R 3 to Rβ only can be a radical -SO3H, at least one of the radicals R 3 to R denoting the radical -SO3H when R 2 is a hydrogen atom. One or more -SO3H functions can also be neutralized.
On peut citer comme exemples particuliers les composés suivants de formule (11) dans laquelle :Mention may be made, as specific examples, of the following compounds of formula (11) in which:
• R4 désigne le radical -SO3H en position para du benzylidènecamphre et R2, R3, R5 et R6 désignent chacun un atome d'hydrogène, c'est-à-dire l'acide 4'-sulfo 3-benzylidènecamphre (nom CTFA : Benzylidene Camphor Sulfonic Acid), fabriqué sous le nom « MEXORYL SL» par la société CHIMEX,• R 4 denotes the radical -SO 3 H in the para position of the benzylidenecamphor and R 2 , R 3 , R 5 and R 6 each denote a hydrogen atom, that is to say the 4'-sulfo 3-benzylidenecamphor acid (CTFA name: Benzylidene Camphor Sulfonic Acid), manufactured under the name "MEXORYL SL" by the company CHIMEX,
• R3, R4, R5 et R6 désignent chacun un atome d'hydrogène et R2 désigne un radical -SO3H, c'est-à-dire l'acide 3-benzylidène campho-10 sulfonique.• R 3 , R 4 , R 5 and R 6 each denote a hydrogen atom and R 2 denotes a radical -SO 3 H, that is to say 3-benzylidene camphor-10 sulfonic acid.
• R4 désigne un radical méthyle en position para du benzylidènecamphre, R5 un radical -SO3H et R2, R3 et R@ représentent un atome d'hydrogène, c'est-à-dire l'acide 4'-méthyl 3'-sulfo 3-benzylidènecamphre. • R4 désigne un atome de chlore en position para du benzylidènecamphre, R5 un radical -SO3H et R2, R3 et Rβ représentent un atome d'hydrogène, c'est-à-dire l'acide 4'-chloro 3'-sulfo 3-benzylidènecamphre.• R4 denotes a methyl radical in the para position of the benzylidenecamphor, R5 a radical -SO3H and R 2 , R 3 and R @ represent a hydrogen atom, that is to say 4'-methyl 3'- acid sulfo 3-benzylidenecamphor. • R 4 denotes a chlorine atom in the para position of the benzylidenecamphor, R 5 a radical -SO3H and R 2 , R 3 and Rβ represent a hydrogen atom, that is to say 4'-chloro 3 acid '-sulfo 3-benzylidenecamphor.
• R4 désigne un radical méthyle en position para du benzylidènecamphre, R3, R5 et Rβ désignent un atome d'hydrogène et R2 désigne un radical -SO3H, c'est-à- dire l'acide 4'-méthyl 3-benzylidène campho 10-sulfonique.• R 4 denotes a methyl radical in the para position of the benzylidenecamphor, R 3 , R 5 and Rβ denote a hydrogen atom and R 2 denotes a radical -SO3H, that is to say 4'-methyl 3 acid -benzylidene camphor 10-sulfonic.
• R2 représente un radical -SO3H, R3 est un radical méthyle, R4 un atome d'hydrogène, R5 un radical tertiobutyle, Rβ un radical hydroxyle, c'est-à-dire l'acide (3-t-butyl 2-hydroxy 5-méthyl) 3-benzylidène campho-10-sulfonique.• R 2 represents a radical -SO3H, R 3 is a methyl radical, R 4 a hydrogen atom, R5 a tert-butyl radical, Rβ a hydroxyl radical, that is to say (3-t-butyl acid 2-hydroxy 5-methyl) 3-benzylidene camphor-10-sulfonic.
• R2 représente un radical -SO3H, R3 est un radical méthoxy, R4 un atome d'hydrogène, R5 un radical tertiobutyle, R6 un radical hydroxyle, c'est-à-dire l'acide (3-t-butyl 2-hydroxy 5-méthoxy) 3-benzylidène campho-10-sulfonique.• R 2 represents a radical -SO3H, R 3 is a methoxy radical, R 4 a hydrogen atom, R 5 a tert-butyl radical, R 6 a hydroxyl radical, that is to say the acid (3-t -butyl 2-hydroxy 5-methoxy) 3-benzylidene camphor-10-sulfonic.
• R2 représente un radical -SO3H, R3 et R5 désignent chacun un radical tertiobutyle, R4 un radical hydroxyle, RQ un atome d'hydrogène, c'est-à-dire l'acide (3,5-diterbutyl 4-hydroxy) 3-benzylidène campho-10-sulfonique.• R 2 represents a radical -SO3H, R 3 and R 5 each denote a tert-butyl radical, R 4 a hydroxyl radical, RQ a hydrogen atom, that is to say acid (3,5-diterbutyl 4 -hydroxy) 3-benzylidene camphor-10-sulfonic.
• R4 représente un radical méthoxy en para, R5 représente -SO3H, les radicaux• R 4 represents a methoxy radical in para, R 5 represents -SO3H, the radicals
R2, R3 et R6 représentent H, c'est-à-dire l'acide 4'-méthoxy 3'-sulfo-3-benzylidène camphre.R 2 , R 3 and R 6 represent H, that is to say 4'-methoxy 3'-sulfo-3-benzylidene camphor acid.
• R2 désigne un radical -SO3H, R3 et Rβ représentent H, Rψ et R5 formant un radical méthylènedioxy, c'est-à-dire l'acide 3-(4,5-méthylènedioxy) benzylidene campho-10-sulfonique.• R 2 denotes a radical -SO3H, R 3 and Rβ represent H, Rψ and R 5 forming a methylenedioxy radical, that is to say 3- (4,5-methylenedioxy) benzylidene campho-10-sulfonic acid .
• R2 représente un radical -SO3H, R4 un radical méthoxy et les radicaux R3, R5 et R6 représentent H, c'est-à-dire l'acide 3-(4-méthoxy) benzylidene campho-10- sulfonique. • R2 représente un radical -SO3H, j et R5 sont tous deux un radical méthoxy et les radicaux R3 et R6 représentent H, c'est-à-dire l'acide 3-(4,5-diméthoxy) benzylidene campho-10-sulfonique.• R2 represents a radical -SO3H, R 4 a methoxy radical and the radicals R 3 , R 5 and R 6 represent H, that is to say 3- (4-methoxy) benzylidene campho-10-sulfonic acid . • R 2 represents a radical -SO3H, j and R 5 are both a methoxy radical and the radicals R 3 and R 6 represent H, that is to say 3- (4,5-dimethoxy) benzylidene acid camphor-10-sulfonic acid.
• R2 représente un radical -SO3H, R4 est un radical n-butoxy et les radicaux R3,• R 2 represents a radical -SO3H, R 4 is an n-butoxy radical and the radicals R 3 ,
R5 et Re représentent un atome d'hydrogène, c'est-à-dire l'acide 3-(4-n.butoxy) benzylidene campho-10-sulfonique.R 5 and Re represent a hydrogen atom, that is to say 3- (4-n.butoxy) benzylidene campho-10-sulfonic acid.
• R2 représente un radical -SO3H, i est un radical n-butoxy, R5 est un radical méthoxy et R3 et Rβ désignent tous deux un atome d'hydrogène, c'est-à-dire l'acide 3-(4-n.butoxy 5-méthoxy) benzylidene campho-10-sulfonique.• R 2 represents a radical -SO3H, i is an n-butoxy radical, R 5 is a methoxy radical and R 3 and Rβ both denote a hydrogen atom, that is to say 3- ( 4-n.butoxy 5-methoxy) benzylidene campho-10-sulfonic.
Formule (III)Formula (III)
Figure imgf000012_0001
Figure imgf000012_0001
dans laquelle :in which :
- Ru désigne un atome d'hydrogène, un radical alkyle ou alcoxy, linéaire ou ramifié, contenant de 1 à 6 atomes de carbone environ ou un radical -SO3H,Ru denotes a hydrogen atom, an alkyl or alkoxy radical, linear or branched, containing from 1 to 6 carbon atoms approximately or a radical -SO3H,
- R12 désigne un atome d'hydrogène, un radical alkyle ou alcoxy, linéaire ou ramifié, contenant de 1 à 6 atomes de carbone environ,R 12 denotes a hydrogen atom, an alkyl or alkoxy radical, linear or branched, containing from 1 to 6 carbon atoms approximately,
- R13 désigne un atome d'hydrogène ou un radical -SO3H,- R 13 denotes a hydrogen atom or a radical -SO3H,
l'un au moins des radicaux Ru et R13 désignant un radical -SO3H, - X est un atome d'oxygène ou de soufre ou un groupement -NR-, R étant un atome d'hydrogène ou un radical alkyle, linéaire ou ramifié, contenant de préférence de 1 à 6 atomes de carbone.at least one of the radicals Ru and R 13 denoting a radical -SO3H, - X is an oxygen or sulfur atom or a group -NR-, R being a hydrogen atom or an alkyl radical, linear or branched, preferably containing from 1 to 6 carbon atoms.
On peut citer comme exemple particulier de composé de formule (III) : le composé dans lequel X désigne un radical -NH-, Ru désigne un radical -SO3H,As a particular example of a compound of formula (III), the compound in which X denotes a radical -NH-, Ru denotes a radical -SO3H,
R12 et R13 désignent tous deux un atome d'hydrogène, c'est-à-dire l'acide 2-[4- (camphométhylidène) phényl] benzimidazole-5-sulfonique.R 12 and R 13 both denote a hydrogen atom, that is to say 2- [4- (camphomethylidene) phenyl] benzimidazole-5-sulfonic acid.
Les composés de structures (I), (II), (III) sont décrits dans les documents US-A- 4,585,597, FR-A-2,236,515, FR-A-2,282,426, FR-A-2,645,148, FR-A-2,430,938, et FR-A-2,592,380.The compounds of structures (I), (II), (III) are described in documents US-A-4,585,597, FR-A-2,236,515, FR-A-2,282,426, FR-A-2,645,148, FR-A-2,430,938, and FR-A-2,592,380.
On peut citer comme autres exemples de dérivés du benzylidene camphre utilisables dans l'invention les composés de formule générale (b) suivante :As other examples of benzylidene camphor derivatives which can be used in the invention, mention may be made of the compounds of general formula (b) below:
Figure imgf000013_0001
Figure imgf000013_0001
dans laquelle :in which :
- R9 désigne un radical divalent : -(CH2)πr oυ _CH2 -CHOH-CH2- , m étant un nombre entier allant de 1 à 10 (1 ≤ m ≤ 10),- R 9 denotes a divalent radical: - (CH2) πr oυ _CH 2 -CHOH-CH2-, m being an integer ranging from 1 to 10 (1 ≤ m ≤ 10),
- R10 désigne un atome d'hydrogène, un radical alcoxy contenant de 1 à 4 atomes de carbone environ ou un radical divalent - O - relié au radical Rg lorsque celui-ci est divalent lui aussi, - Y et Y' désignent un atome d'hydrogène ou un radical -SO3H, au moins un de ces radicaux Y ou Y' est différent de l'hydrogène. Là encore la fonction -SO3H peut être neutralisée.- R1 0 denotes a hydrogen atom, an alkoxy radical containing from 1 to 4 carbon atoms approximately or a divalent radical - O - linked to the radical Rg when the latter is also divalent, - Y and Y 'denote a hydrogen atom or a radical -SO3H, at least one of these radicals Y or Y' is different from hydrogen. Again the -SO3H function can be neutralized.
