WO2009074409A1 - S-triazine compounds containing one aminosiloxane group and two particular para-aminobenzalmalonate groups; cosmetic compositions containing said derivatives; uses of said s-triazine derivatives - Google Patents

S-triazine compounds containing one aminosiloxane group and two particular para-aminobenzalmalonate groups; cosmetic compositions containing said derivatives; uses of said s-triazine derivatives Download PDF

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Publication number
WO2009074409A1
WO2009074409A1 PCT/EP2008/065115 EP2008065115W WO2009074409A1 WO 2009074409 A1 WO2009074409 A1 WO 2009074409A1 EP 2008065115 W EP2008065115 W EP 2008065115W WO 2009074409 A1 WO2009074409 A1 WO 2009074409A1
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derivatives
trade name
sold
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under
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PCT/EP2008/065115
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French (fr)
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Hervé Richard
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L'oreal
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/58—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing atoms other than carbon, hydrogen, halogen, oxygen, nitrogen, sulfur or phosphorus
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P17/00—Drugs for dermatological disorders
    • A61P17/16—Emollients or protectives, e.g. against radiation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0834—Compounds having one or more O-Si linkage
    • C07F7/0838—Compounds with one or more Si-O-Si sequences

Definitions

  • the invention relates to novel s-triazine compounds containing one aminosiloxane group and two particular para-aminobenzalmalonate groups with formula (I) which will be defined in detail below, and to their uses in cosmetics.
  • the invention also relates to cosmetic or dermatological compositions intended for the photoprotection of keratinous materials comprising, in a cosmetically acceptable medium, at least one s- triazine compound containing one aminosiloxane group and two grafted para-aminobenzalmalonate groups with formula (I) which will be defined in detail below.
  • the invention also relates to the use of at least one s-triazine compound containing one aminosiloxane group and two grafted para-aminobenzalmalonate groups with formula (I) which will be defined in detail below in a cosmetic composition as a UV-A radiation filtering agent.
  • Radiation with wavelengths in the range 280 nm to 400 nm is known to promote tanning of the human epidermis, and radiation with wavelengths in the range 280 nm to 320 nm, known as UV-B radiation, is known to cause erythemas and skin burns which may be harmful to the development of a natural tan.
  • UV-A radiation with wavelengths in the range 320 nm to 400 nm, causing tanning of the skin is known to be capable of inducing alteration therein, especially in the case of sensitive skin and/or skin which is continually exposed to solar radiation.
  • UV-A irradiation causes a loss in the elasticity of the skin and the appearance of wrinkles, promoting premature ageing of the skin. It promotes triggering of the erythemal reaction or amplifies this reaction in certain individuals and may even be the source of phototoxic or photoallergic reactions.
  • the term "sun protection factor” means the ratio of the irradiation period necessary to achieve the erythematogenic threshold in the present of a test filter to the irradiation period necessary to reach that same threshold in the absence of a filter.
  • the photoprotective compounds sought must also have good cosmetic properties, good solubility in the usual solvents and in particular in fatty substances such as oils and fats, as well as good resistance to water and to perspiration (persistence) , and satisfactory photostability .
  • the Applicant has surprisingly discovered a novel family of s-triazine derivatives carrying one aminosiloxane group and two particular para- aminobenzalmalonate groups having good absorption properties in the long UV-A radiation range and having a solublity in fatty substances, a photostability, as well as cosmetic qualities which are substantially improved with respect to the prior art s-triazine derivatives grafted with aminobenzalmalonates mentioned above .
  • the invention concerns a novel family of s-triazine derivatives carrying one aminosiloxane group and two particular para-aminobenzalmalonate groups with formula (I) which will be defined in detail below.
  • the invention also concerns a cosmetic or dermatological composition intended for the photoprotection of keratinous materials, containing at least one compound with formula (I) in a cosmetically acceptable medium.
  • the invention also concerns the use of at least one s- triazine compound containing one aminosiloxane group and two grafted para-aminobenzalmalonate groups with formula (I) which will be defined below in detail in a cosmetic composition as a UV-A radiation filtering agent .
  • the compounds of the present invention have the following general formula (I) or one of its tautomeric forms:
  • • (X) which may be identical or different, represent a linear or branched C1-C30 alkyl radical, optionally halogenated or unsaturated, a - A -
  • R which may be identical or different, designate a group with formula (III) :
  • Ri and R2 which may be identical or different, represent a linear or branched Ci-Cs alkyl group
  • Ri and R2 may form a C 5 -Cs cycle, optionally substituted with 1, 2 or 3 linear or branched Ci-C 4 alkyl groups;
  • (Z) is a linear or branched, saturated or unsaturated Ci-Cio alkylene diradical, optionally substituted with a hydroxy radical or oxygens and which may optionally contain an amino group;
  • W represents a hydrogen atom, a hydroxy radical or a linear or branched Ci-Cs alkyl radical.
  • the organosiloxane may comprise units with formula -(X)b-(Si) (O) ⁇ 4-b)/2 in which:
  • the s-triazine compounds of the invention are represented by the following formulae (Ia) or (Ib) :
  • R 6 which may be identical or different, are selected from linear or branched C1-C20 alkyl, phenyl, 3, 3, 3-trifluoropropyl and trimethylsilyloxy radicals, at least 80% by number of radicals Re being methyl;
  • Linear diorganosiloxanes with formula (Ia) are particularly preferred.
  • linear or cyclic diorganosiloxanes with formula (Ia) or (Ib) used in the context of the present invention are random oligomers or polymers preferably having at least one and more preferably all of the following characteristics :
  • Re is alkyl; more preferably, it is methyl
  • the alkyl radicals may be linear or branched and in particular are selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert- butyl, n-amyl, isoamyl, neopentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl and tert-octyl radicals.
  • the alkyl radical is the methyl radical.
  • the cycloalkyl radicals may in particular be selected from cyclopentyl, cyclohexyl and cycloheptyl radicals. Particularly preferably, the cycloalkyl radical is the cyclohexyl radical. These radicals may be substituted with Ci-C 4 alkyl radicals, preferably selected from methyl, isopropyl and tert-butyl.
  • Preferred compounds with formula (I) which may be cited include those in which (X) is the methyl radical and A is the propyl diradical.
  • Ri, R2 and R3 designate a Ci-C 4 alkyl and more particularly methyl, or R 3 designates hydrogen and Ri and R2 form a C 5 -Cs cycle, optionally substituted with 1 or two alkyl radicals, more particularly cyclohexyl.
  • Ri and R2 designate a Ci-C 4 alkyl, more particularly methyl.
  • the derivatives with formula ( I ) may be obtained in accordance with the fol lowing reaction scheme :
  • R, A, X and a satisfy the above definitions and Y represents a halogen, in particular chlorine or bromine .
  • the reagents may be introduced in any order, 2 equivalents of the derivative with formula (III) followed by one equivalent of the derivative with formula (IV) (route Ia) or 1 equivalent of the derivative with formula (IV) followed by 2 equivalents of the derivative with formula (III) (route Ib) .
  • the above reactions may optionally be carried out in the presence of a solvent (for example toluene, xylene or acetone/water) at a temperature in the range 0 0 C to 250 0 C, more particularly in the range 5°C to 150 0 C; the introduction order must be sequenced but the intermediate products may or may not be isolated.
  • a solvent for example toluene, xylene or acetone/water
  • the above reactions may optionally be carried out in the presence of a solvent (for example : THF, methyl ethyl ketone, ethyl acetate or acetone/water for the first step; toluene, xylene, ethyl acetate, methylethyl ketone or 1, 2-dichloroethane for the second step), at a temperature in the range 0 0 C to 200 0 C, more particularly in the range 0 0 C to 20 0 C for the first step and in the range 50 0 C to 120 0 C for the second step and in the presence or absence of a base to trap the acid formed (for example : sodium bicarbonate, sodium carbonate, aqueous sodium hydroxide, triethylamine or pyridine) .
  • a solvent for example : THF, methyl ethyl ketone, ethyl acetate or acetone/water for the first step; toluene, xy
  • a microwave oven in the presence or absence of a solvent (for example : toluene, xylene or 1, 2-dichloroethane) or in the presence or absence of 10% of graphite, at a temperature of 50°C to 150°C, at a power of 50-150 watts for a period of 10 to 30 minutes.
  • a solvent for example : toluene, xylene or 1, 2-dichloroethane
  • 10% of graphite at a temperature of 50°C to 150°C, at a power of 50-150 watts for a period of 10 to 30 minutes.
  • the monomeric alkoxysilane derivatives may be polymerized using conventional methods of silicone chemistry.
  • the compounds with formula (III) may be prepared using the known methods described in patents FR-2 385 685 or FR-2 888 113.
  • the amino-containing silicones with formula (IV) may be obtained from Dow Corning Toray Silicone Co Ltd, such as those with an ⁇ , ⁇ -diamino structure such as BY16-853 (viscosity: 30; NH 2 equivalent: 650) or BY16-853B (viscosity: 80; NH 2 equivalent: 2200) or those with pendent groups, such as BY16-828 (viscosity: 120; NH 2 equivalent: 3500) or BY16-850 (viscosity: 1100; NH 2 equivalent: 4000) .
  • BY16-853 viscosity: 30; NH 2 equivalent: 650
  • BY16-853B viscosity: 80; NH 2 equivalent: 2200
  • pendent groups such as BY16-828 (viscosity: 120; NH 2 equivalent: 3500) or BY16-850 (viscosity: 1100; NH 2 equivalent: 4000) .
  • the invention also concerns cosmetic or dermatological compositions intended for the photoprotection of keratinous materials comprising, in a cosmetically acceptable medium, at least one s-triazine compound containing one aminosiloxane group and two grafted para-aminobenzalmalonate groups with formula (I) as defined above.
  • cosmetically acceptable medium means a non-toxic medium which is capable of being applied to human keratinous materials comprising the skin, face, lips, nails, hair and scalp.
  • the compounds with formula (I) are generally present in the composition of the invention in proportions in the range 0.01% to 20% by weight, preferably in the range 0.1% to 10% by weight, with respect to the total composition weight.
  • compositions of the invention may in addition contain at least one mineral UV filter and/or at least one complementary organic UV filter.
  • organic UV filters are selected from hydrosoluble organic filters, liposoluble organic filters or organic filters which are insoluble in the solvents which are routinely used in anti-sun products and mixtures thereof .
  • organic UV filters are selected from cinnamic derivatives; anthranilates; salicylic derivatives, dibenzoylmethane derivatives, camphor derivatives; benzophenone derivatives; ⁇ / ⁇ diphenylacrylate derivatives; triazine derivatives; benzotriazole derivatives; benzalmalonate derivatives in particular those cited in patent US-5 624 663; benzimidazole derivatives; imidazolines; bis- benzoazolyl derivatives such as those described in patents EP-O 669 323 and US-2 463 264; p- aminobenzoic acid (PABA) derivatives; methylene bis- (hydroxyphenyl benzotriazole) derivatives such as those described in US-5 237 071, US-5 166 355, GB-2 303 549, DE-197 26
  • Ethylhexyl Methoxycinnamate sold in particular under the trade name PARSOL MCX by DSM NUTRITIONAL PRODUCTS, INC.;
  • Dibenzoylmethane derivatives Butyl Methoxydibenzoylmethane, sold in particular under the trade name PARSOL 1789 by DSM NUTRITIONAL PRODUCTS, INC . ; Isopropyl Dibenzoylmethane;
  • Ethylhexyl Dimethyl PABA in particular sold under the name "ESCALOL 507" by ISP; Glyceryl PABA; PEG-25 PABA sold under the name "UVINUL P25" by BASF;
  • Salicylic derivatives Homosalate sold under the name "Eusolex HMS” by Rona/EM
  • Dipropyleneglycol Salicylate sold under the name "DIPSAL” by SCHER;
  • TEA Salicylate sold under the name "NEO HELIOPAN TS” by SYMRISE;
  • J3, J3-diphenylacrylate derivatives Octocrylene sold in particular under the trade name "UVINUL N539" by BASF;
  • Etocrylene sold in particular under the trade name "UVINUL N35" by BASF;
  • UVINUL 400 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
  • Benzophenone-4 sold under the trade name "UVINUL MS40" by BASF; Benzophenone-5;
  • Benzophenone-6 sold under the trade name "Helisorb 11" by Norquay;
  • Benzophenone-8 sold under the trade name "Spectra-Sorb
  • UV-24 by American Cyanamid
  • Benzophenone-9 sold under the trade name "UVINUL DS-49" by BASF;
  • Benzophenone-12 n-hexyl 2- (4-diethylamino-2-hydroxybenzoyl) -benzoate sold under the trade name "UVINUL A+" by BASF;
  • Camphor Benzalkonium Methosulphate produced under the name "MEXORYL SO” by CHIMEX
  • Terephthalylidene Dicamphor Sulphonic Acid produced under the name "MEXORYL SX” by CHIMEX;
  • Phenylbenzimidazole Sulphonic Acid sold in particular under the trade name "EUSOLEX 232" by MERCK;
  • UV-ASORB HEB Diethylhexyl Butamido Triazone sold under the trade name "UV-ASORB HEB” by SIGMA 3V;
  • Anthranilic derivatives Menthyl anthranilate sold under the trade name "NEO HELIOPAN MA" by HAARMANN and REIMER;
  • Imidazoline derivatives Ethylhexyl Dimethoxybenzylidene Dioxoimidazoline Propionate;
  • Benzalmalonate derivatives Polyorganosiloxane with benzalmalonate functions such as Polysilicone-15 sold under the trade name "PARSOL SLX” by DSM NUTRITIONAL PRODUCTS, INC.;
  • Preferred organic filters are selected from :
  • the complementary organic filters of the invention generally represent 0.1% to 30%, preferably 1% to 25% of the total composition weight.
  • the complementary inorganic UV filters used in accordance with the present invention are metal oxide pigments. More preferably, the inorganic UV filters of the invention are metal oxide particles having a mean elementary particle size of 500 nm or less, more preferably in the range 5 nm to 500 nm, and still more preferably in the range 10 nm to 100 nm, preferably in the range 15 nm to 50 nm.
  • They may in particular be selected from oxides of titanium, zinc, iron, zirconium, cerium or mixtures thereof, and more particularly titanium oxides.
  • Such metal oxide pigments which may be coated or non- coated, are described in particular in patent application EP-A-O 518 773. Examples of commercially available pigments which may be mentioned are the products sold by Kemira, Tayca, Merck and Degussa.
  • the metal oxide pigments may be coated or non-coated.