On peut citer comme exemples particuliers, les composés suivants de formule (b) dans laquelle Y représente -SO3H, Y' est -H, R 0 est H et Rg est -CH2-CH2-, c'est à dire l'acide éthylène bis [(4'-oxy benzylidene) 3-campho-10 sulfonique].Mention may be made, as specific examples, of the following compounds of formula (b) in which Y represents -SO3H, Y 'is -H, R 0 is H and Rg is -CH2-CH2-, ie ethylene acid bis [(4'-oxy benzylidene) 3-campho-10 sulfonic].
Comme autre filtre utilisable dans la composition de l'invention, on peut citer aussi l'acide phénylbenzimidazole sulfonique (nom CTFA : Phenylbenzimidazole Sulfonic Acid), commercialisé sous le nom commercial EUSOLEX 232 par la société MERCK.As another filter which can be used in the composition of the invention, mention may also be made of phenylbenzimidazole sulfonic acid (CTFA name: Phenylbenzimidazole Sulfonic Acid), sold under the trade name EUSOLEX 232 by the company MERCK.
La quantité de filtre(s) UN. à fonction sulfonique peut varier dans une large mesure selon la protection solaire recherchée et le SPF souhaité pour la composition.The quantity of UN filter (s). with a sulfonic function can vary to a large extent depending on the sun protection sought and the SPF desired for the composition.
Cette quantité (en matière active) peut aller par exemple 0,01 à 10 % en poids par rapport au poids total de la composition, plus particulièrement de 0,02 à 5 % en poids de matière active par rapport au poids total de la composition.This amount (in active material) can range, for example, from 0.01 to 10% by weight relative to the total weight of the composition, more particularly from 0.02 to 5% by weight of active material relative to the total weight of the composition. .
Autres composésOther compounds
Le milieu physiologiquement acceptable de la composition aqueuse selon l'invention comprend de l'eau. Il peut être plus particulièrement constitué d'eau et éventuellement d'un solvant organique physiologiquement acceptable choisi par exemple parmi les alcools inférieurs comportant de 1 à 8 atomes de carbone et en particulier de 1 à 6 atomes de carbone, comme l'éthanol, l'isopropanol, le propanol, le butanol ; les polyéthylène glycols ayant de 6 à 80 unités oxyde d'éthylène ; les polyols comme le propylène glycol, l'isoprène glycol, le butylène glycol, la glycérine, le sorbitol ; et leurs mélanges.The physiologically acceptable medium of the aqueous composition according to the invention comprises water. It may more particularly consist of water and optionally a physiologically acceptable organic solvent chosen, for example, from lower alcohols having from 1 to 8 carbon atoms and in particular from 1 to 6 carbon atoms, such as ethanol, l isopropanol, propanol, butanol; polyethylene glycols having from 6 to 80 ethylene oxide units; polyols such as propylene glycol, isoprene glycol, butylene glycol, glycerin, sorbitol; and their mixtures.
La composition selon l'invention a généralement un pH compatible avec la peau, allant de préférence de 2 à 7, et mieux de 3 à 6, ce pH variant selon les actifs acides contenus dans la composition. Les compositions selon l'invention peuvent se présenter sous toutes les formes galéniques classiquement utilisées pour une application topique et notamment sous forme de solutions aqueuses ou hydroalcooliques, ou de gels aqueux, ou, quand une phase huileuse est ajoutée, sous forme d'émulsions huile-dans-eau (H/E) ou eau-dans-huile (E/H) ou multiple (triple : E/H/E ou H/E/H), ou de dispersions d'une phase huileuse dans une phase aqueuse à l'aide de sphérules, ces sphérules pouvant être des nanoparticules polymériques telles que les nanosphères et les nanocapsules, ou des vésicules lipidiques de type ionique et/ou non ionique (liposomes, niosomes, oléosomes). Ces compositions sont préparées selon les méthodes usuelles.The composition according to the invention generally has a pH compatible with the skin, preferably ranging from 2 to 7, and better still from 3 to 6, this pH varying according to the acid active agents contained in the composition. The compositions according to the invention can be presented in all the galenical forms conventionally used for a topical application and in particular in the form of aqueous or hydroalcoholic solutions, or aqueous gels, or, when an oily phase is added, in the form of oil emulsions. -in-water (O / W) or water-in-oil (W / O) or multiple (triple: W / O / W or O / W / O), or dispersions of an oily phase in an aqueous phase using spherules, these spherules possibly being polymeric nanoparticles such as nanospheres and nanocapsules, or lipid vesicles of ionic and / or nonionic type (liposomes, niosomes, oleosomes). These compositions are prepared according to the usual methods.
En outre, les compositions utilisées selon l'invention peuvent être plus ou moins fluides et avoir l'aspect d'une crème blanche ou colorée, d'une pommade, d'un lait, d'une lotion, d'un sérum, d'une pâte, d'une mousse. Elles peuvent être éventuellement appliquées sur la peau sous forme d'aérosol. Elles peuvent aussi se présenter sous forme solide, et par exemple sous forme de stick.In addition, the compositions used according to the invention can be more or less fluid and have the appearance of a white or colored cream, an ointment, a milk, a lotion, a serum, 'a paste, a foam. They can optionally be applied to the skin in the form of an aerosol. They can also be in solid form, and for example in the form of a stick.
Quand la composition utilisée selon l'invention comporte une phase huileuse, celle-ci contient de préférence au moins une huile, notamment une huile cosmétique. Elle peut contenir en outre d'autres corps gras.When the composition used according to the invention comprises an oily phase, it preferably contains at least one oil, in particular a cosmetic oil. It may also contain other fatty substances.
Comme huiles utilisables dans la composition de l'invention, on peut citer par exemple : - les huiles hydrocarbonées d'origine animale, telles que le perhydrosqualène ; - les huiles hydrocarbonées d'origine végétale, telles que les triglycérides liquides d'acides gras comportant de 4 à 10 atomes de carbone comme les triglycérides des acides heptanoïque ou octanoïque ou encore, par exemple les huiles de tournesol, de maïs, de soja, de courge, de pépins de raisin, de sésame, de noisette, d'abricot, de macadamia, d'arara, de tournesol, de ricin, d'avocat, les triglycérides des acides caprylique/caprique comme ceux vendus par la société Stearineries Dubois ou ceux vendus sous les dénominations Miglyol 810, 812 et 818 par la société Dynamit Nobel, l'huile de jojoba, l'huile de beurre de karité; - les esters et les éthers de synthèse, notamment d'acides gras, comme les huiles de formules R1COOR2 et R1OR2 dans laquelle R1 représente le reste d'un acide gras comportant de 8 à 29 atomes de carbone, et R2 représente une chaîne hydrocarbonée, ramifiée ou non, contenant de 3 à 30 atomes de carbone, comme par exemple l'huile de Purcellin, l'isononanoate d'isononyle, le myristate d'isopropyle, le palmitate d'éthyl-2-hexyle, le stéarate d'octyl-2-dodécyle, l'érucate d'octyl-2-dodécyle, l'isostéarate d'isostéaryle ; les esters hydroxylés comme l'isostéaryl lactate, l'octylhydroxystéarate, l'hydroxystéarate d'octyldodécyle, le diisostéaryl-malate, le citrate de triisocétyle, les heptanoates, octanoates, decanoates d'alcools gras ; les esters de polyol, comme le dioctanoate de propylène glycol, le diheptanoate de néopentylglycol et le diisononanoate de diéthylèneglycol ; et les esters du pentaérythritol comme le tétraisostéarate de pentaérythri tyle ;As oils which can be used in the composition of the invention, there may be mentioned, for example: - hydrocarbon oils of animal origin, such as perhydrosqualene; - hydrocarbon-based oils of vegetable origin, such as liquid triglycerides of fatty acids comprising from 4 to 10 carbon atoms such as triglycerides of heptanoic or octanoic acids or also, for example sunflower, corn, soybean oils, squash, grapeseed, sesame, hazelnut, apricot, macadamia, macaw, sunflower, castor, avocado, caprylic / capric acid triglycerides like those sold by Stearineries Dubois or those sold under the names Miglyol 810, 812 and 818 by the company Dynamit Nobel, jojoba oil, shea butter oil; - synthetic esters and ethers, in particular of fatty acids, such as oils of formulas R 1 COOR 2 and R 1 OR 2 in which R 1 represents the remainder of a fatty acid containing from 8 to 29 carbon atoms, and R 2 represents a branched or unbranched hydrocarbon chain containing from 3 to 30 carbon atoms, such as for example Purcellin oil, isononyl isononanoate, isopropyl myristate, 2-ethyl palmitate -hexyl, octyl-2-dodecyl stearate, octyl-2-dodecyl erucate, isostearyl isostearate; hydroxylated esters such as isostearyl lactate, octylhydroxystearate, octyldodecyl hydroxystearate, diisostearyl malate, triisoketyl citrate, heptanoates, octanoates, decanoates of fatty alcohols; polyol esters, such as propylene glycol dioctanoate, neopentylglycol diheptanoate and diethylene glycol diisononanoate; and pentaerythritol esters such as pentaerythrityl tetraisostearate;
- les hydrocarbures linéaires ou ramifiés, d'origine minérale ou synthétique, tels que les huiles de paraffine, volatiles ou non, et leurs dérivés, les huiles hydrocarbonées à chaîne ramifiée comportant de 10 à 20 atomes de carbone telles que l'isohexadécane, l'isododécane, les isoparaffines et leurs mélanges, la vaseline, les polydécènes, le polyisobutène hydrogéné tel que l'huile de Parléam® ; - des huiles essentielles naturelles ou synthétiques telles que, par exemple, les huiles d'eucalyptus, de lavandin, de lavande, de vétiver, de litsea cubeba, de citron, de santal, de romarin, de camomille, de sarriette, de noix de muscade, de cannelle, d'hysope, de carvi, d'orange, de géraniol, de cade et de bergamote;- linear or branched hydrocarbons, of mineral or synthetic origin, such as paraffin oils, volatile or not, and their derivatives, branched chain hydrocarbon oils containing from 10 to 20 carbon atoms such as isohexadecane, l 'isododecane, isoparaffins and their mixtures, petrolatum, polydecenes, hydrogenated polyisobutene such as Parléam® oil; - natural or synthetic essential oils such as, for example, eucalyptus, lavandin, lavender, vetiver, litsea cubeba, lemon, sandalwood, rosemary, chamomile, savory, walnut oils nutmeg, cinnamon, hyssop, caraway, orange, geraniol, cade and bergamot;
- les alcools et acides gras ayant de 8 à 26 atomes de carbone, comme l'alcool ou l'acide cetylique, l'alcool stearylique, l'acide stéarique, le mélange d'alcool cetylique et d'alcool stearylique (alcool cétylstéarylique), l'octyl dodécanol, le 2- butyloctanol, le 2-hexyldécanol, le 2-undécylpentadécanol, l'alcool oléique ou l'alcool linoléique ;- alcohols and fatty acids having 8 to 26 carbon atoms, such as alcohol or cetylic acid, stearyl alcohol, stearic acid, the mixture of cetyl alcohol and stearyl alcohol (cetylstearyl alcohol) , octyl dodecanol, 2-butyloctanol, 2-hexyldecanol, 2-undecylpentadecanol, oleic alcohol or linoleic alcohol;
- les huiles fluorées partiellement hydrocarbonées et/ou siliconées comme celles décrites dans le document JP-A-2-295912 ;- partially hydrocarbon and / or silicone fluorinated oils such as those described in document JP-A-2-295912;
- les huiles de silicone comme les polyméthylsiloxanes (PDMS) volatiles ou non à chaîne siliconée linéaire ou cyclique, liquides ou pâteux à température ambiante, notamment les cyclopolydiméthylsiloxanes (cyclométhicones) telles que la cyclohexasiloxane ; les polydiméthylsiloxanes comportant des groupements alkyle, alcoxy ou phényle, pendant ou en bout dé chaîne siliconée, groupements ayant de 2 à 24 atomes de carbone ; les silicones phénylées comme les phényltriméthicones, les phényldiméthicones, les phényltriméthylsiloxydiphényl- siloxanes, les diphényl-diméthicones, les diphénylméthyldiphényl trisiloxanes, les 2-phényléthyltriméthyl-siloxysilicates, et les polyméthylphénylsiloxanes ; - leurs mélanges.- silicone oils such as polymethylsiloxanes (PDMS) volatile or not with a linear or cyclic silicone chain, liquid or pasty at room temperature, in particular cyclopolydimethylsiloxanes (cyclomethicones) such as cyclohexasiloxane; polydimethylsiloxanes comprising groups alkyl, alkoxy or phenyl, during or at the end of the silicone chain, groups having from 2 to 24 carbon atoms; phenylated silicones such as phenyltrimethicones, phenyldimethicones, phenyltrimethylsiloxydiphenyl-siloxanes, diphenyl-dimethicones, diphenylmethyldiphenyl trisiloxanes, 2-phenylethyltrimethyl-siloxysilicates, and polymethylphenyls; - their mixtures.
On entend par « huile hydrocarbonée » dans la liste des huiles citées ci-dessus, toute huile comportant majoritairement des atomes de carbone et d'hydrogène, et éventuellement des groupements ester, éther, fluoré, acide carboxylique et/ou alcool.“Hydrocarbon oil” is understood to mean, in the list of oils mentioned above, any oil mainly comprising carbon and hydrogen atoms, and optionally ester, ether, fluorinated, carboxylic acid and / or alcohol groups.
Les autres corps gras pouvant être présents dans la phase huileuse sont par exemple les acides gras comportant de 8 à 30 atomes de carbone, comme l'acide stéarique, l'acide laurique, l'acide palmitique et l'acide oléique ; les cires comme la lanoline, la cire d'abeille, la cire de Carnauba ou de Candellila, les cires de paraffine, de lignite ou les cires microcristallines, la cérésine ou l'ozokérite, les cires synthétiques comme les cires de polyéthylène, les cires de Fischer- Tropsch ; les résines de silicone telles que la trifluorométhyl-C1-4- alkyldimethicone et la trifluoropropyldimethicone ; et les élastomères de silicone comme les produits commercialisés sous les dénominations « KSG » par la société Shin-Etsu, sous les dénominations « Trefil », « BY29 » ou « EPSX » par la société Dow Corning ou sous les dénominations « Gransil » par la société Grant Industries.The other fatty substances which may be present in the oily phase are, for example, fatty acids containing from 8 to 30 carbon atoms, such as stearic acid, lauric acid, palmitic acid and oleic acid; waxes such as lanolin, beeswax, carnauba or candellila wax, paraffin, lignite or microcrystalline waxes, ceresin or ozokerite, synthetic waxes such as polyethylene waxes, waxes from Fischer-Tropsch; silicone resins such as trifluoromethyl-C1-4-alkyldimethicone and trifluoropropyldimethicone; and silicone elastomers such as the products marketed under the names "KSG" by the company Shin-Etsu, under the names "Trefil", "BY29" or "EPSX" by the company Dow Corning or under the names "Gransil" by the Grant Industries.
Ces corps gras peuvent être choisis de manière variée par l'homme du métier afin de préparer une composition ayant les propriétés, par exemple de consistance ou de texture, souhaitées.These fatty substances can be chosen in a variety of ways by a person skilled in the art in order to prepare a composition having the properties, for example of consistency or texture, desired.
Quand la composition selon l'invention est une émulsion eau-dans-huile (E/H) ou huile-dans-eau (H/E), la proportion de la phase huileuse de l'émulsion peut aller de 5 à 80 % en poids, et de préférence de 5 à 50 % en poids par rapport au poids total de la composition. Les émulsions contiennent généralement au moins un émulsionnant choisi parmi les émulsionnants amphotères, anioniques, cationiques ou non ioniques, utilisés seuls ou en mélange, et éventuellement un co-émulsionnant. Les émulsionnants sont choisis de manière appropriée suivant . émulsion à obtenir (E/H ou H/E). L'émulsionnant et le co-émulsionnant sont généralement présents dans la composition, en une proportion pouvant aller par exemple de 0,3 à 30 % en poids, et de préférence de 0,5 à 20 % en poids par rapport au poids total de la composition.When the composition according to the invention is a water-in-oil (W / O) or oil-in-water (O / W) emulsion, the proportion of the oily phase of the emulsion can range from 5 to 80% by weight, and preferably from 5 to 50% by weight relative to the total weight of the composition. The emulsions generally contain at least one emulsifier chosen from amphoteric, anionic, cationic or nonionic emulsifiers, used alone or as a mixture, and optionally a co-emulsifier. The emulsifiers are appropriately selected as follows. emulsion to be obtained (W / O or O / W). The emulsifier and the co-emulsifier are generally present in the composition, in a proportion which can range, for example, from 0.3 to 30% by weight, and preferably from 0.5 to 20% by weight relative to the total weight of the composition.
Pour les émulsions E/H, on peut citer par exemple comme émulsionnants les dimethicone copolyols tels que le mélange de cyclomethicone et de dimethicone copolyol, vendu sous la dénomination « DC 5225 C » par la société Dow Corning, et les alkyl-dimethicone copolyols tels que le Laurylmethicone copolyol vendu sous la dénomination "Dow Corning 5200 Formulation Aid" par la société Dow Corning et le Cetyl dimethicone copolyol vendu sous la dénomination ABIL EM 90R par la société Goldschmidt, ou le mélange polyglycéryl-4 isostéarate/cétyl dimethicone copolyol/ hexyllaurate vendu sous la dénomination ABIL WE 09 par la société Goldschmidt. On peut y ajouter aussi un ou plusieurs co-émulsionnants. De manière avantageuse, le co-émulsionnant peut être choisi dans le groupe comprenant les esters alkylés de polyol. Comme esters alkylés de polyol, on peut citer notamment les esters de glycérol et/ou de sorbitan et par exemple l'isostéarate de polyglycérol, tel que le produit commercialisé sous la dénomination Isolan Gl 34 par la société Goldschmidt, l'isostéarate de sorbitan, tel que le produit commercialisé sous la dénomination Ariacel 987 par la société ICI, l'isostéarate de sorbitan et de glycérol, tel que le produit commercialisé sous la dénomination Ariacel 986 par la société ICI, et leurs mélanges.For W / O emulsions, dimethicone copolyols such as the mixture of cyclomethicone and dimethicone copolyol, sold under the name "DC 5225 C" by the company Dow Corning, and alkyl dimethicone copolyols, for example, may be mentioned as emulsifiers. that Laurylmethicone copolyol sold under the name "Dow Corning 5200 Formulation Aid" by the company Dow Corning and Cetyl dimethicone copolyol sold under the name ABIL EM 90 R by the company Goldschmidt, or the polyglyceryl-4 isostearate / cetyl dimethicone copolyol / mixture hexyllaurate sold under the name ABIL WE 09 by the company Goldschmidt. One or more co-emulsifiers can also be added. Advantageously, the co-emulsifier can be chosen from the group comprising alkylated polyol esters. As alkylated polyol esters, mention may in particular be made of glycerol and / or sorbitan esters and for example polyglycerol isostearate, such as the product sold under the name Isolan Gl 34 by the company Goldschmidt, sorbitan isostearate, such as the product sold under the name Ariacel 987 by the company ICI, sorbitan and glycerol isostearate, such as the product sold under the name Ariacel 986 by the company ICI, and their mixtures.
On peut aussi utiliser comme tensioactif d'émulsions E/H, un organopolysiloxane solide élastomère réticulé comportant au moins un groupement oxyalkyléne, tel que ceux obtenus selon le mode opératoire des exemples 3, 4 et 8 du documentOne can also use as surfactant of W / O emulsions, a solid crosslinked elastomeric organopolysiloxane comprising at least one oxyalkylene group, such as those obtained according to the procedure of Examples 3, 4 and 8 of the document.
US-A-5, 412,004 et des exemples du document US-A-5, 811 ,487, notamment le produit de l'exemple 3 (exemple de synthèse) du brevet US-A-5,412,004. et tel que celui commercialisé sous la référence KSG 21 par la société Shin Etsu.US-A-5, 412,004 and examples of document US-A-5, 811, 487, in particular the product of Example 3 (synthetic example) of US-A-5,412,004. and such as that marketed under the reference KSG 21 by the company Shin Etsu.
Pour les émulsions H/E, on peut citer par exemple comme émulsionnants, les tensioactifs non ioniques, et notamment les esters de polyols et d'acide gras à chaîne saturée ou insaturée comportant par exemple de 8 à 24 atomes de carbone et mieux de 12 à 22 atomes de carbone, et leurs dérivés oxyalkylénés, c'est-à-dire comportant des unités oxyéthylénés et/ou oxypropylénés, tels les esters de glycéryle et d'acide gras en C8-C24, et leurs dérivés oxyalkylénés ; les esters de polyethylene glycol et d'acide gras en Cs-C24, et leurs dérivés oxyalkylénés ; les esters de sorbitol et d'acide gras en C8-C24, et leurs dérivés oxyalkylénés ; les esters de sucre (sucrose, glucose, alkylglucose) et d'acide gras en C8-C24, et leurs dérivés oxyalkylénés ; les éthers d'alcools gras ; les éthers de sucre et d'alcools gras en C8-C24, et leurs mélanges.For O / W emulsions, non-ionic surfactants may be mentioned, for example, as emulsifiers, and in particular esters of polyols and of fatty acids with saturated or unsaturated chain comprising for example from 8 to 24 carbon atoms and better still from 12 with 22 carbon atoms, and their oxyalkylenated derivatives, that is to say comprising oxyethylenated and / or oxypropylenated units, such as the glyceryl esters of C 8 -C 24 fatty acid, and their oxyalkylenated derivatives; polyethylene glycol and Cs-C 24 fatty acid esters, and their oxyalkylenated derivatives; esters of sorbitol and of C 8 -C 24 fatty acid, and their oxyalkylenated derivatives; esters of sugar (sucrose, glucose, alkylglucose) and of C 8 -C 24 fatty acid, and their oxyalkylenated derivatives; fatty alcohol ethers; sugar ethers and C 8 -C 24 fatty alcohols, and mixtures thereof.