  • the coated pigments are pigments which have undergone one or more surface treatments of a chemical, electronic, mechanochemical and/or mechanical nature with compounds such as amino acids, beeswax, fatty acids, fatty alcohols, anionic surfactants, lecithins, sodium, potassium, zinc, iron or aluminium salts of fatty acids, metal alkoxides (of titanium or aluminium), polyethylene, silicones, proteins
  • the coated pigments are titanium oxides coated: with silica, such as the product "SUNVEIL” from IKEDA; with silica and iron oxide, such as the product “SUNVEIL F” from IKEDA; with silica and alumina, such as the products “MICROTITANIUM DIOXIDE MT 500 SA” and “MICROTITANIUM DIOXIDE MT 100 SA” from TAYCA, "TIOVEIL” from TIOXIDE;
  • Non-coated titanium oxide pigments are, for example, sold by TAYCA under the trade names "MICROTITANIUM DIOXIDE MT 500 B” or “MICROTITANIUM DIOXIDE MT 600 B”, by DEGUSSA under the trade name "P 25”, by WACKER under the trade name "Oxyde de titane transparent PW”, by MIYOSHI KASEI under the trade name "UFTR”, by TOMEN under the trade name "ITS” and by TIOXIDE under the trade name "TIOVEIL AQ”.
  • non-coated zinc oxide pigments examples are:
  • Nanophase Technologies those sold under the trade name "Nanogard WCD 2025" by Nanophase Technologies.
  • non-coated zinc oxide pigments are: - those sold under the trade name "Oxide zinc CS-5" by Toshibi (ZnO coated with polymethylhydrogenesiloxane) ;
  • the non-coated cerium oxide pigments may, for example, be those sold under the trade name "COLLOIDAL CERIUM OXIDE” by RHONE POULENC.
  • non-coated iron oxide pigments are those sold by ARNAUD under the trade names "NANOGARD WCD 2002 (FE 45B)", “NANOGARD IRON FE 45 BL AQ”, “NANOGARD FE 45R AQ, “NANOGARD WCD 2006 (FE 45R)", or by MITSUBISHI under the trade name "TY-220”.
  • coated iron oxide pigments are those sold by ARNAUD under the trade names "NANOGARD WCD 2008
  • NANOGARD FE 45 BL 345" "NANOGARD FE 45 BL"
  • metal oxides may also be cited, in particular of titanium dioxide and cerium dioxide, including the mixture of equal weights of titanium dioxide and cerium dioxide coated with silica sold by IKEDA under the trade name "SUNVEIL A", as well as the mixture of titanium dioxide and zinc dioxide coated with alumina, silica and silicone, such as the product "M 261” sold by KEMIRA or coated with alumina, silica and glycerine such as the product "M 211" sold by KEMIRA.
  • coated or non-coated titanium oxide pigments are particularly preferred.
  • the complementary inorganic filters of the invention generally represent 0.5% to 40%, preferably 1% to 30% of the total composition weight.
  • compositions of the invention may be presented in any of the forms generally used for topical application, in particular in the form of an oil-in-water emulsion (direct emulsion) , water-in-oil emulsion (reverse emulsion) or an aqueous gel.
  • the compositions of the invention may contain any of the additives which are routinely used in cosmetics and have applications in the field of skin care, makeup and anti-sun products.
  • aqueous compositions of the present invention may also comprise conventional cosmetic adjuvants, particularly those selected from fatty substances, organic solvents, ionic or non-ionic, hydrophilic or lipophilic thickeners, demulcents, humectants, opacifying agents, stabilizers, emollients, silicones, anti-foaming agents, fragrances, preservatives, anionic, cationic, non-ionic, zwitterionic or amphoteric surfactants, active ingredients, fillers, polymers, propellants, alkalinizing or acidifying agents or any other ingredient which is routinely used in the cosmetics and/or dermatological field.
  • conventional cosmetic adjuvants particularly those selected from fatty substances, organic solvents, ionic or non-ionic, hydrophilic or lipophilic thickeners, demulcents, humectants, opacifying agents, stabilizers, emollients, silicones, anti-foaming agents, fragrances, preservatives
  • the fatty substances may be constituted by an oil or a wax or mixtures thereof.
  • oil means a compound which is a liquid at ambient temperature.
  • wax means a compound which is solid or substantially solid at ambient temperature, and has a melting point which is generally more than 35°C.
  • Oils which may be cited are mineral oils (paraffin) ; vegetable oils (sweet almond oil, macadamia oil, blackcurrant oil, jojoba oil); synthetic oils such as perhydrosqualene, alcohols, fatty amides (such as isopropyl lauroyl sarcosinate sold under the trade name "Eldew SL-205" by Ajinomoto), fatty acids or esters, such as the C12-C15 alcohol benzoate sold under the trade name "Finsolv TN” or “Witconol TN” by WITCO, phenylethyl benzoate sold under the trade name XTEND- 226 by ISP or SPECTRASOL PEB by CP HALL, octyl palmitate, isopropyl lanolate, triglycerides including those of capric/caprylic acids, dicaprylyl carbonate sold under the trade name "Cetiol CC" by Cognis, oxyethylen
  • Waxy compounds which may be cited include paraffin, carnauba wax, beeswax and hydrogenated castor oil.
  • Organic solvents which may be cited are lower alcohols and polyols. They may be selected from glycols and glycol ethers such as ethylene glycol, propylene glycol, butylene glycol, dipropylene glycol or diethylene glycol.
  • Hydrophilic thickening agents which may be cited are carboxyvinyl polymers such as Carbopols (carbomers) and Pemulens (acrylate/Cio-C3o-alkylacrylate copolymer) ; polyacrylamides such as the cross-linked copolymers sold under the trade names Sepigel 305 (CTFA name: polyacrylamide/Ci 3 -Ci 4 isoparaffin/Laureth 7) or Simulgel 600 (CTFA name: acrylamide/sodium acryloyldimethyltaurate copolymer/isohexadecane/polysorbate 80) by Seppic; polymers and copolymers of 2-acrylamido 2-methylpropane sulphonic acid, which may be cross-linked and/or neutralized, such as poly (2-acrylamido 2-methylpropane sulphonic acid) sold by Hoechst under the trade name "Hostacerin AMPS" (CTFA name: ammonium polyacryldimethylta
  • Lipophilic thickening agents which may be cited are synthetic polymers such as poly (C10-C30) alkyl acrylate sold under the trade name "Doresco IPA 13-1" by Landec or modified clays such as hectorite and its derivatives, such as the products sold under the Bentone trade name.
  • compositions of the invention may be prepared using techniques which are well known to the skilled person.
  • they may be in the form of an emulsion, which may be simple or complex (O/W, W/O, 0/W/O or W/O/W) such as a cream, milk or cream gel; in the form of an aqueous gel; or in the form of a lotion or a stick.
  • They may optionally be packaged as an aerosol and be presented in the form of a foam or spray.
  • compositions of the invention are presented in the form of an oil-in-water or water-in- oil emulsion.
  • the emulsions generally contain at least one emulsifying agent selected from amphoteric, anionic, cationic or non-ionic emulsifying agents, used alone or as a mixture.
  • the emulsifying units are selected in an appropriate manner depending on the emulsion to be obtained (W/O or O/W) .
  • emulsifying surfactants which may be used to prepare W/O emulsions which may be cited are alkyl esters or ethers of sorbitan, glycerol or sugars; silicone surfactants such as dimethicone copolyols, such as a mixture of cyclomethicone and dimethicone copolyol sold under the trade name "DC 5225C” by Dow Corning, and alkyl-dimethicone copolyols such as Laurylmethicone copolyol sold under the trade name "Dow Corning 5200 Formulation Aid” by Dow Corning; cetyl dimethicone copolyol such as the product sold under the trade name Abil EM 9OR by Goldschmidt and the mixture of cetyl dimethicone copolyol, polyglycerol isostearate (4 moles) and hexyl laurate sold under the trade name ABIL WE 09 by Goldschmidt. It is also possible to be
  • Alkylated polyol esters which may be cited include polyethylene glycol esters such as PEG-30 Dipolyhydroxystearate, such as the product sold under the trade name Arlacel P135 by ICI.
  • esters of glycerol and/or sorbitan examples include polyglycerol isostearate, such as the product sold under the trade name Isolan GI 34 by Goldschmidt; sorbitan isostearate, such as the product sold under the trade name Arlacel 987 by ICI; sorbitan isostearate and glycerol, such as the product sold under the trade name Arlacel 986 by ICI, and mixtures thereof .
  • emulsifying agents for O/W emulsions examples include non-ionic emulsifying agents such as oxyalkylenated (more particularly polyoxyethylenated) esters of fatty acids and glycerol; oxyalkylenated esters of fatty acids and sorbitan; esters of oxyalkylenated (oxyethylenated and/or oxypropylenated) fatty acids such as the PEG-100 Stearate/Glyceryl Stearate mixture sold, for example, by ICI under the trade name Arlacel 165; ethers of oxyalkylenated (oxyethylenated and/or oxypropylenated) fatty alcohols; esters of sugars such as sucrose stearate; ethers of fatty alcohols and sugars, in particular alkylpolyglucosides (APG) such as decylglucoside or laurylglucoside sold, for example, by Hen
  • APG al
  • the mixture of alkylpolyglucoside as defined above with the corresponding fatty alcohol may be in the form of a self-emulsifying composition as described, for example, in document WO-A-92/06778.
  • the aqueous phase thereof may comprise a non-ionic vesicular dispersion prepared using known methods (Bangham, Standish and Watkins. J. MoI. Biol. 13, 238 (1965), FR-2 315 991 and FR-2 416 008) .
  • compositions of the invention have applications in a wide variety of treatments, in particular cosmetic, of the skin, lips and hair, including the scalp, especially for the protection and/or care of the skin, lips and/or hair, and or to make up the skin and/or the lips .
  • compositions of the invention as defined above for the production of products for the cosmetic treatment of the skin, lips, nails, hair, eyelashes, eyelids and/or scalp, in particular skin care products, sunscreens and makeup products.
  • the cosmetic compositions of the invention may, for example, be used as a skin care product and/or sunscreen for the face and/or the body with a liquid or semi-liquid consistency, such as lotions, milks, creams of varying oiliness, gels, gel-creams. They may optionally be packaged as an aerosol and be in the form of a foam or spray.
  • compositions of the invention may, for example, be used as a makeup product.
  • the compositions of the invention in the form of vaporizable fluid lotions in accordance with the invention are applied to the skin or hair in the form of fine particles by dint of pressurization devices.
  • the devices in accordance with the invention are well known to the skilled person and comprise non-aerosol pumps or atomizers, the aerosol receptacles comprising a propellant as well as aerosol pumps using compressed air as a propellant. These latter have been described in patents US-4 077 441 and US-4 850 517 (forming and integral part of the contents of the description) .
  • Compositions packaged as a aerosol in accordance with the invention generally contain conventional propellants such as hydrofluorinated compounds, dichlorodifluoromethane, difluoroethane, dimethylether, isobutane, n-butane, propane, trichlorofluoromethane .
  • propellants such as hydrofluorinated compounds, dichlorodifluoromethane, difluoroethane, dimethylether, isobutane, n-butane, propane, trichlorofluoromethane .
  • compositions of the invention may also include additional cosmetic and dermatological active ingredients .
  • the additional active ingredients may in particular be selected from moisturizing agents, desquamating agents, agents improving the barrier function, depigmenting agents, antioxidants, dermorelaxing agents, anti- glycation agents, agents stimulating the synthesis of dermal and/or epidermal macromolecules and/or preventing their degradation, agents stimulating the proliferation of fibroblasts or keratinocytes and/or differentiation of keratinocytes, agents promoting the maturation of the cornified envelope, NO-synthase inhibitors, peripheral benzodiazepine receptor (PBR) antagonists, agents increasing the activity of the sebaceous gland, agents stimulating cell energy metabolism, tightening agents, liporestructuring agents, slimming agents, agents promoting cutaneous micro-circulation, soothing agents and/or anti- irritants, sebo-regulators or anti-seborrheic agents, astringent agents, healing agents, antiinflammatories, and anti-acne agents.
  • moisturizing agents desquamating agents
  • the skilled person will preferably select at least one active ingredient selected from moisturizing agents, desquamating agents, agents improving the barrier function, depigmenting agents, antioxidants, dermorelaxing agents, anti- glycation agents, agents stimulating the synthesis of dermal and/or epidermal macromolecules and/or preventing their degradation, agents stimulating the proliferation or fibroblasts or keratinocytes and/or the differentiation of keratinocytes, agents promoting maturation of the cornified envelope, NO-synthesis inhibitors, peripheral benzodiazepine receptor (PBR) antagonists, agents increasing the activity of the sebaceous gland, agents stimulating cell energy metabolism, lipo-restructuring agents and agents promoting cutaneous micro-circulation for the contour of the eyes.
  • moisturizing agents desquamating agents, agents improving the barrier function
  • depigmenting agents antioxidants, dermorelaxing agents, anti- glycation agents
  • agents stimulating the synthesis of dermal and/or epidermal macromolecules and/or preventing their degradation agents stimulating
  • composition may also comprise at least one ingredient such as fillers with a soft-focus effect or agents promoting the natural skin colour, intended to supplement the biological effect of these active ingredients or provide an immediate visual anti-ageing effect .
  • ingredient such as fillers with a soft-focus effect or agents promoting the natural skin colour, intended to supplement the biological effect of these active ingredients or provide an immediate visual anti-ageing effect .
  • the skilled person will preferably select at least one active ingredient selected from desquamating agents, sebo-regulating or anti-seborrheic agents, and astringent agents.
  • the composition may also comprise at least one additional ingredient intended to supplement the biological effect of said active ingredients or to provide an immediate visual effect; in particular, mattifying agents, fillers with a soft-focus effect, fluorescent agents, agents promoting a natural rosy colour of the skin and abrasive or exfoliating fillers may be cited.
  • Moisturizing or humectant agents which may be cited include glycerol and its derivatives, urea and its derivatives in particular Hydrovance ® sold by National Starch, lactic acids, hyaluronic acid, AHAs, BHAs, sodium pidolate, xylitol, serine, sodium lactate, ectoine and its derivatives, chitosan and its derivatives, collagen, plankton, an imperata cylindra extract sold under the trade name Moist 24 ® by Sederma, acrylic acid homopolymers such as Lipidure-HM ® from NOF Corporation, beta-glucan and in particular sodium carboxymethyl beta-glucan from Mibelle-AG-Biochemistry; a mixture of passiflora, apricot, corn and rice oils sold by Nestle under the trade name NutraLipids ® ; a C- glycoside derivative such as those described in application WO-02/051828 and in particular C- ⁇ -D-xylopy
  • a hydrating agent selected from urea and its derivatives, in particular Hydrovance ® sold by National Starch, hyaluronic acid, AHAs, BHAs, acrylic acid homopolymers such as Lipidure- HM ® from NOF Corporation, beta-glucan and in particular sodium carboxymethyl beta-glucan from Mibelle-AG- Biochemistry; a mixture of passiflora, apricot, corn and rice oils sold by Nestle under the trade name NutraLipids ® ; a C-glycoside derivative such as those described in application WO-02/051828 and in particular C- ⁇ -D-xylopyranoside-2-hydroxy-propane in the form of a 30% by weight of active substance solution in a water/propylene glycol mixture (60/40% by weight) such as the product produced by CHIMEX under the trade name "MEXORYL SBB ® "; a musk rose oil sold by Nestle; an extract from the micro
  • treating agent means any compound which is capable of acting:
  • BHA ⁇ -hydroxyacids
  • AHA ⁇ - hydroxyacids
  • glycolic, citric, lactic, tartaric, malic or mandelic acids 8-hexadecene-l, 16- dicarboxylic acid or 9-octadecene dioic acid
  • urea and its derivatives gentisic acid and its derivatives
  • oligofucoses cinnamic acid; Saphora japonica extract; resveratrol and certain jasmonic acid derivatives; or on the enzymes involved in desquamation or the degradation of corneodesmosomes, glycosidases, stratum corneum chymotryptic enzyme (SCCE) or other proteases (trypsin, chymotrypsin-like) .
  • Aminosulphonic compounds may be cited, in particular 4- (2-
  • procysteine and its derivatives; alpha amino acid derivatives of the glycine type (such as those described in EP-O 852 949, as well as sodium methyl glycine diacetate sold by BASF under the trade name TRILON M) ; honey; sugar derivatives such as O-octanoyl- 6-D-maltose and N-acetyl glucosamine.
  • desquamating agents which may be used in the composition of the invention which may be cited are: oligofructoses, EDTA and its derivatives, laminaria extracts, o-linoleyl-6D-glucose, (3-hydroxy- 2-pentylcyclopentyl) acetic acid, glycerol trilactate, O-octanyl-6' -D-maltose, S-carboxymethyl cysteine, silicon-containing salicylate derivatives, such as those described in EP-O 796 861, oligofucases such as those described in patent EP-O 218 200, 5-acyl salicylic acid salts, active ingredients having effects on transglutaminase, such as those in patent EP- 0 899 330; ficus opuntia indica flower extract such as Exfolactive ® from Silab; - 8-hexadecene 1, 16-dicarboxylic acid; esters of glucose and vitamin F; and mixtures
  • Preferred desquamating agents which may be cited are beta-hydroxyacids, such as n-octanoyl 5-salicylic acid; urea; glycolic, citric, lactic, tartaric, malic or mandelic acid; 4- (2-hydroxyethyl) piperazine-1- propanesulphonic acid (HEPES); Saphora japonica extract; honey; N-acetyl glucosamine; sodium methyl glycine diacetate, and mixtures thereof.
  • beta-hydroxyacids such as n-octanoyl 5-salicylic acid; urea; glycolic, citric, lactic, tartaric, malic or mandelic acid; 4- (2-hydroxyethyl) piperazine-1- propanesulphonic acid (HEPES); Saphora japonica extract; honey; N-acetyl glucosamine; sodium methyl glycine diacetate, and mixtures thereof.
  • compositions of the invention will use a desquamating agent selected from n-octanoyl 5- salicylic acid; urea; 4- (2-hydroxyethyl) piperazine-1- propanesulphonic acid (HEPES); Saphora japonica extract; honey; N-acetyl glucosamine; sodium methyl glycine diacetate, and mixtures thereof.
  • a desquamating agent selected from n-octanoyl 5- salicylic acid; urea; 4- (2-hydroxyethyl) piperazine-1- propanesulphonic acid (HEPES); Saphora japonica extract; honey; N-acetyl glucosamine; sodium methyl glycine diacetate, and mixtures thereof.
  • arginine serine
  • a Thermus thermophilus extract such as Venuceane ® from Sederma
  • a wild yam rhizome extract such as Actigen Y ® from Active Organics
  • plankton extracts such as omega plancton ® from Secma
  • yeast extracts such as Relipidium ® from Coletica
  • a chestnut extract such as Recoverine ® from Silab
  • a cedar bud extract such as Gatuline Zen ® from Gattefosse
  • sphingosines such as salicyloyl sphingosine sold under the trade name "Phytosphingosine ® SLC" by Degussa
  • a mixture of xylitol, xylityl polyglycoside and xylitan such as Aquaxyl ® from Seppic
  • solanacea extracts such as Lipidessence ® from Coletica; uns
  • ceramides or derivatives in particular type 2 ceramides (such as N- oleoyldihydrosphingosine) , type 3 ceramides (such as stearoyl-4-hydroxysphinganine, INCI name) and type 5 ceramides (such as N-2- hydroxypalmitoyldihydrosphingosine, with INCI name: hydroxypalmytoyl sphinganine) , compounds based on sphingoids, glycosphingolipids, phospholipids, cholesterol and its derivatives, phytosterols, essential fatty acids, diacylglycerol, 4-chromanone and chromone derivatives, vaseline, lanolin, shea butters, cocoa butter, lanolin, and PCA salts.
  • type 2 ceramides such as N- oleoyldihydrosphingosine
  • type 3 ceramides such as stearoyl-4-hydroxysphinganine, INCI name
  • Preferred agents having a restructuring effect on the cutaneous barrier which may be cited are a Thermus thermophilus extract, a wild yam rhizome extract
  • serine, aginine or a mixture thereof is used.
  • Depigmenting agents which may in particular be cited include vitamin C and its derivatives, in particular vitamin CG, CP and 3-0 ethyl vitamin C, alpha and beta arbutine, ferulic acid, lucinol and its derivatives, kojic acid, resorcinol and its derivatives, tranexamic acid and its derivatives, gentisic acid, homogentisate, methyl gentisate or homogentisate, dioic acid, D calcium pantheteine sulphonate, lipoic acid, ellagic acid, vitamin B3, linoleic acid and its derivatives, ceramides and their homologues, derivatives for plants such as camomile, bearberry, the aloe family (vera, ferox, bardensis) , mulberry, skullcap; Kiwi fruit water (Actinidia chinensis) sold by Gattefosse, a Paeonia suffructicosa root extract such as that sold by Ichimaru Ph
  • Preferred depigmenting agents which are used are vitamin C and its derivatives and in particular vitamin CG, CP and 3-0 ethyl vitamin C, alpha and beta arbutine, ferulic acid, kojic acid, resorcinol and its derivatives, D calcium pantheteine sulphonate, lipoic acid, ellagic acid, vitamin B3, Kiwi fruit water
  • tocopherol and its esters in particular tocopherol acetate; ascorbic acid and its derivatives, in particular ascorbyl magnesium phosphate and ascorbyl glucoside; ferulic acid; serine; ellagic acid, phloretin, polyphenols, tannins, tannic acid, epoigallocathechins and natural extracts containing them, anthocyans, rosemary extracts, olive leaf extracts such as those from Silab, green tea extracts, resveratrol and its derivatives, ergothineine, N- acetylcysteine, an extract from the brown algae pelvetia canaliculata such as Pelvetiane ® from Secma, chlorogenic acid, biotin, chelating agents such as BHT, BHA, N, N' -bis (3, 4 , 5-trimethoxybenzyl) ethylenediamine and its salts; idebenone, plant
  • anti-ageing agents which may be cited are : DHEA and its derivatives, boswellic acid, rosemary extracts, carotenoids (B carotene, zeaxanthine, luteine) , cysteic acid, copper derivatives, jasmonic acid.
  • Preferred antioxidants which are used are: ferulic acid; serine; phloretin, a pomegranate extract, biotin, chelating agents such as BHT, BHA, N, N' -bis (3, 4, 5- trimethoxybenzyl) ethylenediamine and its salts, caprylyl glycol, phloretine, TotarolTM, a jasmine extract such as that sold by SILAB under the trade name Helisun ® ; hesperitine laurate such as Flavagrum PEG ® from Engelhard Lyon; and a Paeonia suffructicosa root extract such as that sold by Ichimaru Pharcos under the trade name Botanpi Liquid B ® .
  • chelating agents such as BHT, BHA, N, N' -bis (3, 4, 5- trimethoxybenzyl) ethylenediamine and its salts, caprylyl glycol, phloretine, TotarolTM,
  • Examples which may be cited are: manganese gluconate and other salts, adenosine, alverine citrate and its salts, glycine, an Iris pallida extract, a hexapeptide
  • sapogenins which may be cited are those described in patent application WO-02/47650, in particular Wild yam, diosgenin extracted in particular from Dioscorea opposita or any extract comprising one or more sapogenins either naturally or after treatment
  • DMAE dimethyl MEA
  • criste marine extracts ciste de Montpellier, curry plant, aniseed, Para cress, Acmella Oleracea extract such as Gatuline ® from Gattefosse.
  • Preferred dermorelaxants which may be cited are adenosine, manganese gluconate, wild yam, criste marine, glycine and alverine.
  • anti-glycation means a compound preventing and/or reducing the glycation of skin proteins, in particular proteins of the dermis such as collagen.
  • Anti-glycation agents which may in particular be cited are plant extracts from the Ericaceae family such as an extract from blueberries (Vaccinium angusfifollium, Vaccinium myrtillus) , for example that sold under the trade name "BLUEBERRY HERBASOL EXTRACT PG" by COSMETOCHEM, ergothioneine and its derivatives, hydroxystilbenes and their derivatives, such as resveratrol and 3, 3' , 5, 5' -tetrahydroxystilbene (these anti-glycation agents are described in applications FR- 2 802 425, FR-2 810 548, FR-2 796 278 and FR-2 802 420, respectively) , dihydroxystilbenes and their derivatives, arginines and lysine polypeptides such as that sold under the trade name "AMADORINE ® " by SOLABIA, carcinine hydrochloride (sold by Exsymol under the trade name "ALISTIN ®
  • Preferred anti-glycation agents which may be cited are blueberry extracts (Vaccinium myrtillus) and black tea extract . 8. Agents stimulating the synthesis of dermal and/or epidermal macromolecules and/or preventing their degradation :
  • Active ingredients which stimulate dermis macromolecules or prevent their degradation which may be cited are those which act:
  • Medicago sativa (alfafa) extract such as that sold by SILBA under the trade name Vitanol ® ; a peptidic hazelnut extract such as that sold by Solabia under the trade name Nuteline C ® ; and arginine;
  • MMP metalloproteinases
  • retinoids and its derivatives such as Vitanol ® from Silab, an aphanizomenon flos-aquae (cyanophycea) extract sold under the trade name Lanablue ® by Atrium
  • elastin and fibrillin molecules belonging to the elastin family
  • molecules belonging to the elastin family such as: retinol and its derivatives, in particular retinol palmitate; the Saccharomyces Cerivisiae extract sold by LSN under the trade name Cytovitin ® ; and the Macrocystis pyrifera algae extract sold by SECMA under the trade name Kelpadelie ® ; or a peptidic hazelnut extract such as that sold by Solabia under the trade name Nuteline C ® ;
  • elastin such as the peptide extract of Pisum sativum seeds sold by LSN under the trade name Parelastyl ® ; heparinoids; and the N-acylaminoamide compounds described in application WO- 01/94381, such as ⁇ 2- [acetyl- (3-trifluoromethyl- phenyl) -amino] -3-methyl-butyrylamino ⁇ acetic acid, also denoted N-[N-acetyl, N '- (3-trifluoromethyl) phenyl valyl ] glycine or N-acetyl-N- [3-
  • glycosaminoglycans such as the product from fermenting milk with Lactobacillus vulgaris, sold by BROOKS under the trade name Biomin yogurt ® ; the brown algae Padina pavonica extract sold by ALBAN MULLER under the trade name HSP3 ® ; the Saccharomyces cerevisiae extract available from SILAB under the trade name Firmalift ® or from LSN under the trade name Cytovitin ® ; a Laminaria ochroleuca extract such as Lamina ⁇ ne ® from Secma; Mamaku essence from Lucas Meyer, or a cress extract (Odraline ® from Silab) ;
  • fibronectin such as the Salina zooplankton extract sold by SEPORGA under the trade name GP4G ® ; the yeast extract available in particular from ALBAN MULLER under the trade name Drieline ® ; and the palmitoyl pentapeptide sold by SEDERMA under the trade name Matrixil ® .
  • Active ingredients stimulating epidermal macromolecules such as fillagrin and keratins which may be cited are the lupin extract sold by SILAB under the trade name Structurine ® ; Fagus sylvatica beech bud extract sold by GATTEFOSSE under the trade name Gatuline ® RC; and the Salina zooplankton extract sold by SEPORGA under the trade name GP4G ® ; copper Tripeptide from PROCYTE; and a Voandzeia substerranea extract such as that sold by Laboratoires Serobi unanimouss under the trade name Filladyn LS 9397 ® .
  • an active ingredient stimulating the synthesis of dermal and/or epidermal macromolecules and/or preventing their degradation is selected from agents stimulating the synthesis of glycosaminoglycans, agents inhibiting the degradation of elastin, agents stimulating the synthesis of fibronectin, agents stimulating the synthesis of epidermal macromolecules, and mixtures thereof.
  • an active ingredient stimulating the synthesis of glycosaminoglycans is used which is selected from a brown algae Padina pavonica extract, a Saccharomyces cerevisiae extract, a Laminaria ochroleuca extract, Mamaku essence, a cress extract and mixtures thereof.
  • Preferred active ingredients stimulating the synthesis of dermal and/or epidermal macromolecules and/or impeding their degradation which may be cited are: - synthesized peptides such as iamin, biopeptide CL or palmitoyloligopeptide sold by SEDERMA; peptides extracted from plants, such as the soya hydrolysate sold by COLETICA under the trade name Phytokine ® ; rice peptides such as Nutripeptide ® from SILAB, methylsilanol mannuronate such as Algisium C ® sold by Exsymol; folic acid; a Medicago sativa (alfafa) extract such as that sold by SILBA under the trade name Vitanol ® ; a peptidic hazelnut extract such as that sold by Solabia under the trade name Nuteline C ® ; arginine; an aphanizomenon flos-aquae (cyanophycea) extract sold under the trade name Lan
  • agents stimulating the proliferation of fibroblasts which may be used in the composition of the invention may, for example, be selected from plant proteins or polypeptides, in particular extracted from soya (for example a soya extract sold by LSN under the trade name Eleseryl SH-VEG 8 ® or sold by SILAB under the trade name Raffermine ® ) ; a hydrolyzed soya protein extract such as RIDULISSE ® de SILAB; and plant hormones such as giberrellins and cytokinins; and a peptidic hazelnut extract such as that sold by Solabia under the trade name Nuteline C ® .