Comme ester de glycéryle et d'acide gras, on peut citer notamment le stéarate de glycéryle (mono-, di- et ou tri-stéarate de glycéryle) (nom CTFA : glyceryl stéarate) ou le ricinoléate de glycéryle, et leurs mélanges.As glyceryl ester of fatty acid, there may be mentioned in particular glyceryl stearate (mono-, di- and or glyceryl tri-stearate) (CTFA name: glyceryl stearate) or glyceryl ricinoleate, and mixtures thereof.
Comme ester de polyethylene glycol et d'acide gras, on peut citer notamment le stéarate de polyethylene glycol (mono-, di- et/ou tri-stéarate de polyethylene glycol), et plus spécialement le monostéarate de polyethylene glycol 50 OE (nom CTFA : PEG-50 stéarate), le monostéarate de polyethylene glycol 100 OE (nom CTFA : PEG-100 stéarate et leurs mélanges.As polyethylene glycol and fatty acid esters, mention may in particular be made of polyethylene glycol stearate (polyethylene glycol mono-, di- and / or tri-stearate), and more especially polyethylene glycol 50 OE monostearate (CTFA name). : PEG-50 stearate), polyethylene glycol 100 OE monostearate (CTFA name: PEG-100 stearate and mixtures thereof.
On peut aussi utiliser des mélanges de ces tensioactifs, comme par exemple le produit contenant du Glyceryl stéarate et du PEG-100 stéarate, commercialisé sous la dénomination ARLACEL 165 par la société Uniqema, et le produit contenant du Glyceryl stéarate (mono-distéarate de glycéryle) et du stéarate de potassium, commercialisé sous la dénomination TEGIN par la société Goldschmidt (nom CTFA : glyceryl stéarate SE). Comme ester d'acide gras et de glucose ou d'alkylglucose, on peut citer en particulier le palmitate de glucose, les sesquistéarates d'alkylglucose comme le sesquistearate de méthylglucose, les palmitates d'alkylglucose comme le palmitate de méthylglucose ou d'éthylglucose, les esters gras de méthylglucoside et plus spécialement le diester de méthylglucoside et d'acide oléique (nom CTFA : Methyl glucose dioleate) ; l'ester mixte de méthylglucoside et du mélange acide oléique / acide hydroxystéarique (nom CTFA : Methyl glucose dioleate/hydroxystearate) ; l'ester de méthylglucoside et d'acide isostéarique (nom CTFA : Methyl glucose isos tearate) ; l'ester de méthylglucoside et d'acide laurique (nom CTFA : Methyl glucose laurate) ; le mélange de monoester et de diester de méthylglucoside et d'acide isostéarique (nom CTFA : Methyl glucose sesqui- isostearate) ; le mélange de monoester et de diester de méthylglucoside et d'acide stéarique (nom CTFA : Methyl glucose sesquistearate) et en particulier le produit commercialisé sous la dénomination Glucate SS par la société AMERCHOL, et leurs mélanges.It is also possible to use mixtures of these surfactants, such as for example the product containing Glyceryl stearate and PEG-100 stearate, sold under the name ARLACEL 165 by the company Uniqema, and the product containing Glyceryl stearate (glyceryl mono-distearate ) and potassium stearate, sold under the name TEGIN by the company Goldschmidt (name CTFA: glyceryl stearate SE). As fatty acid and glucose or alkylglucose ester, mention may in particular be made of glucose palmitate, alkylglucose sesquistearates such as methylglucose sesquistearate, alkylglucose palmitates such as methylglucose or ethylglucose palmitate, fatty esters of methylglucoside and more especially the diester of methylglucoside and oleic acid (CTFA name: Methyl glucose dioleate); the mixed ester of methylglucoside and of the oleic acid / hydroxystearic acid mixture (CTFA name: Methyl glucose dioleate / hydroxystearate); the ester of methylglucoside and isostearic acid (CTFA name: Methyl glucose isos tearate); the ester of methylglucoside and of lauric acid (CTFA name: Methyl glucose laurate); the mixture of monoester and diester of methylglucoside and isostearic acid (CTFA name: Methyl glucose sesqui-isostearate); the mixture of monoester and diester of methylglucoside and stearic acid (CTFA name: Methyl glucose sesquistearate) and in particular the product marketed under the name Glucate SS by the company AMERCHOL, and their mixtures.
Comme éthers oxyéthylénés d'acide gras et de glucose ou d'alkylglucose, on peut citer par exemple les éthers oxyéthylénés d'acide gras et de méthylglucose, et en particulier l'éther de polyethylene glycol de diester de methyl glucose et d'acide stéarique à environ 20 moles d'oxyde d'éthylene (nom CTFA : PEG-20 methyl glucose distearate) tel que le produit commercialisé sous la dénomination Glucam E-20 distearate par la société AMERCHOL ; l'éther de polyethylene glycol du mélange de monoester et de diester de methyl glucose et d'acide stéarique à environ 20 moles d'oxyde d'éthylene (nom CTFA : PEG-20 methyl glucose sesquistearate) et en particulier le produit commercialisé sous la dénomination Glucamate SSE-20 par la société AMERCHOL et celui commercialisé sous la dénomination Grillocose PSE-20 par la société GOLDSCHMIDT, et leurs mélanges.As oxyethylenated ethers of fatty acid and of glucose or of alkylglucose, mention may, for example, be made of oxyethylenated ethers of fatty acid and of methylglucose, and in particular the polyethylene glycol ether of methyl glucose diester and of stearic acid. about 20 moles of ethylene oxide (CTFA name: PEG-20 methyl glucose distearate) such as the product sold under the name Glucam E-20 distearate by the company AMERCHOL; the polyethylene glycol ether of the mixture of monoester and diester of methyl glucose and stearic acid with approximately 20 moles of ethylene oxide (CTFA name: PEG-20 methyl glucose sesquistearate) and in particular the product sold under the name Glucamate SSE-20 by the company AMERCHOL and that sold under the name Grillocose PSE-20 by the company GOLDSCHMIDT, and their mixtures.
Comme esters de sucrose, on peut citer par exemple le palmito-stéarate de saccharose, le stéarate de saccharose et le mono laurate de saccharose. Comme éthers d'alcools gras, on peut citer par exemple les éthers de polyethylene glycol et d'alcool gras comportant de 8 à 30 atomes de carbone, et notamment de 10 à22 atomes de carbone, tels que les éthers de polyethylene glycol et d'alcools cetylique, stearylique, ce téarylique (mélange d'alcools cetylique et stearylique). On peut citer par exemple les éthers comportant de 1 à 200 et de préférence de 2 à 100 groupes oxyéthylénés, tels que ceux de nom CTFA Ce teareth-20, Ceteareth-30, et leurs mélanges.As sucrose esters, mention may, for example, be made of sucrose palmito-stearate, sucrose stearate and sucrose mono laurate. As fatty alcohol ethers, mention may be made, for example, of polyethylene glycol and fatty alcohol ethers containing from 8 to 30 carbon atoms, and in particular from 10 to 22 carbon atoms, such as polyethylene glycol ethers and cetyl, stearyl, tearyl alcohol (mixture of cetyl and stearyl alcohol). Mention may be made, for example, of ethers comprising from 1 to 200 and preferably from 2 to 100 oxyethylenated groups, such as those of CTFA name Ce teareth-20, Ceteareth-30, and their mixtures.
Comme éthers de sucre, on peut citer notamment les alkylpolyglucosides, et par exemple le decylglucoside comme le produit commercialisé sous la dénomination MYDOL 10 par la société Kao Chemicals, le produit commercialisé sous la dénomination PLANTAREN 2000 par la société Henkel, et le produit commercialisé sous la dénomination ORAMIX NS 10 par la société Seppic ; le caprylyl/capryl glucoside comme le produit commercialisé sous la dénomination ORAMIX CG 110 par la Société Seppic ou sous la dénomination LUTENSOL GD 70 par la Société BASF ; le laurylgiucoside comme les produits commercialisés sous les dénominations PLANTAREN 1200 N et PLANTACARE 1200 par la société Henkel ; le coco-glucoside comme le produit commercialisé sous la dénomination PLANTACARE 818/UP par la société Henkel ; le cétostéaryl glucoside éventuellement en mélange avec l'alcool cétostéarylique, commercialisé par exemple sous la dénomination MONTANOV 68 par la société Seppic, sous la dénomination TEGO-CARE CG90 par la société Goldschmidt et sous la dénomination EMULGADE KE3302 par la société Henkel, ainsi que l'arachidyl glucoside, par exemple sous la forme du mélange d'alcools arachidique et béhénique et d'arachidyl glucoside commercialisé sous la dénomination MONTANOV 202 par la société Seppic. et leurs mélangesAs sugar ethers, mention may in particular be made of alkylpolyglucosides, and for example decylglucoside, such as the product sold under the name MYDOL 10 by the company Kao Chemicals, the product sold under the name PLANTAREN 2000 by the company Henkel, and the product sold under the name ORAMIX NS 10 by the company Seppic; caprylyl / capryl glucoside such as the product sold under the name ORAMIX CG 110 by the company Seppic or under the name LUTENSOL GD 70 by the company BASF; laurylgiucoside such as the products marketed under the names PLANTAREN 1200 N and PLANTACARE 1200 by the company Henkel; coco-glucoside such as the product sold under the name PLANTACARE 818 / UP by the company Henkel; ketostearyl glucoside optionally mixed with cetostearyl alcohol, marketed for example under the name MONTANOV 68 by the company Seppic, under the name TEGO-CARE CG90 by the company Goldschmidt and under the name EMULGADE KE3302 by the company Henkel, as well as l arachidyl glucoside, for example in the form of the mixture of arachidic and behenic alcohols and arachidyl glucoside sold under the name MONTANOV 202 by the company Seppic. and their mixtures
Selon un mode préféré de réalisation de l'invention, la composition se présente sous forme d'émulsions H/E.According to a preferred embodiment of the invention, the composition is in the form of O / W emulsions.
De façon connue, la composition cosmétique ou dermatologique de l'invention peut contenir également un ou plusieurs adjuvants habituels dans le domaine cosmétique ou dermatologique. Comme adjuvants, on peut citer par les gélifiants, les actifs, les conservateurs, les antioxydants, les parfums, les solvants, les charges, les filtres solaires (= filtres UN.) autres que ceux indiqués ci-dessus, les matières colorantes, les agents basiques (triéthanolamine, diéthanolamine, soude) ou acides et encore les vésicules lipidiques ou tout autre type de vecteur (nanocapsules, microcapsules, etc .), et leurs mélanges. Ces adjuvants sont utilisés dans les proportions habituelles dans le domaine cosmétique, et par exemple de 0,01 à 30 % du poids total de la composition, et ils sont, selon leur nature, introduits dans la phase aqueuse de la composition ou dans une phase huileuse quand elle est présente, ou encore dans des vésicules ou tout autre type de vecteur. Ces adjuvants ainsi que leurs concentrations doivent être tels qu'ils ne modifient pas la propriété recherchée pour l'émulsion de l'invention.In known manner, the cosmetic or dermatological composition of the invention may also contain one or more adjuvants customary in the cosmetic or dermatological field. As adjuvants, mention may be made of gelling agents, active ingredients, preservatives, antioxidants, perfumes, solvents, fillers, sun filters (= UN filters) other than those indicated above, coloring matters, basic agents (triethanolamine, diethanolamine, soda) or acids and also lipid vesicles or any other type of vector (nanocapsules, microcapsules, etc.), and their mixtures. These adjuvants are used in the usual proportions in the cosmetic field, and for example from 0.01 to 30% of the total weight of the composition, and they are, depending on their nature, introduced into the aqueous phase of the composition or into a phase oily when it is present, or in vesicles or any other type of vector. These adjuvants and their concentrations must be such that they do not modify the property sought for the emulsion of the invention.