  • soya for example a soya extract sold by LSN under the trade name Eleseryl SH-VEG 8 ® or sold by SILAB under the trade name Raffermine ®
  • soya protein extract such as RIDULISSE ® de SILAB
  • plant hormones such as giberrellins and cytokinins
  • a peptidic hazelnut extract such
  • an agent promoting the proliferation and/or differentiation of keratinocytes is used.
  • Agents stimulating the proliferation of keratinocytes which may be used in the composition of the invention include adenosine; phloroglucinol, hydrangea macrophylla leaf extract such as Amacha liquid E ® from
  • Ichimaru Pharcos a yeast extract such as Stimoderm ® from CLR; Larrea divaricata extract such as Capislow ® from Sederma, mixtures of extracts from papaya, olive leaves and lemon such as Xyleine ® from Vincience, hydrangea macrophylla leaf extract such as Amacha liquid E ® from Ichimaru Pharcos, retinol and its esters including retinyl palmitate, phloroglucinol, walnut shell extracts sold by Gattefosse and solanum tuberosum extracts such as Dermolectine ® sold by Sederma.
  • Larrea divaricata extract such as Capislow ® from Sederma, mixtures of extracts from papaya, olive leaves and lemon such as Xyleine ® from Vincience, hydrangea macrophylla leaf extract such as Amacha liquid E ® from Ichimaru Pharcos, retinol and its esters including retinyl palm
  • agents stimulating the differentiation of keratinocytes include, for example, minerals such as calcium; criste marine, a peptidic lupin extract such as that sold by SILAB under the trade name Structurine ® ; sodium beta-sitosteryl sulphate such as that sold by SEPORGA under the trade name Phytocohesine ® ; and a hydrosoluble corn extract such as that sold by SOLABIA under the trade name Phytovityl ® ; a Voandzeia substerranea extract such as that sold by Laboratoires Serobi unanimouss under the trade name Filladyn LS 9397 ® ; and lignanes such as secoisolariciresinol, retinol and its esters including retinyl palmitate.
  • minerals such as calcium
  • criste marine a peptidic lupin extract
  • sodium beta-sitosteryl sulphate such as that sold by SEPORGA under the trade name Phytoco
  • oestrogens such as oestradiol and homologues
  • cytokines cytokines
  • Preferred active ingredients stimulating the proliferation of fibroblasts or keratinocytes and/or the differentiation of keratinocytes which may be cited are plant proteins or polypeptides, extracted primarily from soya (for example a soya extract sold by LSN under the trade name Eleseryl SH-VEG 8 ® or sold by SILAB under the trade name Raffermine ® ) ; a hydrolyzed soya protein extract such as RIDULISSE ® from SILAB; a peptidic hazelnut extract such as that sold by Solabia under the trade name Nuteline C ® ; adenosine; phloroglucinol, a yeast extract such as Stimoderm ® from CLR; a peptidic lupin extract such as that sold by SILAB under the trade name Structurine ® ; a hydrosoluble corn extract such as that sold by SOLABIA under the trade name Phytovityl ® ; a peptidic Voandzeia substerrane
  • agents which are involved in maturation of the cornified envelope which changes with age and induces a reduction in transglutaminase activity.
  • agents which may be cited are urea and its derivatives, in particular Hydrovance ® from National Starch and other active ingredients mentioned in L' OREAL ⁇ s application FR-2 877 220 (not published) .
  • the agent having an NO synthase inhibiting activity may be selected from PCOs (procyanidolic oligomers) ; plant extracts from the species Vitis vinifera, in particular those sold by Euromed under the trade name Leucocyanidines de raisins extra, or by Indena under the trade name Leucoselect ® , or finally by Hansen under the trade name Extrait de marc de raisin; plant extracts from the species Olea europaea, preferably obtained from olive leaves and in particular sold by VINYALS in the dry form, or by Biologia & Technologia under the trade name Eurol ® BT; extracts from the species Gingko biloba, preferably a dried aqueous extract from this plant sold by Beaufour under the trade name Ginkgo biloba 1% standard, and mixtures thereof .
  • PCOs procyanidolic oligomers
  • PBR Peripheral benzodiazepine receptor
  • Agents promoting sebaceous gland activity examples which may be cited are methyl dehydroj asmonate, hecogenin, hedione, o-linoleyl-6D- glucose and mixtures thereof.
  • the active ingredient stimulating cell energy metabolism may, for example, be selected from biotin, an extract from Saccharomyces cerevisiae such as Phosphovital ® from Sederma, a mixture of sodium, manganese, zinc and magnesium salts of pyrrolidone carboxylic acid such as Physiogenyl ® from Solabia, a mixture of zinc, copper and magnesium gluconate such as Sepitonic M3 ® from Seppic and mixtures thereof; and a beta-glucan derived from Saccharomyces cerevisiae, such as that sold by Mibelle AG Biochemistry.
  • tightening agent means compounds which may have a tightening effect, i.e. which may tense the skin.
  • the term "tightening agent" as used in the context of the invention means any compounds which are soluble in or dispersible in water at a temperature of
  • the maximum concentration at which a medium which is homogeneous in appearance is determined to ⁇ 10% and preferably to ⁇ 5%.
  • the term "medium with a homogeneous appearance” means a medium which does not have any aggregates which are visible to the naked eye.
  • the tightening agent is slowly added to water with stirring using a deflocculator at a temperature of 25°C to 50 0 C, then the mixture is stirred for one hour. After 24 hours, observations are made to ascertain whether the mixture which has been prepared has a homogeneous appearance (absence of aggregates which are visible to the naked eye) .
  • the tightening effect may be characterized by an in-vitro shrinkage test.
  • a mixture is prepared as described above which is a homogeneous mixture of the tightening agent in water at a concentration of 7% by weight or at the maximum concentration defined above.
  • the elastomer specimen After drying for 3 h at 22 ⁇ 3°C and 40+10% relative humidity HR, the elastomer specimen has a retracted width, denoted L3h, due to the tension exerted by the deposited tightening agent.
  • the tightening agent may be selected from: plant or animal proteins and their hydrolysates; polysaccharides of natural origin; mixed silicates; colloidal particles of inorganic fillers; synthetic polymers; and mixtures thereof.
  • proteins and hydrolysates of plant proteins in particular of corn, rye, wheat, buckwheat, sesame, spelt, pea, broad bean, lentil, soya and lupin
  • polysaccharides of natural origin especially (a) polyholosides, for example (i) in the form of starch in particular derived from rice, corn, potato, cassava, pea, wheat, oats, etc; or (ii) in the form of carragheenans, alginates, agars, gellanes, cellulosic polymers and pectins, advantageously in an aqueous dispersion of gel microparticles, and (b) latexes constituted by shellac resin, sandarac gum, dammars, elemi, copals, cellulosic derivatives and mixtures thereof; (c) mixed silicates, especially phyllosilicates and in particular laponites;
  • colloidal inorganic filler particles with a number average diameter in the range 0.1 to 100 nm, preferably in the range 3 to 30 nm, and selected, for example, from: silica, silica-alumina composites, cerium oxide, zirconium oxide, alumina, calcium carbonate, barium sulphate, calcium sulphate, zinc oxide and titanium dioxide.
  • colloidal silica-alumina colloidal particles which may be used in the compositions of the invention which may be cited are those sold by Grace with the names Ludox AM, Ludox AM-X 6021, Ludox HSA and Ludox TMA.
  • synthetic polymers such as polyurethane latexes or acrylic-silicone latexes, in particular those described in patent application EP-A-I 038 519, such as a propylthio (polymethyl acrylate) , propylthio (polymethyl methacrylate) or propylthio (polymethacrylic acid) grafted polydimethylsiloxane, or a propylthio (polyisobutyl methacrylate) or propylthio (polymethacrylic acid) grafted polydimethylsiloxane.
  • grafted silicone polymers are in particular sold by 3M under the trade names VS 80, VS 70 or LO21 .
  • the tightening agent is present in the composition in a quantity which is effective to obtain the desired biological effect in accordance with the invention.
  • the tightening agent may be included in the composition of the invention in an amount of 0.01% to 30% by weight of active substance, preferably 1% to 30% by weight of active substance, with respect to the total composition weight.
  • active substance is intended to exclude the medium in which the tightening agent is optionally dissolved or in dispersion in its commercially available form, for example in the case of dispersions of colloidal particles.
  • agents which promote the expression of mechanoreceptors such as agents promoting the expression of integrins
  • a rye seed extract may be cited, such as that sold SILAB under the trade name Coheliss ⁇ .
  • liporestructuring agents means agents which are capable of stimulating lipogenesis and promoting adipocyte differentiation, thereby avoiding or slowing the melting of fats contained in the skin support tissues, also termed “melting of the skin lipostructure” .
  • skin lipostructure means the network of lipid cells which forms volumes on which the skin of the face rests and to which it moulds.
  • These agents are intended to reduce the loss of skin density and/or melting of the lipostructure of the skin, in particular at the cheeks and the contour of the eye, and/or to avoid sinking and/or hollowing of the curves of the face, a loss of consistency of the skin and/or its support, in particular at the cheeks and the contour of the eye, and/or to improve the supports which subtend the skin of the face and/or the neck, in particular at the cheeks, the outline of the face and the contour of the eye, and/or to improve the density, resilience and support of the skin, in particular at the cheeks, the outline of the face and the contour of the eye, and/or to remodel the lines of the face, in particular the outline of the face.
  • liporestructuring agents examples include black tea extract, such as fermented black tea extract sold by Sederma under the trade name Kombuchka ® , and an extract of Artemesia abrotanum, such as that sold by Silab under the trade name Pulpactyl ® .
  • Slimming agents which may in particular be cited are caffeine, theophyllin and its derivatives, theobromine, sericosine, asiatic acid, acefylline, aminophylline, chloroethyltheophylline, diprofylline, diniprophylline, etamiphylline and its derivatives, etofylline, proxyphylline; tea, coffee, guarana, mate, cola (Cola Nitida) extracts and in particular dry guarana fruit extract (Paulina sorbilis) containing 8% to 10% of caffeine; extracts of common ivy (Hedera helix) , arnica (Arnica montana L) , rosemary
  • the active ingredient acting on cutaneous microcirculation may be used to avoid fading of the skin and/or to improve the appearance of the eye contour, and in particular to reduce blemishes. It may, for example, be selected from a maritime pine bark extract such as Pycnogenol ® from Bio prises, manganese gluconate (Givobio GMn ® from Seppic) , an extract of Ammi visnaga such as Visnadine from Indena, lupin extract (Eclaline ® from Silab) , hydrolyzed wheat protein/ palmitic acid coupled with palmitic acid such as Epaline 100 from Laboratoires Carilene, Seville orange flower extract (Remoduline ® from Silab) , vitamin P and its derivatives such as sodium methyl-4 esculetol mono-ethanoate sold under the trade name Permethol ® by Sephytal, ruscus extracts, horse chestnut extracts, ivy extract, ginseng extract and melilot extract, caffeine,
  • Preferred agents promoting cutaneous microcirculation which may be cited are, caffeine, Seville orange flower extract, black tea extract, rutine salts, and corallina officinalis algae extract.
  • smoothing agent means a compound which can reduce the sensation of tingling, itching or pulling of the skin.
  • Examples of soothing agents which may be used in the composition of the invention which may be cited are: procyannidolic oligomers, vitamins E, C, B5, B3, caffeine and its derivatives, pentacyclic triterpenes and extracts from plants containing them, ⁇ - glycyrrhetinic acid and its salts or derivatives
  • Preferred soothing agents used in accordance with the invention are: ⁇ -glycyrrhetinic acid and its salts or derivatives (stearyl glycyrrhetate, 3-stearoyloxy glycyrrhetic acid, glycyrrhetinic acid monoglucuronide) and plants containing them (for example: Glycyrrhiza glabra); ursolic acid and its salts; Centella asiatica extracts, Canola oil, bisabolol; camomile extracts, allantoin; a mixture of water lily flower extract and palmitoylproline such as that sold under the trade name "Seppicalm VG ® " by Seppic; aloe vera, rose water, mint extract, in particular from mint leaves such as Calmiskin ® from Silab, filamentous bacteria such as Vitreoscilla filiformis as described in patent EP-O 761 204 and sold by Chimex under the trade name Mexo
  • sibo-regulating or anti-seborrheic agent means agents which are capable of regulating the activity of sebaceous glands.
  • zinc salts such as zinc gluconate, zinc pyrrolidone carboxylate (or zinc pidolate) , zinc lactate, zinc aspartate, zinc carboxylate, zinc salicylate, zinc cysteate; copper derivatives, and in particular copper pidolate, such as Cuivridone ® from Solabia; plant extracts from the species Arnica montana, Cinchona succirubra, Eugenia caryophyllata, Humulus lupulus, Hypericum perforatum, Mentha piperita,
  • Rosmarinus officinalis Salvia oficinalis and Thymus vulgaris, all sold, for example, by MARUZEN; - European meadowsweet extracts (spiraea ulamaria) such as that sold under the trade name Sebonormine ® by Silab; laminaria saccharina algae extracts, such as that sold under the trade name Phlorogine ® by Biotechmarine; mixtures of pimpernel root (sanguisorba officinalis/poterium officinale) , ginger rhizomes
  • Linumine ® sold under the trade name Linumine ® by Lucas Meyer;
  • Phellodendron extracts such as those sold under the trade name Phellodendron extract BG by Maruzen or Oubaku liquid B by Ichimaru Pharcos;
  • laminaria algae extracts such as that sold under the trade name Laminarghane ® by Biotechmarine
  • oligosaccharides from the algae laminaria digitata such as that sold under the trade name Phycosaccharide AC by Codif
  • sebacic acid in particular sold in the form of a sodium polyacrylate gel under the trade name Sebosoft ® by Sederma; glucomannans extracted from konjac tubers and modified by alkylsulphonate chains such as that sold under the trade name Biopol Beta by Arch Chemical;
  • 10-hydroxydecanoic acid and in particular mixtures of 10-hydroxydecanoic acid, sebacic acid and 1,10- decandiol such as that sold under the trade name Acnacidol ® BG by Vincience; and
  • anti-seborrheic agents which may be cited are :
  • zinc salts such as zinc gluconate, zinc pyrrolidone carboxylate (or zinc pidolate) , zinc lactate, zinc aspartate, zinc carboxylate, zinc salicylate, zinc cysteate;
  • 10-hydroxydecanoic acid and in particular mixtures of 10-hydroxydecanoic acid, sebacic acid and 1,10- decandiol such as that sold under the trade name Acnacidol ® BG by Vincience;
  • the anti-seborrheic agent is selected from: - zinc salts such as zinc gluconate, zinc pyrrolidone carboxylate (or zinc pidolate) , zinc lactate, zinc aspartate, zinc carboxylate, zinc salicylate, zinc cysteate; and preferably zinc pyrrolidone carboxylate (or zinc pidolate) or zinc salicylate;
  • the anti-seborrheic agent is, for example, present in an amount of 0.1% to 10% by weight, preferably 0.1% to 5% by weight, and preferably 0.5% to 3% by weight, with respect to the total composition weight.