Ainsi, selon la fluidité de la composition . que l'on souhaite obtenir, on peut incorporer dans la composition, un ou plusieurs gélifiants, notamment hydrophiles, c'est- à-dire solubles ou dispersibles dans l'eau. Comme gélifiants hydrophiles, on peut citer par exemple les polymères carboxyvinyliques modifiés ou non, tels que les produits commercialisés sous les dénominations Carbopol (nom CTFA : carbomer) et Pemulen (nom CTFA : Acrylates/C 10-30 akyl acrylate crosspolymer) par la société Goodrich ; les polyacrylamides ; les polymères et copolymères d'acide 2-acrylamido 2-méthylpropane sulfonique, éventuellement réticulés et/ou neutralisés, comme le poly(acide 2-acrylamido 2-méthylpropane sulfonique) commercialisé par la société Hoechst sous la dénomination « Hostacerin AMPS » (nom GTFA : ammonium polyacr yldime.hyltaur amide) ; les copolymères anioniques réticulés d'acrylamide et d'AMPS, se présentant sous la forme d'une émulsion E/H, tels ceux commercialisés sous le nom de SEPIGEL 305 (nom C.T.F.A. : Polyacrylamide / C13-14 Isoparaffin / Laureth-7) et sous le nom de SIMULGEL 600 (nom C.T.F.A. : Acrylamide / Sodium acryloyldimethyltaurate copolymer / Isohexadecane / Polysorbate 80) par la société SEPPIC ; les biopolymères polysaccharidiques comme la gomme de xanthane, la gomme de guar, les alginates, les celluloses modifiées ; et leurs mélanges. La quantité de gélifiants dépend du but recherché. La quantité de gélifiants peut aller par exemple de 0,01 à 10 % et de préférence de 0,5 à 5 % en poids par rapport au poids total de la composition.Thus, depending on the fluidity of the composition. that it is desired to obtain, one or more gelling agents, in particular hydrophilic, that is to say soluble or dispersible in water, can be incorporated into the composition. As hydrophilic gelling agents, mention may, for example, be made of carboxyvinyl polymers, modified or not, such as the products sold under the names Carbopol (name CTFA: carbomer) and Pemulen (name CTFA: Acrylates / C 10-30 akyl acrylate crosspolymer) by the company Goodrich; polyacrylamides; polymers and copolymers of 2-acrylamido 2-methylpropane sulfonic acid, optionally crosslinked and / or neutralized, such as the poly (2-acrylamido 2-methylpropane sulfonic acid) sold by the company Hoechst under the name "Hostacerin AMPS" (name GTFA : ammonium polyacr yldime.hyltaur amide); crosslinked anionic copolymers of acrylamide and AMPS, in the form of a W / O emulsion, such as those marketed under the name of SEPIGEL 305 (CTFA name: Polyacrylamide / C13-14 Isoparaffin / Laureth-7) and under the name of SIMULGEL 600 (CTFA name: Acrylamide / Sodium acryloyldimethyltaurate copolymer / Isohexadecane / Polysorbate 80) by the company SEPPIC; polysaccharide biopolymers such as xanthan gum, guar gum, alginates, modified celluloses; and their mixtures. The amount of gelling agents depends on the aim sought. The amount of gelling agents can range, for example, from 0.01 to 10% and preferably from 0.5 to 5% by weight relative to the total weight of the composition.
Les charges qui peuvent être utilisées dans la composition de l'invention, on peut citer par exemple, outre les pigments, la poudre de silice ; le talc ; les particules de polyamide et notamment celles vendues sous la dénomination ORGASOL par la société Atochem ; les poudres de polyethylene ; les micro-sphères à base de copolymères acryliques, telles que celles en copolymère diméthacrylate d'éthylene glycol/ methacrylate de lauryle vendues par la société Dow Corning sous la dénomination de POLYTRAP ; les poudres expansées telles que les microsphères creuses et notamment, les microsphères commercialisées sous la dénomination EXPANCEL par la société Kemanord Plast ou sous la dénomination MICROPEARL F 80 ED par la société Matsumoto ; les microbilles de résine de silicone telles que celles commercialisées sous la dénomination TOSPEARL par la société Toshiba Silicone ; et leurs mélanges. Ces charges peuvent être présentes dans des quantités allant de 0 à 20 % en poids et de préférence de 1 à 10 % en poids par rapport au poids total de la composition.The fillers which can be used in the composition of the invention include, for example, in addition to pigments, silica powder; talc; polyamide particles and in particular those sold under the name ORGASOL by the company Atochem; polyethylene powders; microspheres based on acrylic copolymers, such as those in ethylene glycol dimethacrylate / lauryl methacrylate copolymer sold by the company Dow Corning under the name of POLYTRAP; expanded powders such as hollow microspheres and in particular, microspheres marketed under the name EXPANCEL by the company Kemanord Plast or under the name MICROPEARL F 80 ED by the company Matsumoto; silicone resin microbeads such as those sold under the name TOSPEARL by the company Toshiba Silicone; and their mixtures. These fillers can be present in amounts ranging from 0 to 20% by weight and preferably from 1 to 10% by weight relative to the total weight of the composition.
Comme actifs utilisables dans la composition de l'invention, on peut citer par exemple, les enzymes (par exemple lactoperoxydase, lipase, protéase, phospholipase, cellulases) ; les flavonoïdes ; les agents hydratants tels que les hydrolysats de protéines ; le hyaluronate de sodium ; les polyols comme la glycérine, les glycols comme les polyethylene glycols, et les dérivés de sucre ; les anti-inflammatoires ; les oligomères procyannidoliques ; les vitamines comme la vitamine A (rétinol), la vitamine E (tocophérol), la vitamine C (acide ascorbique), la vitamine B5 (panthenol), la vitamine B3 (niacinamide), les dérivés de ces vitamines (notamment esters) et leurs mélanges ; l'urée ; la caféine ; les dépigmentants tels que l'acide kojique, l'hydroquinone et l'acide caféique ; l'acide salicylique et ses dérivés ; les alpha-hydroxyacides tels que l'acide lactique et l'acide glycolique et leurs dérivés ; les rétinoïdes tels que les caroténoïdes et les dérivés de vitamine A ; l'hydrocortisone ; la melatonine ; les extraits d'algues, de champignons, de végétaux, de levures, de bactéries ; les stéroïdes ; les actifs anti-bactériens comme le 2,4,4'-trichloro-2'-hydroxy diphényl éther (ou triclosan), le 3,4,4'-trichlorocarbanilide (ou triclocarban) et les acides indiqués ci-dessus et notamment l'acide salicylique et ses dérivés ; les agents matifiants comme les fibres ; les agents tenseurs ; les ceramides ; les huiles essentielles ; et leurs mélanges ; et tout actif approprié pour le but final de la composition. Comme exemples de stéroïdes, on peut citer la déhydroépiandrostérone (ou DHEA), ainsi que (1) ses précurseurs et dérivés biologiques, en particulier les sels et esters de DHEA, tels que le sulfate et le salicylate de DHEA, la 7-hydroxy DHEA, la 7-céto DHEA, les esters de 7-hydroxy et 7-céto DHEA, notamment la 3- beta-acétoxy-7-oxo DHEA, et (2) ses précurseurs et dérivés chimiques, en particulier les sapogénines telles que la diosgénine ou l'hécogénine, et/ou leurs dérivés tels que l'acétate d'hécogénine, et/ou les extraits naturels en contenant et notamment les extraits de Dioscorées, tels que l'igname sauvage (Wild Yam).As active agents which can be used in the composition of the invention, mention may, for example, be made of enzymes (for example lactoperoxidase, lipase, protease, phospholipase, cellulases); flavonoids; moisturizers such as protein hydrolysates; sodium hyaluronate; polyols such as glycerin, glycols such as polyethylene glycols, and sugar derivatives; anti-inflammatory drugs; procyannidolic oligomers; vitamins such as vitamin A (retinol), vitamin E (tocopherol), vitamin C (ascorbic acid), vitamin B5 (panthenol), vitamin B3 (niacinamide), derivatives of these vitamins (especially esters) and their mixtures; urea; caffeine; depigmentants such as kojic acid, hydroquinone and caffeic acid; salicylic acid and its derivatives; alpha-hydroxy acids such as lactic acid and glycolic acid and their derivatives; retinoids such as carotenoids and vitamin A derivatives; hydrocortisone; melatonin; extracts of algae, fungi, plants, yeasts, bacteria; steroids; anti-bacterial active ingredients such as 2,4,4'-trichloro-2'-hydroxy diphenyl ether (or triclosan), 3,4,4'-trichlorocarbanilide (or triclocarban) and the acids indicated above and in particular l salicylic acid and its derivatives; matting agents such as fibers; tensing agents; ceramides; essential oils ; and their mixtures; and any active suitable for the final purpose of the composition. Examples of steroids include dehydroepiandrosterone (or DHEA), as well as (1) its precursors and biological derivatives, in particular the salts and esters of DHEA, such as DHEA sulfate and salicylate, 7-hydroxy DHEA , 7-keto DHEA, esters of 7-hydroxy and 7-keto DHEA, in particular 3-beta-acetoxy-7-oxo DHEA, and (2) its precursors and chemical derivatives, in particular sapogenins such as diosgenin or hecogenin, and / or their derivatives such as hecogenin acetate, and / or natural extracts containing it and in particular extracts of Dioscorea, such as wild yam (Wild Yam).
Les filtres U.V. organiques autres que ceux à fonction sulfonique décrits ci- dessus, peuvent être présents en une quantité en matière active allant de 0,01 à 20 % en poids de matière active, de préférence de 0,1 à 15 % en poids, et mieux 0,2 à 10 % en poids par rapport au poids total de la composition.The organic UV filters other than those with a sulfonic function described above, can be present in an amount of active material ranging from 0.01 to 20% by weight of active material, preferably from 0.1 to 15% by weight, and better 0.2 to 10% by weight relative to the total weight of the composition.