  • astringent agents as used in the invention means agents which can combat the dilation of sebaceous follicles .
  • Astringent agents which may be used in the composition of the invention which may be cited are extracts from mushroom pulp (polyporus officinalis) such as "Laricyl LS8865 ® " from Cognis, extracts from Terminalia catappa and sambucus nigra such as Phytofirm LS9120 ® from Cognis, nut gall extracts such as Tanlex VE ® from Ichimaru Pharcos, aluminium hydroxychloride, extracts of centella (for example Plantactiv centella from Cognis), dicetyl dimethyl ammonium chloride such as Varisoft 432 CG ® from Degussa, extracts of horse chestnut, extracts of mallow, Hammamelis extracts, sweet almond extracts, extracts from marsh mallows and from linseed such as Almondermin LS 3380 ® from Cognis, extracts of bardane, nettle extracts, birch extracts, horsetail extracts, camomile
  • Preferred astringent agents for use in the invention are extracts of Scutellaria, extracts of meadowsweet, extracts of European meadowsweet, extracts of gentian, extracts of bardane and mixtures thereof.
  • healing agents which may be cited are: allantoin, urea, certain amino acids such as hydroxyproline, arginine, serine, and also white lily extracts (such as Phytelene Lys 37EG 16295 from Indena) , a yeast extract such as the LS LO/7225B healing agent from Laboratoires Seriobiiquess) , tamanu oil, saccharomyces cerevisiae extract such as Biodynes ® TRF ® from Arch Chemical, oat extracts, chitosan and derivatives such as chitosan glutamate, carrot extracts, artemia extract such as GP4G ® from Vincience, sodium acexamate, lavender extracts, propolis extracts, ximeninic acid and its salts, rosa rugosa oil, extracts from marigold such as Marigold Ami ® Liposoluble from Alban Muller, extracts from horsetail, lemon peel extracts such as Herbasol ® lemon from Co
  • Particular anti-inflammatories which may be used in accordance with the invention which may be cited are cortisone, hydrocortisone, indomethacine, betamethasone, azealic acid, acetominophene, diclofenac, clobetasol propionate, folic acid; an Eperua falcata bark extract such as that sold by COGNIS under the trade name Eperuline ® ; a Paeonia suffructicosa root extract such as that sold by Ichimaru Pharcos under the trade name Botanpi Liquid B ® ; and mixtures thereof.
  • Preferred anti-inflammatories which may be cited are azelaic acid, folic acid, Eperua falcata bark extract such as that sold by COGNIS under the trade name Eperuline ® ; a Paeonia suffructicosa root extract such as that sold by Ichimaru Pharcos under the trade name Botanpi Liquid B ® ; and mixtures thereof.
  • the composition may also comprise at least one anti-acne agent.
  • anti-acne agent means any active ingredient which has effects on the specific flora of oily skin, such as Propionibacterium acnes (P acnes), for example.
  • Anti-bactericidal agents which may in particular be cited are as follows: the active ingredients and preservatives with an anti-microbial activity cited in application DE-103 24 567, hereby incorporated into the present invention by reference; - asiatic acid; the monoethanolamine salt of l-hydroxy-4-methyl 6- trimethylpentyl 2-pyridone (INCI name: piroctone olamine) , in particular that sold under the trade name Octopirox ® by Clariant; - citronellic acid, perillic acid (or 4- isopropenylcyclohex-1-enecarboxylic acid) ; glycerol 2-ethyl hexyl ether (INCI name: ethylhexylglycerine) , for example that sold under the trade name Sensiva SC 50 ® by Shulke & Mayr; - glyceryl caprylate/caprate, for example that sold under the trade name Capmul MCM ® by ABITEC; calcium
  • Angus malachite powder, zinc oxide such as Zincare ® from Elementis GmbH, octadecenedioic acid such as
  • Arlatone dioic DCA ® from Uniqema; ellagic acid; 2,4,4'- trichloro-2' -hydroxy diphenyl ether (or triclosan) , 1-
  • surfactants with an antimicrobial effect such as sodium cocoamphoacetate or disodium diacetate such as Miranol C2M CONC NP, betaines such as cocoyl betaine Genagen KB from Clariant, sodium lauryl ether sulphate such as Emal 270 D from Kao, decyl glucoside such as Plantacare 2000 UP, branched C12-C13 dialcohol malates such as Cosmacol EMI, propylene glycol monoesters such as propylene glycol monolaurate, monocaprylate, monocaprate, lauryl dimethylamine betaine such as Empigen BB/LS as well as quaternary polyammoniums such as Quaternium-24 or Bardac 2050 from Lonza and those described in FR 0 108 283, and mixtures thereof.
  • betaines such as cocoyl betaine Genagen KB from Clariant
  • sodium lauryl ether sulphate such as Emal 270 D from Kao
  • Preferred antimicrobial agents which may be used in the compositions of the invention are agents selected from octoglycerine and octoxyglycerine, 10-hydroxy-2- decanoic acid, and mixtures thereof.
  • anti-acne agents may be added to the anti-acne agents cited above.
  • Particular agents preventing and/or reducing the adhesion of micro-organisms which may be cited are: phytanetriol and its derivatives as described in patent application EP-I 529 523, vegetable oils such as wheat germ oil, calendula oil, castor oil, olive oil, avocado oil, sweet almond oil, peanut oil, jojoba oil, sesame seed oil, apricot kernel oil, sunflower seed oil, or macadamia nut oil described in patent EP-I 133 979, or certain surfactants such as disodium cocoamphodiacetate, oxyethylenated (7 OE) glyceryl cocoate, hexadecenylsuccinate 18, octoxyglyceryl palmitate, octoxyglyceryl behenate, dioctyl adipate, PPG-15 stearyl ether, branched Ci 2 -Ci 3 di-alcohol tartrate described in patent EP-I 129 694, and mixtures thereof .
  • pentylene glycol such as Celvol 540 PV alcohol ® from Celanese Chemical
  • rapeseed oil such as Akorex L ® from Karlshamns
  • fructose derivatives and mixtures thereof may be cited : pentylene glycol, nylon-66 (fibres of polyamide 66) , castor oil, polyvinyl alcohol such as Celvol 540 PV alcohol ® from Celanese Chemical, rapeseed oil such as Akorex L ® from Karlshamns, and fructose derivatives and mixtures thereof.
  • the active ingredient countering acne may be present in an amount of 0.01% to 10% by weight, preferably 0.05% to 5% by weight with respect to the total composition weight .
  • Lipophilic active ingredients which may be used in the kit or in at least one of the compositions of the invention which may in particular be cited are D- ⁇ - tocopherol, DL- ⁇ -tocopherol, D- ⁇ -tocopherol acetate, DL- ⁇ -tocopherol acetate, ascorbyl palmitate, vitamin F glycerides, the vitamin D group, vitamin D2, vitamin D3, retinol, retinol esters, retinol palmitate, retinol propionate, carotenes including ⁇ carotene, D- panthenol, farnesol, farnesyl acetate, salicylic acid and its derivatives such as n-octanoyl-5 salicylic acid, ⁇ -hydroxyacid alkyl esters such as citric acid, lactic acid, glycolic acid, asiatic acid, madecassic acid, asiaticoside, centella asiatica total extract, ⁇ - glycyrrhetin
  • the cosmetic and/or dermatological agents are present in the kit or one of the compositions of the invention in an amount of 0.001% to 20% by weight with respect to the total composition weight, preferably in the range 0.01% to 10%, more preferably in the range 0.5% to 5% and still more preferably in the range 0.1% to 1% by weight with respect to the total composition weight.
  • the amounts of cosmetic and/or dermatological agents may be from 1% to 50% by weight with respect to the total composition weight, preferably 1% to 30% by weight with respect to the total composition weight.
  • Peeling is a well known method for improving the appearance and/or texture of the skin and/or scalp, in particular of improving radiance and homogeneity of the skin and/or of reducing visible and/or tactile irregularities in the skin, and in particular of improving the surface appearance of the skin surface, to reduce actinic lentigo, acne or chicken pox scars and to prevent, reduce or combat the signs of skin ageing, and in particular to smooth out irregularities in the texture of the skin such as wrinkles and fine lines.
  • these additional ingredients may provide an immediate visual effect which will be relayed by the biological effect of the active ingredients cited above. They may also, via a mechanical action (for example: abrasive fillers) amplify the effect of the biological agents cited above.
  • composition of the invention may also comprise at least one agent selected from mattifying agents, fillers with a soft-focus effect, fluorescent agents, agents promoting the natural pink colour of the skin, abrasive fillers or exfoliating agents and mixtures thereof.
  • mattifying agent means agents which are intended to render the skin visibly more matt, and less shiny.
  • the mattifying effect of the agent and/or the composition containing it may in particular be evaluated using a gonioreflectometer, by measuring the ratio R between the specular reflection and the diffuse reflection.
  • a value for R of 2 or less is generally considered to be a mattifying effect.
  • the mattifying agent may in particular be selected from a rice starch or corn starch, kaolinite, talc, a pumpkin seed extract, cellulose microbeads, plant fibres, synthetic fibres, in particular polyamides, microspheres of expanded acrylic copolymers, polyamide powders, silica powders, polytetrafluoroethylene powders, silicone resin powders, acrylic polymer powders, powdered waxes, polyethylene powders, cross- linked organopolysiloxane elastomer powders coated with silicone resin, composite talc/titanium dioxide/alumina/silica powders, mixed amorphous silicate powders, silicate particles in particular of mixed silicates, and mixtures thereof.
  • mattifying agents which may be cited are: rice or corn starch, in particular an octenyl succinate aluminium starch sold under the trade name Dry Flo ® by National Starch;
  • a pumpkin seed extract such as that sold under the trade name Curbilene ® by Indena
  • cellulose microbeads such as those described in patent application EP-I 562 562
  • fibres such as silk, cotton, wool, linseed, cellulose extracted from wood in particular, plant or algae fibres
  • polyamide (Nylon ® ) modified cellulose, poly-p-phenylene terephthamide, acrylic, polyolefin, glass, silica, aramide, carbon, Teflon ® , insoluble collagen, polyesters, polyvinyl or vinylidene chloride, polyvinyl alcohol, polyacrylonitrile, chitosan, polyurethane, polyethylene phthalate, fibres formed from a mixture of polymers, resorbable synthetic fibres, and mixtures thereof described in patent application EP-I 151 742;
  • silica powders for example SB150 Silica beads from Miyoshi with a mean dimension of 5 microns and a refractive index of 1.45; polytetrafluoroethylene powders, such as PTFE Ceridust 9205F from Clariant with a mean dimension of 8 microns and a refractive index of 1.36;
  • silicon resin powders such as Silicon resin Tospearl 145A from GE Silicone with a mean dimension of 4.5 microns and a refractive index of 1.41,
  • acrylic copolymer powders especially of polymethyl methacrylate, such as PMMA Jurymer MBI particles from Nihon Junyoki with a mean dimension of 8 microns and a refractive index of 1.49, or Micropearl M100 ® and F 80 ED ® particles from Matsumoto Yushi-Seiyaku;
  • - powdered waxes such as Paraffin wax microease 114S from Micropowders with a mean dimension of 7 microns and a refractive index of 1.54
  • - polyethylene powders especially comprising at least one ethylene/acrylic acid copolymer, in particular constituted by ethylene/acrylic acid copolymers such as Flobeads EA 209 particles from Sumitomo (with a mean dimension of 10 microns and a refractive index of 1.48);
  • silica powders such as the porous silica microspheres sold under the trade name "SILICA BEADS
  • polymethyl methacrylate such as, for example, "COVABEAD ® LH85” sold by WACKER
  • polymethyl methacrylate/ ethylene glycol dimethacrylate such as, for example, "DOW CORNING 5640 MICROSPONGE ® SKIN OIL ADSORBER” sold by DOW CORNING, or "GANZPEARL ® GMP-0820” sold by GANZ CHEMICAL
  • allyl polymethacrylate/ethylene glycol dimethacrylate such as, for example, "POLY-PORE ® L200" or “POLY-PORE ® E200” sold by AMCOL
  • ethylene glycol dimethacrylate/lauryl methacrylate copolymer such as, for example, "POLYTRAP ® 6603" sold by DOW CORNING
  • polymethyl methacrylate such as, for example, "COVABEAD ® LH85” sold by WACKER
  • - silicate particles such as alumina silicate
  • - mixed silicate particles such as:
  • aluminium and magnesium silicate such as magnesium saponite or silicate and aluminium hydrate with sodium sulphate sold under the trade name Sumecton ® by Kunimine
  • Preferred mattifying agents which may be used in accordance with the invention are an extract of pumpkin seeds, a rice or corn starch, kaolinite, silicas, talc, polyamide powders, polyethylene powders, acrylic copolymer powders, microspheres of expanded acrylic copolymers, silicone resin microbeads, mixed silicate particles and mixtures thereof.
  • Fillers with a soft-focus effect may be any material which is capable of modifying wrinkles by its intrinsic physical properties and of masking them. These fillers may in particular modify wrinkles by a tightening effect, a camouflage effect or a soft-focus effect.
  • silica microparticules such as, for example, Silica Beads ® SB 150 and SB 700 from Myochi with a mean dimension of 5 ⁇ m and SUNSPHERES ® series H from Asahi Glass such as H33, H51 with respective dimensions of 3.5 and 5 ⁇ m; hollow hemispherical particles of silicone resins such as NLK 500 ® , NLK 506 ® and NLK 510 ® from Takemoto Oil and Fat, in particular as described in EP-A-I 579 849;
  • silicone resin powders such as, for example, SILICON Resin Tospearl ® 145 A DE GE silicone with a mean dimension of 4.5 ⁇ m; acrylic copolymer powders, in particular of polymethyl methacrylate such as, for example, PMMA Jurimer MBI ® particles from Nihon Junyoki with a mean dimension of 8 ⁇ m, hollow PMMA spheres sold under the trade name COVABEAD ® LH 85 by Wacker and expanded vinylidene/acrylonitrile/methyl methacrylate microspheres sold under the trade name Expancel ® ;
  • - polyethylene powders especially those comprising at least one ethylene/acrylic acid copolymer such as, for example, FLOBEADS ® EA 209 E from Sumimoto with a mean dimension of 10 ⁇ m; - cross-linked elastomeric organopolysiloxane powders coated with silicone resin, especially with silsesquioxane under the trade name KSP 100 ® , KSP IOI 3 KSP 102 ® , KSP 103 ® , KSP 104 ® and KSP 105 ® by Shin Etsu; composite talc/titanium dioxide/alumina/silica powders such as, for example, Coverleaf AR 80 ® from Catalyst & Chemical; talc, mica, kaolin, lauryl glycine, starch powders cross-linked with octeanyl succinate anhydride, boron nitride, polytetrafluoroethylene powders, precipitated calcium carbonate, magnesium hydrocarbonate
  • Particular fillers having an effect on the signs of ageing are selected from porous silica microparticles, hollow hemispherical silicone particles, silicone resin powders, acrylic copolymer powders, polyethylene powders, cross-linked elastomeric organopolysiloxane powders coated with silicone resin, composite talc/titanium dioxide/alumina/silica powders, precipitated calcium carbonate, magnesium hydrocarbonate carbonate, barium sulphate, hydroxyapatite, calcium silicate, cerium dioxide and glass or ceramic microcapsules, silk fibres, cotton fibres, and mixtures thereof.
  • the filler may be a "soft-focus" filler.
  • soft-focus means a filler which in addition provides the skin with both transparency and a soft- focussed effect.
  • soft-focus fillers have a mean particle size of 15 microns or less. These particles may have any shape, and in particular they may be spherical or non-spherical. Preferably again, these fillers are non-spherical.
  • Soft-focus fillers may be selected from powdered silica and silicates, in particular of alumina, powders of the polymethyl methacrylate (PMMA) type, talc, silica/Tic ⁇ composites or silica/zinc oxide composites, polyethylene powders, starch powders, polyamide powders, styrene/acrylic copolymer powders, silicone elastomers, and mixtures thereof.
  • PMMA polymethyl methacrylate
  • talc silica/Tic ⁇ composites or silica/zinc oxide composites
  • polyethylene powders starch powders
  • polyamide powders polyamide powders
  • styrene/acrylic copolymer powders silicone elastomers, and mixtures thereof.
  • talc with a number average dimension of 3 microns or less, for example talc with a number average dimension of 1.8 microns and in particular that sold under the trade name Talc P3 ® by Nippon Talc, Nylon ® 12 powder, in particular that sold under the trade name Orgasol 2002 Extra D Nat Cos ® by Atochem, silica particles surface treated with a 1% to 2% mineral wax (INCI name: hydrated silica (and) paraffin) , such as those sold by Degussa, amorphous silica microspheres such as those sold under the trade name Sunsphere, for example with reference H-53 ® from Asahi Glass, and silica micro- beads such as those sold under the trade name SB-700 ® or SB-150 ® by Miyoshi; this list is not limiting.
  • Talc P3 ® by Nippon Talc
  • Nylon ® 12 powder in particular that sold under the trade name Orgasol 2002 Extra D Nat Cos ® by Ato
  • concentration of these fillers having an effect on the signs of ageing in the compositions of the invention may be in the range 0.1% to 40%, or even in the range 0.1% to 20% by weight with respect to the total composition weight.
  • fluorescent agent means a substance which, under the effect of ultraviolet radiation and/or visible light, re-emits in the visible the portion of light which it has absorbed with the same colour as that which it naturally reflects. The naturally reflected colour is thus reinforced by the re-emitted colour and appears extremely bright.
  • coloured resins of polyamide and/or formaldehyde/benzoguanamine and/or melamine/formaldehyde/sulphonamide from coloured aminotriazine/formaldehyde/sulphonamide co-condensates and/or from metallized polyester flakes and/or mixtures thereof.
  • These fluorescent pigments may also be in the form of aqueous dispersions of fluorescent pigments.
  • organic fluorescent substances When the organic fluorescent substances are white, they may also be termed optical brighteners .
  • the optical brightener intensifies the radiance and enlivens the colours of cosmetic compositions comprising them when applied to the skin.
  • optical brighteners which may be cited are stilbene derivatives, in particular polystyrylstilbenes and triazinstilbenes, coumarin derivatives, in particular hydroxycoumarins and les aminocoumarins, oxazole, benzoxazole, imidazole, triazole, pyrazoline derivatives, pyrene derivatives and derivatives of porphyrin and/or mixtures thereof.
  • Such compounds are, for example, available under the trade names Tinopal SOP ® and Uvitex OB ® from CIBA GEIGY.
  • Preferred optical brighteners which may be used are sodium 4 , 4 ' -bis [ (4 , 6-dianilino-l , 3, 5-triazin-2- yl) amino] stilbene-2, 2 ' -disulphonate, 2, 5-thiophene di- yl bis (5-ter-butyl-l, 3-benzoxazole) , disodium di- styryl-4, 4' -biphenyl sulphonate and/or mixtures thereof.
  • a self-tanning agent i.e. an agent which, when applied to the skin, in particular to the face, can produce a tanned effect which bears a reasonable similarity to that which can result from prolonged exposure to the sun (natural tanning) or under a UV 1 amp ;
  • an additional colouring agent i.e. any compound having a particular affinity for the skin which can endow it with a durable colour, and with no coverage
  • Such a durable colour is thus distinguished from the superficial, momentary colour provided, for example, by a makeup pigment; and mixtures thereof.
  • DHA dihydroxyacetone
  • erythrulose erythrulose
  • a catalytic system combination formed by: manganese and/or zinc salts and oxides; and alkali or alkaline-earth bicarbonates .
  • the self-tanning agents are generally selected from mono- or polycarbonylated compounds such as, for example, isatine, alloxane, ninhydrin, glyceraldehyde, mesotartaric aldehyde, glutaraldehyde, erythrulose, pyrazolin-4, 5-dione derivatives such as those described in FR-2 466 492 and WO-97/35842, dihydroxyacetone (DHA) , 4, 4-dihydroxypyrazolin-5-one derivatives such as those described in patent application EP-O 903 342.
  • DHA dihydroxyacetone
  • the DHA may be used in the free and/or encapsulated form, for example in lipid vesicles such as liposomes, described in particular in application WO-97/25970.
  • the self-tanning agent is present in a quantity of 0.01% to 20% by weight, preferably in a quantity in the range 0.1% to 10% of the total composition weight.
  • Said dyes may be selected from direct synthetic or natural dyes.
  • Said dyes may, for example, be selected from red or orange fluorane type dyes such as those described in patent application FR-2 840 806.
  • the following dyes may, for example, be cited :
  • These dyes may also be selected from anthraquinones, caramel, carmine, carbon black, azulene blues, methoxalene, trioxalene, guajazulene, chamuzulene, bengal rose, cosine 1OB, cyanosine, and daphinine.
  • dyes may also be selected from indole derivatives such as monohydroxyindoles for example those described in FR-2 651 126 (i.e.: 4-, 5-, 6- or 7-hydroxyindole) or di-hydroxyindoles such as those described in EP-B-O 425 324 (i.e.: 5, 6-dihydroxyindole, 2-methyl 5,6- dihydroxyindole, 3-methyl 5, 6-dihydroxyindole, 2,3- dimethyl 5, 6-dihydroxyindole) .
  • indole derivatives such as monohydroxyindoles for example those described in FR-2 651 126 (i.e.: 4-, 5-, 6- or 7-hydroxyindole) or di-hydroxyindoles such as those described in EP-B-O 425 324 (i.e.: 5, 6-dihydroxyindole, 2-methyl 5,6- dihydroxyindole, 3-methyl 5, 6-dihydroxyindole, 2,3- dimethyl 5, 6-dihydroxyind
  • Exfoliating agents which may be used in rinsing compositions of the invention which may, for example, be cited are exfoliating or buffing particles of mineral, vegetable or organic origin.
  • polyethylene beads or powder may be used, also nylon powder, polyvinyl chloride powder, pumice stone, ground apricot kernels or hazelnut shells, sawdust, glass beads, alumina and mixtures thereof.
  • Exfogreen ® from Solabia (bamboo extract) , extracts from strawberry seeds (Akenes de fraise from Greentech) , powdered peach kernel, powdered apricot kernel, and finally in the field of vegetable powders with an abrasive effect, we can cite cranberry seed powder.
  • Preferred abrasive fillers or exfoliating agents of the invention which may be cited are peach kernel powder, apricot kernel powder, cranberry seed powder, extracts from strawberry seeds, and bamboo extracts.
  • EXAMPLE 1 Preparation of 2, 4-bis- (neopentyl 4'- aminobenzalmalonate)-6-[ (3- ⁇ l, 3, 3, 3-tetramethyl-l- [ (trimethylsilyl) oxy] disiloxanyl ⁇ propyl) amino] -1,3,5- triazine :
  • EXAMPLE 2 Preparation of 2 , 4-bis- ( 4-methyl-2-pentanyl 4 / -aminobenzalmalonate) -6- [ (3- ⁇ l , 3 , 3 , 3-tetramethyl-l- [ (trimethylsilyl) oxy] disiloxanyl ⁇ propyl) amino] -1 , 3 , 5- triazine :
  • the derivative from the preceding step (8.5 g, 0.0255 mole) was dissolved in 80 ml of isopropanol with stirring and a nitrogen bubble-through. 50 ml of a 2N HCl solution was added thereto. The mixture was heated under reflux for 24 hours. After cooling, the reaction mixture was extracted with 2 x 100 ml of dichloromethane. The organic phase was washed twice with a saturated sodium bicarbonate solution, then with water and then was dried over sodium sulphate. After concentration under reduced pressure, a brown oil was obtained which was purified by passing over a silica column (eluent: CH 2 CI 2 ) . 3.83 g (51% yield) of clean fractions of isopropyl 4-aminobenzalmalonate was recovered in the form of an orangey yellow oil and used, as is, in the next step.
  • EXAMPLE 4 Preparation of tetrakis (cyclohexylmethyl) 2 , 2 ' - [ ⁇ 6- [ (3- ⁇ 1 , 3 , 3 , 3-tetramethyl-l- [ (trimethylsilyl) - oxy] disiloxanyl ⁇ propyl) amino] -1,3, 5-triazine-2, 4-diyl ⁇ - bis (iminobenzene-4, 1-diylmethylidene) ] dipropanedioate :
  • p-Acetamidobenzaldehyde (7.12 g, 0.436 mole) and bis (cyclohexylmethyl) malonate (12.93 g, 0.436 mole) in 120 ml of toluene are brought to reflux in a reactor surmounted by Dean Stark apparatus while sparging with nitrogen.
  • the mixture is brought to reflux with stirring for 12 hours and the water formed is removed via the Dean Stark apparatus.
  • the cooled reaction mixture is poured into water and extracted with dichloromethane .
  • the organic phase is washed with water and then dried and concentrated under reduced pressure.
  • the derivative from the preceding step (15.5 g, 0.0255 mole) is dissolved in 120 ml of isopropanol with stirring and sparging with nitrogen. 35 ml of 5N HCl solution are added thereto. The mixture is heated at reflux for 12 hours. After cooling, the reaction mixture is extracted with 2 x 100 ml of dichloromethane. The organic phase is washed twice with a saturated sodium bicarbonate solution and with water and is then dried over sodium sulphate. After concentrating under reduced pressure, a yellow gum is obtained and is purified by passing through a silica column (eluent: CH 2 Cl 2 ) .
  • EXAMPLE 5 Preparation of tetracyclohexyl 2, 2' - [ ⁇ 6- [ (3- ⁇ 1, 3, 3, 3-tetramethyl-l- [ (trimethylsilyl) oxy] di- siloxanyl ⁇ propyl) amino] -1,3, 5-triazine-2, 4-diyl ⁇ bis- (iminobenzene-4, 1-diylmethylidene) ] dipropanedioate :
  • the derivative from the preceding step (11.55 g, 0.0278 mole) is dissolved in 90 ml of isopropanol with stirring and sparging with nitrogen. 35 ml of 5N HCl solution are added thereto. The mixture is heated at reflux for 12 hours. After cooling, the reaction mixture is extracted with 2 x 100 ml of dichloromethane . The organic phase is washed twice with a saturated sodium bicarbonate solution and with water and is then dried over sodium sulphate. After concentrating under reduced pressure, a brown gum is obtained and is purified by passing through a silica column (eluent: CH2CI2) . 3.73 g (yield 36%) of the clean biscyclohexyl 4-aminobenzalmalonate fractions are recovered in the form of a yellow powder used as is in the following step.
  • the two products were dissolved at 2% by weight in Miglyol 812 oil. Approximately 10 mg of the Miglyol 812 solution was spread onto 10 cm 2 of the surface of a hollow ground glass disc; the quantity was determined by weighing.
  • Capric/Caprylic Triglycerides (Miglyol 812) :
  • X mg of product are introduced into Y mg of the oil; with gentle heating ( ⁇ 40°C) and the use of an ultrasound generator for 1 minute, the solution obtained is left at laboratory temperature for 2 weeks; the condition of this solution is observed; if no crystal or oily deposit is visible, the solubility of the product is regarded as greater than X x 100/ (X + Y) as weight/weight.

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Abstract

The invention concerns novel s-triazine compounds containing one aminosiloxane group and two particular para-aminobenzalmalonate groups. The invention also concerns cosmetic or dermatological compositions intended for the photoprotection of keratinous materials, comprising at least one s-triazine compound containing one aminosiloxane group and two particular grafted para-aminobenzalmalonate groups in a cosmetically acceptable medium. The invention also concerns the use of at least one s-triazine compound containing one aminosiloxane group and two particular grafted para-aminobenzalmalonate groups in a cosmetic composition, as an agent for filtering for UV-A radiation.