Comme exemples de filtres organiques, actifs dans l'UV-A et/ou l'UV-B, pouvant être ajoutés dans la composition de l'invention, on peut citer par exemple, les dérivés de l'acide para-aminobenzoique ; les dérivés salicyliques tels que le salicylate d'éthyl hexyle vendu sous le nom commercial NEO HELIOPAN OS par Haarmann et Reimer ; les dérivés du dibenzoylméthane tels que le Butyl Methoxydibenzoylmethane vendu notamment sous le nom commercial PARSOL 1789 par Hoffmann La Roche ; les dérivés cinnamiques tels que l'éthylhexyl Methoxycinnamate vendu notamment sous le nom commercial PARSOL MCX par Hoffmann La Roche ; les dérivés de β,β'-diphénylacrylate tels que l'octocrylene (α- cyano-β,β-diphénylacrylate de 2-éthylhexyle) vendu sous le nom commercial UVINUL N539 par la société BASF ; les dérivés de la benzophénone tels que la Benzophénone- 1 vendu sous le nom commercial UVINUL 400 par BASF, la Benzophenone-2 vendu sous le nom commercial UVINUL D50 par BASF, la Benzophenone-3 ou Oxybenzone, vendu sous le nom commercial UVINUL M40 par BASF, la Benzophenone-4 vendu sous le nom commercial UVINUL MS40 par BASF ; les Dérivés du benzylidene camphre tels que le 4-Methylbenzylidene camphre vendu sous le nom commercial EUSOLEX 6300 par MERCK ; les dérivés du phenyl benzimidazole tels que le Benzimidazilate vendu sous le nom commercial NEO HELIOPAN AP par Haarmann et Reimer ; les dérivés de la triazine tels que l'Anisotriazine vendu sous le nom commercial TINOSORB S par CIBA GE1GY et l'éthylhexyl triazone vendu notamment sous le nom commercial UVINUL T150 par BASF ; les dérivés du phenyl benzotriazole tels que Drometrizole Trisiloxane vendu sous le nom commercial SILATRIZOLE par Rhodia Chimie ; les dérivés anthraniliques tels que le Menthyl anthranilate vendu sous le nom commercial NEO HELIOPAN MA par Haarmann et Reimer ; les dérivés d'imidazolines ; les dérivés du benzalmalonate ; et leurs mélanges.As examples of organic filters, active in UV-A and / or UV-B, which can be added to the composition of the invention, mention may, for example, be made of para-aminobenzoic acid derivatives; salicylic derivatives such as ethyl hexyl salicylate sold under the trade name NEO HELIOPAN OS by Haarmann and Reimer; dibenzoylmethane derivatives such as Butyl Methoxydibenzoylmethane sold in particular under the trade name PARSOL 1789 by Hoffmann La Roche; cinnamic derivatives such as ethylhexyl Methoxycinnamate sold in particular under the trade name PARSOL MCX by Hoffmann La Roche; derivatives of β, β'-diphenylacrylate such as octocrylene (2-ethylhexyl α-cyano-β, β-diphenylacrylate) sold under the trade name UVINUL N539 by the company BASF; Benzophenone derivatives such as Benzophenone-1 sold under the trade name UVINUL 400 by BASF, Benzophenone-2 sold under the trade name UVINUL D50 by BASF, Benzophenone-3 or Oxybenzone, sold under the trade name UVINUL M40 by BASF, Benzophenone-4 sold under the trade name UVINUL MS40 by BASF; Benzylidene camphor derivatives such as 4-Methylbenzylidene camphor sold under the trade name EUSOLEX 6300 by MERCK; phenyl benzimidazole derivatives such as Benzimidazilate sold under the trade name NEO HELIOPAN AP by Haarmann and Reimer; derivatives of the triazine such as Anisotriazine sold under the trade name TINOSORB S by CIBA GE1GY and ethylhexyl triazone sold in particular under the trade name UVINUL T150 by BASF; phenyl benzotriazole derivatives such as Drometrizole Trisiloxane sold under the trade name SILATRIZOLE by Rhodia Chimie; anthranilic derivatives such as Menthyl anthranilate sold under the trade name NEO HELIOPAN MA by Haarmann and Reimer; imidazoline derivatives; benzalmalonate derivatives; and their mixtures.
La composition selon l'invention peut constituer une composition cosmétique ou dermatologique et elle peut être utilisée dans toutes les applications habituelles de la vitamine C et de ses dérivés. Elle peut être utilisée notamment pour dépigmenter et/ou blanchir la peau, prévenir et/ou lutter contre les taches cutanées, les rides et/ou les ridules de la peau, pour prévenir et/ou lutter contre les signes du vieillissement cutané et/ou contre les méfaits des rayonnements UV. Elle peut aussi permettre de tonifier, régénérer et/ou lisser les ridules de la peau, et/ou pour renforcer les tissus cutanés contre les agressions de l'environnement. Elle peut être utilisée aussi pour traiter les taches de vieillissement qui apparaissent sur la peau avec l'âge.The composition according to the invention can constitute a cosmetic or dermatological composition and it can be used in all the usual applications of vitamin C and its derivatives. It can be used in particular to depigment and / or whiten the skin, prevent and / or fight against skin spots, wrinkles and / or fine lines of the skin, to prevent and / or fight against the signs of skin aging and / or against the harmful effects of UV radiation. It can also make it possible to tone, regenerate and / or smooth the fine lines of the skin, and / or to strengthen the skin tissues against environmental aggressions. It can also be used to treat age spots that appear on the skin with age.
Aussi, l'invention a encore pour objet l'utilisation cosmétique de la composition telle que définie ci-dessus pour dépigmenter et/ou blanchir la peau, prévenir et/ou lutter contre les taches cutanées, les rides et/ou les ridules de la peau, pour prévenir et/ou lutter contre les signes du vieillissement cutané et/ou contre les méfaits des rayonnements UN.Also, the subject of the invention is also the cosmetic use of the composition as defined above for depigmenting and / or bleaching the skin, preventing and / or combating skin spots, wrinkles and / or fine lines on the skin. skin, to prevent and / or fight against the signs of skin aging and / or against the harmful effects of UN radiation.
L'invention a aussi pour objet un procédé de traitement cosmétique destiné à dépigmenter et/ou blanchir la peau, prévenir et/ou lutter contre les taches cutanées, les rides et/ou les ridules de la peau, prévenir et/ou lutter contre les signes du vieillissement cutané et/ou contre les méfaits des rayonnements UV, comprenant l'application sur la peau d'une composition telle que définie ci- dessus. Elle a encore pour objet l'utilisation de la composition telle que définie ci-dessus pour la fabrication d'une pommade destinée à traiter les taches de vieillissement.The subject of the invention is also a cosmetic treatment process intended for depigmenting and / or bleaching the skin, preventing and / or combating skin spots, wrinkles and / or fine lines on the skin, preventing and / or combating signs of skin aging and / or against the harmful effects of UV radiation, comprising the application to the skin of a composition as defined above. It also relates to the use of the composition as defined above for the manufacture of an ointment intended for treating aging spots.
Les exemples ci-après de compositions selon l'invention sont donnés à titre d'illustration et sans caractère limitatif. Les noms sont donnés en dénominations CTFA ou en noms chimiques. Les quantités y sont données en % en poids, sauf mention contraire.The following examples of compositions according to the invention are given by way of illustration and without limitation. The names are given in CTFA names or in chemical names. The quantities are given in% by weight, unless otherwise stated.
Exemple 1 selon l'inventionExample 1 according to the invention
Eau 95,8 %Water 95.8%
Magnésium ascorbyl phosphate 0,1 %Magnesium ascorbyl phosphate 0.1%
Sodium tyrene/maleic acid copolymer (SMA1000HNa) 1 % Terephthalylidene dicamphor sulfonic acid (matière première à 33 % en matière active dans l'eau) 3,1 %Sodium tyrene / maleic acid copolymer (SMA1000HNa) 1% Terephthalylidene dicamphor sulfonic acid (raw material at 33% active ingredient in water) 3.1%
(soit 1 % de matière active)(i.e. 1% of active ingredient)
Le pH de la solution est de 2,0. On obtient une solution limpide.The pH of the solution is 2.0. A clear solution is obtained.
Exemple 2 comparatifComparative example 2
Eau 96,4 % Ascorbyl phosphate de magnésium 0,1 % Disodium EDTA 0,4 %Water 96.4% Ascorbyl magnesium phosphate 0.1% Disodium EDTA 0.4%
Terephthalylidene dicamphor sulfonic acid (matière première à 33 % en matière active dans l'eau) 3,1 %Terephthalylidene dicamphor sulfonic acid (raw material 33% active ingredient in water) 3.1%
(soit 1 % de matière active)(i.e. 1% of active ingredient)
Le pH de la solution est de 2,0. Il se forme un précipité dans la solution. Cet exemple montre que l'EDTA connu comme chélatant ne permet pas de résoudre le problème d'incompatibilité entre l'ascorbyl phosphate de magnésium et le filtre sulfonique.The pH of the solution is 2.0. A precipitate forms in the solution. This example shows that EDTA known as chelating does not solve the problem of incompatibility between magnesium ascorbyl phosphate and the sulfonic filter.
Exemple 3 comparatifComparative example 3
Eau 96,8 %Water 96.8%
Magnésium ascorbyl phosphate 0,1 %Magnesium ascorbyl phosphate 0.1%
Terephthalylidene dicamphor sulfonic acid (matière première à 33 % en matière active dans l'eau) 3,1 %Terephthalylidene dicamphor sulfonic acid (raw material 33% active ingredient in water) 3.1%
(soit 1 % de matière active)(i.e. 1% of active ingredient)
Le pH de la solution est de 1,5. Il se forme un précipité dans la solution. Cet exemple montre l'incompatibilité entre l'ascorbyl phosphate de magnésium et le filtre sulfonique.The pH of the solution is 1.5. A precipitate forms in the solution. This example shows the incompatibility between the magnesium ascorbyl phosphate and the sulfonic filter.
Pour les exemples 1 à 3, le mode opératoire est le suivant : On met dans l'eau l'ascorbyl phosphate de magnésium, ou ajoute le polymère ou l'EDTA puis le filtre UN.For examples 1 to 3, the procedure is as follows: The magnesium ascorbyl phosphate is placed in water, or the polymer or EDTA is added, then the UN filter.
Exemple 4 comparatif Phase A : Glycérine 3 %Comparative Example 4 Phase A: Glycerin 3%
Methyl paraben (conservateur) 0,25 %Methyl paraben (preservative) 0.25%
Phenoxyethanol (conservateur) 0,5 %Phenoxyethanol (preservative) 0.5%
Eau - qsp 100 %Water - qs 100%
Phase B :Phase B:
Gomme de xanthane 0,2 %0.2% xanthan gum
Ammonium polyacryloyldime thtyl taurate (Hostacerin AMPS) 1 %Ammonium polyacryloyldime thtyl taurate (Hostacerin AMPS) 1%
Acrylates/C10-30 akyl acrylate crosspolymer 0,2 % Phase C :Acrylates / C10-30 akyl acrylate crosspolymer 0.2% Phase C:
Triethanolamine 0,2 %0.2% triethanolamine
Phase D :Phase D:
Eau 2 %Water 2%
Terephthalylidene dicamphor sulfonic acid (matière première à 33 % en matière active dans l'eau) 3,1 %Terephthalylidene dicamphor sulfonic acid (raw material 33% active ingredient in water) 3.1%
(soit 1 % de matière active)(i.e. 1% of active ingredient)
Triethanolamine 0,25 %0.25% triethanolamine
Phase E :Phase E:
Dimethicone 1 %Dimethicone 1%
Isononyl isononate 1 %Isononyl isononate 1%
Cetearyl alcohol (and) Ceteareth-30 (Emulgator E-2209 de la société Goldschmidt) 1 %Cetearyl alcohol (and) Ceteareth-30 (Emulgator E-2209 from Goldschmidt) 1%
Ethylhexyl methoxycinnamate 1 %Ethylhexyl methoxycinnamate 1%
Acrylates copolymer 0,25 %Acrylates copolymer 0.25%
Cyclopentasiloxane 0,5 %Cyclopentasiloxane 0.5%
Phase F :Phase F:
Eau 2 %Water 2%
Magnésium ascorbyl phosphate 0,1 %Magnesium ascorbyl phosphate 0.1%
Tetrasodium EDTA 0,2 %Tetrasodium EDTA 0.2%
Mode opératoire : on mélange successivement les phases A à F introduisant l'une après l'autre.Procedure: successively mixing phases A to F, introducing one after the other.
La composition obtenue n'est pas homogène et contient de nombreux cristaux. Cet exemple montre que l'EDTA connu comme chélatant ne permet pas de résoudre le problème d'incompatibilité entre l'ascorbyl phosphate de magnésium et le filtre sulfonique. Exemple 5 selon l'invention .Emulsion H/ E.The composition obtained is not homogeneous and contains many crystals. This example shows that EDTA known as chelating does not solve the problem of incompatibility between magnesium ascorbyl phosphate and the sulfonic filter. Example 5 according to the invention. O / W emulsion
Phase A :Phase A:
Glycérine 3 %Glycerin 3%
Methyl paraben (conservateur) 0,25 %Methyl paraben (preservative) 0.25%
Phenoxyethanol (conservateur) 0,5 %Phenoxyethanol (preservative) 0.5%
Eau qsp 100 %Water qs 100%
Phase B : Gomme de xanthane 0,2 %Phase B: 0.2% xanthan gum
Ammonium polyacryloyldimethtyl taurate (Hostacerin AMPS) 1 %Ammonium polyacryloyldimethtyl taurate (Hostacerin AMPS) 1%
Acrylates/C 10-30 akyl acrylate crosspolymer (Pemulen) 0,2 %Acrylates / C 10-30 akyl acrylate crosspolymer (Pemulen) 0.2%
Phase C : Triethanolamine 0,2 %Phase C: Triethanolamine 0.2%
Phase D :Phase D:
Eau 2 %Water 2%
Terephthalylidene dicamphor sulfonic acid (matière première à 33 % en matière active dans l'eau) 3,1 %Terephthalylidene dicamphor sulfonic acid (raw material 33% active ingredient in water) 3.1%
(soit 1 % de matière active) Triethanolamine 0,25 %(i.e. 1% of active ingredient) Triethanolamine 0.25%
Phase t : Dimethicone 1 %Phase t: Dimethicone 1%
Isononyl isononate 1 %Isononyl isononate 1%
Cetearyl alcohol (and) Ceteareth- •30 (Emulgator E-2209 de la société Goldschmidt) 1 %Cetearyl alcohol (and) Ceteareth- • 30 (Emulgator E-2209 from Goldschmidt) 1%
Ethylhexyl methoxycinnamate 1 %Ethylhexyl methoxycinnamate 1%
Acrylates copolymer 0,25 %Acrylates copolymer 0.25%
Cyclopentasiloxane 0,5 %Cyclopentasiloxane 0.5%
Phase F : Eau 2 %Phase F: Water 2%
Magnésium ascorbyl phosphate 0,1 %Magnesium ascorbyl phosphate 0.1%
Sodium tyrene/maleic acid copolymer (SMA1000HNa) 1 %Sodium tyrene / maleic acid copolymer (SMA1000HNa) 1%
La composition obtenue est fluide, lisse et homogène à l'œil nu. Elle peut être utilisée comme composition photoprotectrice permettant de traiter et de lutter contre les signes du vieillissement cutané (anti-âge).The composition obtained is fluid, smooth and homogeneous to the naked eye. It can be used as a photoprotective composition for treating and combating the signs of skin aging (anti-aging).
Exemple 6 selon l'invention (Emulsion H/E)Example 6 according to the invention (O / W emulsion)
Phase A :Phase A:
Glycérine 3 %Glycerin 3%
Methyl paraben (conservateur) 0,25 %Methyl paraben (preservative) 0.25%
Phenoxyethanol (conservateur) 0,5 % Acide kojique 1 %Phenoxyethanol (preservative) 0.5% Kojic acid 1%
Eau qsp 100 %Water qs 100%
Phase B :Phase B:
Gomme de xanthane 0,2 %0.2% xanthan gum
Ammonium polyacryloyldimethtyl taurate (Hostacerin AMPS) 1 %Ammonium polyacryloyldimethtyl taurate (Hostacerin AMPS) 1%
Acrylates/C 10-30 akyl acrylate crosspolymer (Pemulen) 0,2 %Acrylates / C 10-30 akyl acrylate crosspolymer (Pemulen) 0.2%
Phase C : Triethanolamine 0,2 %Phase C: Triethanolamine 0.2%
Phase D :Phase D:
Eau 2 %Water 2%
Terephthalylidene dicamphor sulfonic acid (matière première à 33 % en matière active dans l'eau) 3,1 %Terephthalylidene dicamphor sulfonic acid (raw material 33% active ingredient in water) 3.1%
(soit 1 % de matière active) Triethanolamine 0,25 %(i.e. 1% of active ingredient) Triethanolamine 0.25%
Phase E . Dimethicone 1 %Phase E. Dimethicone 1%
Isononyl isononate 1 %Isononyl isononate 1%
Cetearyl alcohol (and) Ceteareth-30 (Emulgator E-2209 de la société Goldschmidt) 1 %Cetearyl alcohol (and) Ceteareth-30 (Emulgator E-2209 from Goldschmidt) 1%
Ethylhexyl methoxycinnamate 1 %Ethylhexyl methoxycinnamate 1%
Acrylates copolymer 0,25 %Acrylates copolymer 0.25%
Cyclopentasiloxane 0,5 %Cyclopentasiloxane 0.5%
Phase F : Eau 2 %Phase F: Water 2%
Magnésium ascorbyl phosphate 0,1 %Magnesium ascorbyl phosphate 0.1%
Sodium tyrene/maleic acid copolymer (SMA1000HNa) 1 %Sodium tyrene / maleic acid copolymer (SMA1000HNa) 1%
La composition obtenue est fluide, lisse et homogène à l'œil nu. Elle peut être utilisée comme composition dépigmentante et photoprotectrice, permettant de lutter contre l'apparition des taches. The composition obtained is fluid, smooth and homogeneous to the naked eye. It can be used as a depigmenting and photoprotective composition, making it possible to combat the appearance of spots.

Claims

REVENDICATIONS
1. Composition aqueuse comprenant dans un milieu physiologiquement acceptable, au moins un sel métallique d'acide ascorbique phosphorylé, au moins un filtre UN. hydrosoluble comportant au moins une fonction sulfonique, et au moins un polymère d'anhydride maléique.1. An aqueous composition comprising, in a physiologically acceptable medium, at least one metal salt of phosphorylated ascorbic acid, at least one UN filter. water-soluble comprising at least one sulphonic function, and at least one polymer of maleic anhydride.
2. Composition selon la revendication 1, caractérisée en ce que le polymère est un homopolymère ou un copolymère.2. Composition according to claim 1, characterized in that the polymer is a homopolymer or a copolymer.
3. Composition selon l'une quelconque des revendications précédentes, caratérisée en ce que les unités anhydride maléique du polymère sont sous forme hydrolysée et sous forme de sels alcalins.3. Composition according to any one of the preceding claims, characterized in that the maleic anhydride units of the polymer are in hydrolyzed form and in the form of alkaline salts.
4. Composition selon l'une quelconque des revendications précédentes, caractérisée en ce que le polymère est un copolymère comportant des monomères anhydride maléique et des co-monomères choisis parmi l'acétate de vinyle, l'alcool vinylique, la vinylpyrrolidone, les oléfines comportant de 4 à 12 atomes de carbone, les alkylvinyléthers, le styrène, et leurs mélanges.4. Composition according to any one of the preceding claims, characterized in that the polymer is a copolymer comprising maleic anhydride monomers and co-monomers chosen from vinyl acetate, vinyl alcohol, vinylpyrrolidone, olefins comprising from 4 to 12 carbon atoms, alkylvinyl ethers, styrene, and their mixtures.
5. Composition selon l'une quelconque des revendications précédentes, caractérisée en ce que le polymère possède une fraction molaire en unité anhydride maléique comprise entre 0,1 et 1.5. Composition according to any one of the preceding claims, characterized in that the polymer has a molar fraction in maleic anhydride unit of between 0.1 and 1.
6. Composition selon l'une quelconque des revendications précédentes, caractérisée en ce que le polymère est sous forme de sel de sodium.6. Composition according to any one of the preceding claims, characterized in that the polymer is in the form of the sodium salt.
7. Composition selon l'une quelconque des revendications précédentes, caractérisée en ce que le polymère est un copolymère de styrène et d'anhydride maléique.7. Composition according to any one of the preceding claims, characterized in that the polymer is a copolymer of styrene and maleic anhydride.
8. Composition selon la revendication précédente, caractérisée en ce que le copolymère de styrène et d'anhydride maléique est dans un rapport 50/50. 8. Composition according to the preceding claim, characterized in that the copolymer of styrene and maleic anhydride is in a 50/50 ratio.
9. Composition selon l'une quelconque des revendications précédentes, caractérisée en ce que le rapport molaire entre la quantité d'unités anhydride maléique et le sel métallique d'acide ascorbique phosphorylé va de 0,005 à 10.9. Composition according to any one of the preceding claims, characterized in that the molar ratio between the quantity of maleic anhydride units and the metal salt of phosphorylated ascorbic acid ranges from 0.005 to 10.
10. Composition selon l'une quelconque des revendications précédentes, caractérisée en ce que le polymère est présent en une quantité allant de 0,05 à 30 % en poids par rapport au poids total de la composition.10. Composition according to any one of the preceding claims, characterized in that the polymer is present in an amount ranging from 0.05 to 30% by weight relative to the total weight of the composition.
11. Composition selon l'une quelconque des revendications précédentes, caractérisée en ce que le sel métallique d'acide ascorbique phosphorylé est choisi parmi les ascorbyl phosphates de métal alcalin, les ascorbyl phosphates de métal alcalino-terreux, les ascorbyl phosphates de métal de transition, et leurs mélanges.11. Composition according to any one of the preceding claims, characterized in that the metal salt of phosphorylated ascorbic acid is chosen from ascorbyl phosphates of alkali metal, ascorbyl phosphates of alkaline earth metal, ascorbyl phosphates of transition metal , and mixtures thereof.
12. Composition selon l'une quelconque des revendications précédentes, caractérisée en ce que le sel métallique d'acide ascorbique phosphorylé est l'ascorbyl phosphate de magnésium.12. Composition according to any one of the preceding claims, characterized in that the metal salt of phosphorylated ascorbic acid is magnesium ascorbyl phosphate.