Description

S-TRIAZINE COMPOUNDS CONTAINING ONE AMINOS ILOXANE GROUP
AND TWO PARTICULAR PARA-AMINOBENZALMALONATE GROUPS; COSMETIC COMPOSITIONS CONTAINING SAID DERIVATIVES; USES
OF SAID s-TRIAZINE DERIVATIVES
The invention relates to novel s-triazine compounds containing one aminosiloxane group and two particular para-aminobenzalmalonate groups with formula (I) which will be defined in detail below, and to their uses in cosmetics.
The invention also relates to cosmetic or dermatological compositions intended for the photoprotection of keratinous materials comprising, in a cosmetically acceptable medium, at least one s- triazine compound containing one aminosiloxane group and two grafted para-aminobenzalmalonate groups with formula (I) which will be defined in detail below.
The invention also relates to the use of at least one s-triazine compound containing one aminosiloxane group and two grafted para-aminobenzalmalonate groups with formula (I) which will be defined in detail below in a cosmetic composition as a UV-A radiation filtering agent.
Radiation with wavelengths in the range 280 nm to 400 nm is known to promote tanning of the human epidermis, and radiation with wavelengths in the range 280 nm to 320 nm, known as UV-B radiation, is known to cause erythemas and skin burns which may be harmful to the development of a natural tan.
UV-A radiation, with wavelengths in the range 320 nm to 400 nm, causing tanning of the skin is known to be capable of inducing alteration therein, especially in the case of sensitive skin and/or skin which is continually exposed to solar radiation. In particular, UV-A irradiation causes a loss in the elasticity of the skin and the appearance of wrinkles, promoting premature ageing of the skin. It promotes triggering of the erythemal reaction or amplifies this reaction in certain individuals and may even be the source of phototoxic or photoallergic reactions. Thus, for aesthetic and cosmetic reasons such as retaining the natural elasticity of the skin, more and more people wish to control the effect of UV-A radiation on their skin. The term "sun protection factor" means the ratio of the irradiation period necessary to achieve the erythematogenic threshold in the present of a test filter to the irradiation period necessary to reach that same threshold in the absence of a filter.
Thus, the availability of compounds which could absorb UV-A radiation would be desirable.
In addition to their UV-A radiation filtering power, the photoprotective compounds sought must also have good cosmetic properties, good solubility in the usual solvents and in particular in fatty substances such as oils and fats, as well as good resistance to water and to perspiration (persistence) , and satisfactory photostability .
Among all the compounds which have been recommended for this purpose, the s-triazine derivatives cited in the Applicant's patent application EP-O 841 341 carrying at least one silicone group and at least one UV-B and/or UV-A chromophore, in particular the aminobenzalmalonate chromophore, may be cited. However, the liposolubility and photochemical stability of said compounds are not yet entirely satisfactory.
The Applicant has surprisingly discovered a novel family of s-triazine derivatives carrying one aminosiloxane group and two particular para- aminobenzalmalonate groups having good absorption properties in the long UV-A radiation range and having a solublity in fatty substances, a photostability, as well as cosmetic qualities which are substantially improved with respect to the prior art s-triazine derivatives grafted with aminobenzalmalonates mentioned above .
The invention concerns a novel family of s-triazine derivatives carrying one aminosiloxane group and two particular para-aminobenzalmalonate groups with formula (I) which will be defined in detail below.
The invention also concerns a cosmetic or dermatological composition intended for the photoprotection of keratinous materials, containing at least one compound with formula (I) in a cosmetically acceptable medium.
The invention also concerns the use of at least one s- triazine compound containing one aminosiloxane group and two grafted para-aminobenzalmalonate groups with formula (I) which will be defined below in detail in a cosmetic composition as a UV-A radiation filtering agent .
Other aspects will become apparent from the description .
The compounds of the present invention have the following general formula (I) or one of its tautomeric forms:
Figure imgf000004_0001
in which • (X) , which may be identical or different, represent a linear or branched C1-C30 alkyl radical, optionally halogenated or unsaturated, a - A -
Cδ-Ci2 aryl radi cal , a Ci -Cio al koxy radi cal or the trimethyl s i l yl oxy group ;
• a = 1 to 3 ;
• group (D) designates an s-triazine compound with the following formula (II) :
Figure imgf000005_0001
in which:
R, which may be identical or different, designate a group with formula (III) :
Figure imgf000005_0002
in which:
Ri and R2, which may be identical or different, represent a linear or branched Ci-Cs alkyl group;
Ri and R2 may form a C5-Cs cycle, optionally substituted with 1, 2 or 3 linear or branched Ci-C4 alkyl groups;
R3, R4 and R5, which may be identical or different, represent a hydrogen atom or a linear or branched Ci-C4 alkyl group; n is 0 or 1; m is 0 or 1; provided that:
(i) when n = 1 and R4 designates hydrogen, then m = 0 and R3 is different from hydrogen;
(ii) when Ri and R2 form a Ci-Cs cycle, then the sum n + m is different from 2; • A is a divalent radical with the following formula :
(Z)-CH-CH2- W
in which:
• (Z) is a linear or branched, saturated or unsaturated Ci-Cio alkylene diradical, optionally substituted with a hydroxy radical or oxygens and which may optionally contain an amino group;
• W represents a hydrogen atom, a hydroxy radical or a linear or branched Ci-Cs alkyl radical.
In addition to units with formula -(Si) (X) a (O) (3-a) /2, the organosiloxane may comprise units with formula -(X)b-(Si) (O) <4-b)/2 in which:
(X) has the same meaning as in formula (I) ; b = 1-3.
Preferably, the s-triazine compounds of the invention are represented by the following formulae (Ia) or (Ib) :
Figure imgf000006_0001
R6 R6
(Ib) R. (D)
in which: • (D) has formula (II) as defined above;
• R6, which may be identical or different, are selected from linear or branched C1-C20 alkyl, phenyl, 3, 3, 3-trifluoropropyl and trimethylsilyloxy radicals, at least 80% by number of radicals Re being methyl;
• (B) , which may be identical or different, are selected from radicals Re and radical (D) ,
• r is a whole number in the range 0 to 200 inclusive;
• s is a whole number from 0 to 50 and if s = 0, at least one of the two symbols (B) designates (D) ; • u is a whole number from 1 to 10;
• t is a whole number from 0 to 10, given that t + u is 3 or more.
Linear diorganosiloxanes with formula (Ia) are particularly preferred.
The linear or cyclic diorganosiloxanes with formula (Ia) or (Ib) used in the context of the present invention are random oligomers or polymers preferably having at least one and more preferably all of the following characteristics :
• Re is alkyl; more preferably, it is methyl;
• (B) is preferably methyl (case of linear compounds with formula (Ia) ) .
In formula (I) above, the alkyl radicals may be linear or branched and in particular are selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert- butyl, n-amyl, isoamyl, neopentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl and tert-octyl radicals. Particularly preferably, the alkyl radical is the methyl radical.
The cycloalkyl radicals may in particular be selected from cyclopentyl, cyclohexyl and cycloheptyl radicals. Particularly preferably, the cycloalkyl radical is the cyclohexyl radical. These radicals may be substituted with Ci-C4 alkyl radicals, preferably selected from methyl, isopropyl and tert-butyl.
Preferred compounds with formula (I) which may be cited include those in which (X) is the methyl radical and A is the propyl diradical.
Preferred compounds with formula (I) which may be cited include those in which the following two conditions are combined :
(a) n = m = 0 ; and
(b) Ri, R2 and R3 designate a Ci-C4 alkyl and more particularly methyl, or R3 designates hydrogen and Ri and R2 form a C5-Cs cycle, optionally substituted with 1 or two alkyl radicals, more particularly cyclohexyl.
Preferred compounds with formula (I) which may be cited include those in which the following two conditions are combined:
(a) n = 1 and R4 designates an alkyl, in particular methyl, or m = 1 and R5 designates an alkyl, in particular methyl; and
(b) Ri and R2 designate a Ci-C4 alkyl, more particularly methyl.
More particularly preferred compounds with formula (I) which may be cited include those with the following formulae (1) to (10) :
Figure imgf000008_0001
(1)
(2)
Figure imgf000009_0001
(3) (4)
Figure imgf000009_0002
(5) (6)
Figure imgf000009_0003
(7)
Figure imgf000010_0001
where r = 8 . 1
Figure imgf000010_0002
(10)
where r = s = 6 .
The derivatives with formula ( I ) may be obtained in accordance with the fol lowing reaction scheme :
Figure imgf000010_0003
in which R, A, X and a satisfy the above definitions and Y represents a halogen, in particular chlorine or bromine .
The reagents may be introduced in any order, 2 equivalents of the derivative with formula (III) followed by one equivalent of the derivative with formula (IV) (route Ia) or 1 equivalent of the derivative with formula (IV) followed by 2 equivalents of the derivative with formula (III) (route Ib) .
The above reactions may optionally be carried out in the presence of a solvent (for example toluene, xylene or acetone/water) at a temperature in the range 00C to 2500C, more particularly in the range 5°C to 1500C; the introduction order must be sequenced but the intermediate products may or may not be isolated.
The above reactions may optionally be carried out in the presence of a solvent (for example : THF, methyl ethyl ketone, ethyl acetate or acetone/water for the first step; toluene, xylene, ethyl acetate, methylethyl ketone or 1, 2-dichloroethane for the second step), at a temperature in the range 00C to 2000C, more particularly in the range 00C to 200C for the first step and in the range 500C to 1200C for the second step and in the presence or absence of a base to trap the acid formed (for example : sodium bicarbonate, sodium carbonate, aqueous sodium hydroxide, triethylamine or pyridine) . They may also be carried out in a microwave oven in the presence or absence of a solvent (for example : toluene, xylene or 1, 2-dichloroethane) or in the presence or absence of 10% of graphite, at a temperature of 50°C to 150°C, at a power of 50-150 watts for a period of 10 to 30 minutes.
When a equals 1-3 and R is an alkoxy, the monomeric alkoxysilane derivatives may be polymerized using conventional methods of silicone chemistry.
The compounds with formula (III) may be prepared using the known methods described in patents FR-2 385 685 or FR-2 888 113.
The amino-containing silicones with formula (IV) may be obtained from Dow Corning Toray Silicone Co Ltd, such as those with an α,ω-diamino structure such as BY16-853 (viscosity: 30; NH2 equivalent: 650) or BY16-853B (viscosity: 80; NH2 equivalent: 2200) or those with pendent groups, such as BY16-828 (viscosity: 120; NH2 equivalent: 3500) or BY16-850 (viscosity: 1100; NH2 equivalent: 4000) .
The invention also concerns cosmetic or dermatological compositions intended for the photoprotection of keratinous materials comprising, in a cosmetically acceptable medium, at least one s-triazine compound containing one aminosiloxane group and two grafted para-aminobenzalmalonate groups with formula (I) as defined above.
The term "cosmetically acceptable medium" as used in the composition of the invention means a non-toxic medium which is capable of being applied to human keratinous materials comprising the skin, face, lips, nails, hair and scalp.
The compounds with formula (I) are generally present in the composition of the invention in proportions in the range 0.01% to 20% by weight, preferably in the range 0.1% to 10% by weight, with respect to the total composition weight.
The compositions of the invention may in addition contain at least one mineral UV filter and/or at least one complementary organic UV filter.
The organic UV filters are selected from hydrosoluble organic filters, liposoluble organic filters or organic filters which are insoluble in the solvents which are routinely used in anti-sun products and mixtures thereof . In particular, organic UV filters are selected from cinnamic derivatives; anthranilates; salicylic derivatives, dibenzoylmethane derivatives, camphor derivatives; benzophenone derivatives; β/β~ diphenylacrylate derivatives; triazine derivatives; benzotriazole derivatives; benzalmalonate derivatives in particular those cited in patent US-5 624 663; benzimidazole derivatives; imidazolines; bis- benzoazolyl derivatives such as those described in patents EP-O 669 323 and US-2 463 264; p- aminobenzoic acid (PABA) derivatives; methylene bis- (hydroxyphenyl benzotriazole) derivatives such as those described in US-5 237 071, US-5 166 355, GB-2 303 549, DE-197 26 184 and EP-O 893 119; benzoxazole derivatives such as those described in patent applications EP-O 832 642, EP-I 027 883, EP-I 300 137 and DE 101 62 844; polymer filters and silicone filters, such as those described in particular in application WO-93/04665; dimers derived from α-alkylstyrene such as those described in patent application DE-198 55 649; 4,4- diarylbutadienes such as those described in applications EP-O 967 200, DE 197 46 654, DE 197 55 649, EP-A-I 008 586, EP-I 133 980 and EP-O 133 981; and merocyanine derivatives such as those described in applications WO-04/006878, WO-05/058269 and WO- 06/032741 and mixtures thereof.