13. Composition selon l'une quelconque des revendications précédentes, caractérisée en ce que le sel métallique d'acide ascorbique phosphorylé est présent en une quantité allant de 0,1 à 20 % en poids par rapport au poids total de la composition.13. Composition according to any one of the preceding claims, characterized in that the metal salt of phosphorylated ascorbic acid is present in an amount ranging from 0.1 to 20% by weight relative to the total weight of the composition.
14. Composition selon l'une quelconque des revendications précédentes, caractérisée en ce que le filtre peut être choisi parmi les dérivés sulfones ou sulfonates du benzylidene camphre, de la benzophénone, du phénylbenzimidazole, et leurs mélanges.14. Composition according to any one of the preceding claims, characterized in that the filter can be chosen from sulfone or sulfonate derivatives of benzylidene camphor, benzophenone, phenylbenzimidazole, and mixtures thereof.
15. Composition selon l'une quelconque des revendications précédentes, caractérisée en ce que le filtre est un dérivé du benzylidene camphre présentant la formule (I) suivante :
Figure imgf000034_0001
dans laquelle
15. Composition according to any one of the preceding claims, characterized in that the filter is a benzylidene camphor derivative having the following formula (I):
Figure imgf000034_0001
in which
Z désigne un groupementZ denotes a group
Figure imgf000034_0002
Figure imgf000034_0002
dans lequel Y représente -H ou -SO3H, éventuellement neutralisé,in which Y represents -H or -SO3H, possibly neutralized,
- n est égal à 0 ou est un nombre allant de 1 à 4,- n is equal to 0 or is a number ranging from 1 to 4,
- Ri représente un ou plusieurs radicaux alkyle ou alkoxy, identiques ou différents, linéaires ou ramifiés, contenant de 1 à 4 atomes de carbone.- Ri represents one or more alkyl or alkoxy radicals, identical or different, linear or branched, containing from 1 to 4 carbon atoms.
16. Composition selon la revendication précédente, caractérisée en ce que le filtre est l'acide benzène 1 ,4 [di(3-méthylidène campho-10-sulfonique)].16. Composition according to the preceding claim, characterized in that the filter is benzene acid 1, 4 [di (3-methylidene campho-10-sulfonic)].
17. Composition selon l'une quelconque des revendications précédentes, caractérisée en ce que le filtre est un dérivé du benzylidene camphre présentant la formule (II) suivante :17. Composition according to any one of the preceding claims, characterized in that the filter is a derivative of benzylidene camphor having the following formula (II):
Figure imgf000034_0003
dans laquelle : R2 désigne un atome d'hydrogène ou un radical 7SO3H,
Figure imgf000034_0003
in which : R 2 denotes a hydrogen atom or a 7SO3H radical,
- R3, R4, R5 et Rβ, identiques ou différents, représentent un groupement hydroxyle, un radical alkyle ayant de 1 à 4 atomes de carbone environ, linéaire ou ramifié, un radical alcenyle ayant de 2 à 4 atomes de carbone environ, linéaire ou ramifié, un radical alcoxy ayant de 1 à 4 atomes de carbone, linéaire ou ramifié, un radical alcényloxy ayant de 2 à 4 atomes de carbone, linéaire ou ramifié, un radical halogéno ; de plus un radical R3 à R6 seulement peut être un radical -SO3H, au moins un des radicaux R3 à Rβ désignant le radical -SO3H quand R2 est un atome d'hydrogène.- R 3 , R 4 , R 5 and Rβ, identical or different, represent a hydroxyl group, an alkyl radical having from 1 to 4 carbon atoms approximately, linear or branched, an alkenyl radical having from 2 to 4 carbon atoms approximately , linear or branched, an alkoxy radical having from 1 to 4 carbon atoms, linear or branched, an alkenyloxy radical having from 2 to 4 carbon atoms, linear or branched, a halo radical; moreover, a radical R3 to R 6 only can be a radical -SO3H, at least one of the radicals R 3 to Rβ denoting the radical -SO3H when R 2 is a hydrogen atom.
18. Composition selon l'une quelconque des revendications précédentes, caractérisée en ce que le filtre est un dérivé du benzylidene camphre présentant la formule (III) suivante :18. Composition according to any one of the preceding claims, characterized in that the filter is a benzylidene camphor derivative having the following formula (III):
Figure imgf000035_0001
dans laquelle :
Figure imgf000035_0001
in which :
- Ru désigne un atome d'hydrogène, un radical alkyle ou alcoxy, linéaire ou ramifié, contenant de 1 à 6 atomes de carbone environ ou un radical -SO3H,Ru denotes a hydrogen atom, an alkyl or alkoxy radical, linear or branched, containing from 1 to 6 carbon atoms approximately or a radical -SO3H,
- R12 désigne un atome d'hydrogène, un radical alkyle ou alcoxy, linéaire ou ramifié, contenant de 1 à 6 atomes de carbone environ,- R12 denotes a hydrogen atom, an alkyl or alkoxy radical, linear or branched, containing from 1 to 6 carbon atoms approximately,
- R13 désigne un atome d'hydrogène ou un radical -SO3H,- R13 denotes a hydrogen atom or a radical -SO3H,
l'un au moins des radicaux R-n et Ri3 désignant un radical -SO3H, - X est un atome d'oxygène ou de soufre ou un groupement -NR-, R étant un atome d'hydrogène ou un radical alkyle, linéaire ou ramifié, contenant de 1 à 6 atomes de carbone.at least one of the radicals Rn and R i3 denoting a radical -SO3H, - X is an oxygen or sulfur atom or a group -NR-, R being a hydrogen atom or an alkyl radical, linear or branched, containing from 1 to 6 carbon atoms.
19. Composition selon l'une quelconque des revendications précédentes, caractérisée en ce que la quantité de filtre(s) va de 0,01 à 10 % en poids par rapport au poids total de la composition.19. Composition according to any one of the preceding claims, characterized in that the quantity of filter (s) ranges from 0.01 to 10% by weight relative to the total weight of the composition.
20. Composition selon l'une quelconque des revendications précédentes, caractérisée en ce qu'elle se présente sous forme d'une émulsion, de préférence une émulsion H/E.20. Composition according to any one of the preceding claims, characterized in that it is in the form of an emulsion, preferably an O / W emulsion.
21. Composition selon l'une quelconque des revendications précédentes, caractérisée en ce qu'elle constitue une composition cosmétique ou dermatologique.21. Composition according to any one of the preceding claims, characterized in that it constitutes a cosmetic or dermatological composition.
22. Utilisation cosmétique d'une composition cosmétique selon l'une des revendications 1 à 20, pour dépigmenter et/ou blanchir la peau, prévenir et/ou lutter contre les taches cutanées, les rides et/ou les ridules de la peau, pour prévenir et/ou lutter contre les signes du vieillissement cutané et/ou contre les méfaits des rayonnements UN.22. Cosmetic use of a cosmetic composition according to one of claims 1 to 20, for depigmenting and / or bleaching the skin, preventing and / or combating skin spots, wrinkles and / or fine lines on the skin, for prevent and / or fight against the signs of skin aging and / or against the harmful effects of UN radiation.
23. Procédé de traitement cosmétique de la peau, destiné à dépigmenter et/ou blanchir la peau, prévenir et/ou lutter contre les taches cutanées, les rides et/ou les ridules de la peau, prévenir et/ou lutter contre les signes du vieillissement cutané et ou contre les méfaits des rayonnements UN., comprenant l'application sur la peau, d'une composition cosmétique selon l'une quelconque des revendications 1 à 20.23. Cosmetic skin treatment process, intended to depigment and / or whiten the skin, prevent and / or fight against skin spots, wrinkles and / or fine lines on the skin, prevent and / or fight against signs of skin aging and or against the harmful effects of UN radiation, comprising the application to the skin of a cosmetic composition according to any one of claims 1 to 20.
24. Utilisation de la composition selon l'une quelconque des revendications 1 à 20, pour la fabrication d'une pommade destinée à traiter les taches de vieillissement.24. Use of the composition according to any one of claims 1 to 20, for the manufacture of an ointment intended to treat age spots.
25. Utilisation d'un polymère d'anhydride maléique, pour obtenir une composition aqueuse homogène contenant au moins un sel métallique d'acide ascorbique phosphorylé et au moins un filtre UN. hydrosoluble comportant au moins une fonction sulfonique. 25. Use of a polymer of maleic anhydride to obtain a homogeneous aqueous composition containing at least one metal salt of ascorbic acid phosphorylated and at least one UN filter. water-soluble comprising at least one sulphonic function.
PCT/FR2003/002626 2002-09-30 2003-09-02 Cosmetic or dermatological composition containing an ascorbic acid derivative and a filter WO2004028483A2 (en)

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FR2903004A1 (en) * 2006-07-03 2008-01-04 Oreal Cosmetic use of a synergistic combination of a C-glycoside derivative with ascorbic acid, its derivatives or analogs useful e.g. to treat or prevent the chronobiological or photo-induced aging signs of body/face skin
US7691903B2 (en) 2002-06-20 2010-04-06 L'oreal Oxidation-sensitive hydrophilic active principle containing composition and use thereof
US9421157B2 (en) 2006-07-03 2016-08-23 L'oreal Use of C-glycoside derivatives as pro-desquamating active agents

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FR2905859B1 (en) * 2006-09-15 2008-11-14 Oreal COMPOSITION AGAINST LOCALIZED HYPERPIGMENTATION OF DARK SKINS
FR2905856A1 (en) * 2006-09-15 2008-03-21 Oreal Composition, useful to treat and/or prevent cutaneous sign of aging, comprises copolymer of styrenic monomer and carboxylic diacid with ethylene unsaturation, and active agent e.g. agents having restructuring effect of cutaneous barrier
CN101621987B (en) * 2007-02-28 2013-08-21 宝洁公司 Personal care composition comprising botanical extract of ficus benghalensis
US9125825B2 (en) * 2009-04-22 2015-09-08 Medskin Solutions Dr. Suwelack Ag Freeze-dried molded article containing magnesium ascorbyl phosphate
WO2015005488A1 (en) * 2013-07-09 2015-01-15 L'oreal Long- wear cosmetic composition

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WO1999033439A1 (en) * 1997-12-24 1999-07-08 Shaklee Corporation Composition with high efficiency skin protection from damaging effects of ultraviolet light

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US7691903B2 (en) 2002-06-20 2010-04-06 L'oreal Oxidation-sensitive hydrophilic active principle containing composition and use thereof
FR2897268A1 (en) * 2006-02-10 2007-08-17 Oreal Use of a copolymer of styrenic monomer and carboxylic diacid with ethylene unsaturation, to depigment and/or to bleach the skin, preferably to eliminate the pigmentary spots, age spots and/or as anti-pigmenting agent
FR2903004A1 (en) * 2006-07-03 2008-01-04 Oreal Cosmetic use of a synergistic combination of a C-glycoside derivative with ascorbic acid, its derivatives or analogs useful e.g. to treat or prevent the chronobiological or photo-induced aging signs of body/face skin
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US9421157B2 (en) 2006-07-03 2016-08-23 L'oreal Use of C-glycoside derivatives as pro-desquamating active agents

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