Examples of complementary organic photoprotective agents which may be cited are those designated hereinbelow under their INCI name :
Cinnamic derivatives:
Ethylhexyl Methoxycinnamate sold in particular under the trade name PARSOL MCX by DSM NUTRITIONAL PRODUCTS, INC.;
Isopropyl Methoxycinnamate;
Isoamyl Methoxycinnamate sold under the trade name NEO
HELIOPAN E 1000 by SYMRISE;
DEA Methoxycinnamate; Diisopropyl Methylcinnamate;
Glyceryl Ethylhexanoate Dimethoxycinnamate;
Dibenzoylmethane derivatives: Butyl Methoxydibenzoylmethane, sold in particular under the trade name PARSOL 1789 by DSM NUTRITIONAL PRODUCTS, INC . ; Isopropyl Dibenzoylmethane;
Para-aminobenzoic acid derivatives:
PABA;
Ethyl PABA;
Ethyl Dihydroxypropyl PABA;
Ethylhexyl Dimethyl PABA in particular sold under the name "ESCALOL 507" by ISP; Glyceryl PABA; PEG-25 PABA sold under the name "UVINUL P25" by BASF;
Salicylic derivatives: Homosalate sold under the name "Eusolex HMS" by Rona/EM
Industries;
Ethylhexyl Salicylate sold under the name "NEO HELIOPAN
OS" by SYMRISE;
Dipropyleneglycol Salicylate sold under the name "DIPSAL" by SCHER;
TEA Salicylate, sold under the name "NEO HELIOPAN TS" by SYMRISE;
J3, J3-diphenylacrylate derivatives : Octocrylene sold in particular under the trade name "UVINUL N539" by BASF;
Etocrylene, sold in particular under the trade name "UVINUL N35" by BASF;
Benzophenone derivatives:
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; Benzophenone-5;
Benzophenone-6 sold under the trade name "Helisorb 11" by Norquay;
Benzophenone-8 sold under the trade name "Spectra-Sorb
UV-24" by American Cyanamid; Benzophenone-9 sold under the trade name "UVINUL DS-49" by BASF;
Benzophenone-12 ; n-hexyl 2- (4-diethylamino-2-hydroxybenzoyl) -benzoate sold under the trade name "UVINUL A+" by BASF;
Benzylidene camphor derivatives:
3-Benzylidene camphor produced under the name "MEXORYL
SD" by CHIMEX;
4-Methylbenzylidene camphor sold under the name "EUSOLEX 6300" by MERCK;
Benzylidene Camphor Sulphonic Acid produced under the name "MEXORYL SL" by CHIMEX;
Camphor Benzalkonium Methosulphate produced under the name "MEXORYL SO" by CHIMEX; Terephthalylidene Dicamphor Sulphonic Acid produced under the name "MEXORYL SX" by CHIMEX;
Polyacrylamidomethyl Benzylidene Camphor produced under the name "MEXORYL SW" by CHIMEX;
Phenyl benzimidazole derivatives:
Phenylbenzimidazole Sulphonic Acid sold in particular under the trade name "EUSOLEX 232" by MERCK;
Disodium Phenyl Dibenzimidazole Tetra-sulphonate sold under the trade name "NEO HELIOPAN AP" by SYMRISE;
Phenyl benzotriazole derivatives:
Drometrizole Trisiloxane sold under the name
"Silatrizole" by RHODIA CHIMIE; Methylene bis-Benzotriazolyl Tetramethylbutylphenol, sold in the solid form under the trade name "MIXXIM BB/100" by FAIRMOUNT CHEMICAL or in the micronized form in aqueous dispersion under the trade name "TINOSORB M" by CIBA SPECIALTY CHEMICALS;
Triazine derivatives:
Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine sold under the trade name "TINOSORB S" by CIBA GEIGY; - Ethylhexyl triazone sold in particular under the trade name "UVINUL T150" by BASF;
- Diethylhexyl Butamido Triazone sold under the trade name "UV-ASORB HEB" by SIGMA 3V;
2 , 4 , 6-tris (dineopentyl 4' -amino benzalmalonate) -s- triazine;
2 , 4 , 6-tris- (diisobutyl 4' -amino benzalmalonate) -s- triazine;
2 , 4-bis (n-butyl 4' -aminobenzoate) -6-
(aminopropyltrisiloxane) -s-triazine; - 2 , 4-bis (dineopentyl 4' -aminobenzalmalonate) -6- (n- butyl 4' -aminobenzoate) -s-triazine;
- symmetrical triazine filters described in patent US-6 225 467, application WO-2004/085412 (see compounds 6 and 9) or the document "Symmetrical Triazine Derivatives" IP.COM Journal, IP.COM INC WEST HENRIETTA,
NY, US (20 September 2004) in particular 2,4,6-tris-
(biphenyl) -1, 3, 5-triazines (in particular 2,4,6- tris (biphenyl-4-yl-l, 3, 5-triazine and 2,4,6- tris (terphenyl) -1, 3, 5-triazine which are described in patent applications WO-06/035000, WO-06/034982, WO-06/034991, WO-06/035007, WO-2006/034992 and WO-2006/034985;
Anthranilic derivatives: Menthyl anthranilate sold under the trade name "NEO HELIOPAN MA" by HAARMANN and REIMER;
Imidazoline derivatives: Ethylhexyl Dimethoxybenzylidene Dioxoimidazoline Propionate;
Benzalmalonate derivatives: Polyorganosiloxane with benzalmalonate functions such as Polysilicone-15 sold under the trade name "PARSOL SLX" by DSM NUTRITIONAL PRODUCTS, INC.;
4 , 4-diarylbutadiene derivatives: -1, 1-dicarboxy (2, 2 ' -dimethyl-propyl) -4, 4- diphenylbutadiene ;
Benzoxazole derivatives:
2, 4 -bis- [5-1 (dimethylpropyl) benzoxazol-2-yl- (4 -phenyl) - imino] -6- (2-ethylhexyl) -imino-1, 3, 5-triazine sold under the name UV-Asorb K2A by Sigma 3V; and mixtures thereof.
Merocyanine derivatives Octyl 5-N, N-diethylamino-2-phenylsulphonyl-2, 4-penta- dienoate;
Preferred organic filters are selected from :
Ethylhexyl Methoxycinnamate; Ethylhexyl Salicylate;
Homosalate;
Butyl Methoxydibenzoylmethane;
Octocrylene;
Phenylbenzimidazole Sulphonic Acid; Benzophenone-3;
Benzophenone-4 ;
Benzophenone-5; n-hexyl 2- (4-diethylamino-2-hydroxybenzoyl) -benzoate;
4-Methylbenzylidene camphor; Terephthalylidene Dicamphor Sulphonic Acid;
Disodium Phenyl Dibenzimidazole Tetra-sulphonate;
Methylene bis-Benzotriazolyl Tetramethylbutylphenol;
Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine;
Ethylhexyl triazone; Diethylhexyl Butamido Triazone;
2,4, 6-tris (dineopentyl 4' -aminobenzalmalonate) -s- triazine;
2,4, 6-tris (diisobutyl 4' -aminobenzalmalonate) -s- triazine;
2, 4-bis (n-butyl 4' -aminobenzoate) -6-
(aminopropyltrisiloxane) -s-triazine;
2, 4-bis (dineopentyl 4' -aminobenzalmalonate) -6- (n-butyl
4' -aminobenzoate) -s-triazine; 2,4, 6-tris (biphenyl-4-yl-l, 3, 5-triazine;
2,4, 6-tris (terphenyl) -1, 3, 5-triazine;
Drometrizole Trisiloxane;
Polysilicone-15;
1, 1-dicarboxy- (2,2' -dimethylpropyl) -4, 4- diphenylbutadiene;
2, 4-bis- [5-1 (dimethylpropyl) benzoxazol-2-yl- (4 -phenyl) - imino] -6- (2-ethylhexyl) -imino-1, 3, 5-triazine;
Octyl 5-N, N-diethylamino-2-phenylsulphonyl-2 , 4-penta- dienoate; and mixtures thereof.
The complementary organic filters of the invention generally represent 0.1% to 30%, preferably 1% to 25% of the total composition weight.
The complementary inorganic UV filters used in accordance with the present invention are metal oxide pigments. More preferably, the inorganic UV filters of the invention are metal oxide particles having a mean elementary particle size of 500 nm or less, more preferably in the range 5 nm to 500 nm, and still more preferably in the range 10 nm to 100 nm, preferably in the range 15 nm to 50 nm.
They may in particular be selected from oxides of titanium, zinc, iron, zirconium, cerium or mixtures thereof, and more particularly titanium oxides. Such metal oxide pigments, which may be coated or non- coated, are described in particular in patent application EP-A-O 518 773. Examples of commercially available pigments which may be mentioned are the products sold by Kemira, Tayca, Merck and Degussa.
The metal oxide pigments may be coated or non-coated.
The coated pigments are pigments which have undergone one or more surface treatments of a chemical, electronic, mechanochemical and/or mechanical nature with compounds such as amino acids, beeswax, fatty acids, fatty alcohols, anionic surfactants, lecithins, sodium, potassium, zinc, iron or aluminium salts of fatty acids, metal alkoxides (of titanium or aluminium), polyethylene, silicones, proteins
(collagen, elastin) , alkanolamines, silicon oxides, metal oxides or sodium hexametaphosphate .
More particularly, the coated pigments are titanium oxides coated: with silica, such as the product "SUNVEIL" from IKEDA; with silica and iron oxide, such as the product "SUNVEIL F" from IKEDA; with silica and alumina, such as the products "MICROTITANIUM DIOXIDE MT 500 SA" and "MICROTITANIUM DIOXIDE MT 100 SA" from TAYCA, "TIOVEIL" from TIOXIDE;
- with alumina, such as the products "TIPAQUE TTO-55 (B) " and "TIPAQUE TTO-55 (A) " from ISHIHARA, and "UVT
14/4" from KEMIRA; with alumina and aluminium stearate, such as the products "MICROTITANIUM DIOXIDE MT 100 T, MT 100 TX, MT
100 Z, MT-Ol" from TAYCA, the products "Solaveil CT-IO W" and "Solaveil CT 100" from UNIQEMA and the product
"Eusolex T-AVO" from MERCK;
- with silica, alumina and alginic acid, such as the product "MT-100 AQ" from TAYCA; with alumina and aluminium laurate, such as the product "MICROTITANIUM DIOXIDE MT 100 S" from TAYCA; with iron oxide and iron stearate, such as the product "MICROTITANIUM DIOXIDE MT 100 F" from TAYCA; with zinc oxide and zinc stearate, such as the product "BR 351" from TAYCA;
- with silica and alumina and treated with a silicone, such as the products "MICROTITANIUM DIOXIDE MT 600 SAS", "MICROTITANIUM DIOXIDE MT 500 SAS" or "MICROTITANIUM DIOXIDE MT 100 SAS" from TAYCA; - with silica, alumina, aluminium stearate and treated with a silicone, such as the product "STT-30-DS" from TITAN KOGYO;
- with silica and treated with a silicone, such as the product "UV-TITAN X 195" from KEMIRA; - with alumina and treated with a silicone, such as the products "TIPAQUE TTO-55 (S)" from ISHIHARA, or "UV TITAN M 262" from KEMIRA;
- with triethanolamine such as the product "STT-65-S" from TITAN KOGYO; - with stearic acid, such as the product "TIPAQUE TTO- 55 (C) " from ISHIHARA;
- with sodium hexametaphosphate, such as the product "MICROTITANIUM DIOXIDE MT 150 W" from TAYCA;
- Tiθ2 treated with octyl trimethyl silane sold under the trade name "T 805" by DEGUSSA SILICES;
- Tiθ2 treated with a polydimethylsiloxane sold under the trade name "70250 Cardre UF TiO2SI3" by CARDRE;
Tiθ2 anatase/rutile treated with a polydimethylhydrogenosiloxane sold under the trade name "MICROTITANIUM DIOXYDE USP GRADE HYDROPHOBIC" by COLOR TECHNIC.
Non-coated titanium oxide pigments are, for example, sold by TAYCA under the trade names "MICROTITANIUM DIOXIDE MT 500 B" or "MICROTITANIUM DIOXIDE MT 600 B", by DEGUSSA under the trade name "P 25", by WACKER under the trade name "Oxyde de titane transparent PW", by MIYOSHI KASEI under the trade name "UFTR", by TOMEN under the trade name "ITS" and by TIOXIDE under the trade name "TIOVEIL AQ".
Examples of non-coated zinc oxide pigments are:
- those sold under the trade name "Z-cote" by Sunsmart; - those sold under the trade name "Nanox" by Elementis;
- those sold under the trade name "Nanogard WCD 2025" by Nanophase Technologies.
Examples of non-coated zinc oxide pigments are: - those sold under the trade name "Oxide zinc CS-5" by Toshibi (ZnO coated with polymethylhydrogenesiloxane) ;
- those sold under the trade name "Nanogard Zinc Oxide FN" by Nanophase Technologies (at 40% dispersion in Finsolv TN, C12-C15 alcohol benzoate) ; - those sold under the trade name "DAITOPERSION ZN-30" and "DAITOPERSION Zn-50" by Daito (dispersions in cyclopolymethylsiloxane/oxyethylenated polydimethylsiloxane, containing 30% or 50% of zinc nano-oxides coated with silica and polymethylhydrogenesiloxane) ;
- those sold under the trade name "NFD Ultrafine ZnO" by Daikin (ZnO coated with perfluoroalkyl phosphate and copolymer based on perfluoroalkylethyl in dispersion in cyclopentasiloxane) ; - those sold under the trade name "SPD-Zl" by Shin-Etsu (ZnO coated with silicone grafted acrylic polymer, dispersed in cyclodimethylsiloxane) ;
- those sold under the trade name "Escalol ZlOO" by ISP (ZnO treated alumina dispersed in an ethylhexyl methoxycinnamate/PVP-hexadecene copolymer/methicone mixture) ;
- those sold under the trade name "Fuji ZnO-SMS-IO" by Fuji Pigment (ZnO coated with silica and polymethylsilsesquioxane) ; - those sold under the trade name "Nanox Gel TN" by Elementis (ZnO dispersed to 55% in C12-C15 alcohol benzoate with hydroxystearic acid polycondensate) .
The non-coated cerium oxide pigments may, for example, be those sold under the trade name "COLLOIDAL CERIUM OXIDE" by RHONE POULENC.
Examples of non-coated iron oxide pigments are those sold by ARNAUD under the trade names "NANOGARD WCD 2002 (FE 45B)", "NANOGARD IRON FE 45 BL AQ", "NANOGARD FE 45R AQ, "NANOGARD WCD 2006 (FE 45R)", or by MITSUBISHI under the trade name "TY-220".
Examples of coated iron oxide pigments are those sold by ARNAUD under the trade names "NANOGARD WCD 2008
(FE 45B FN)", "NANOGARD WCD 2009 (FE 45B 556)",
"NANOGARD FE 45 BL 345", "NANOGARD FE 45 BL", or by
BASF under the trade name "OXYDE DE FER TRANSPARENT".
Mixtures of metal oxides may also be cited, in particular of titanium dioxide and cerium dioxide, including the mixture of equal weights of titanium dioxide and cerium dioxide coated with silica sold by IKEDA under the trade name "SUNVEIL A", as well as the mixture of titanium dioxide and zinc dioxide coated with alumina, silica and silicone, such as the product "M 261" sold by KEMIRA or coated with alumina, silica and glycerine such as the product "M 211" sold by KEMIRA.
In accordance with the invention, coated or non-coated titanium oxide pigments are particularly preferred.
The complementary inorganic filters of the invention generally represent 0.5% to 40%, preferably 1% to 30% of the total composition weight.
The aqueous compositions of the invention may be presented in any of the forms generally used for topical application, in particular in the form of an oil-in-water emulsion (direct emulsion) , water-in-oil emulsion (reverse emulsion) or an aqueous gel. The compositions of the invention may contain any of the additives which are routinely used in cosmetics and have applications in the field of skin care, makeup and anti-sun products.
The aqueous compositions of the present invention may also comprise conventional cosmetic adjuvants, particularly those selected from fatty substances, organic solvents, ionic or non-ionic, hydrophilic or lipophilic thickeners, demulcents, humectants, opacifying agents, stabilizers, emollients, silicones, anti-foaming agents, fragrances, preservatives, anionic, cationic, non-ionic, zwitterionic or amphoteric surfactants, active ingredients, fillers, polymers, propellants, alkalinizing or acidifying agents or any other ingredient which is routinely used in the cosmetics and/or dermatological field.
The fatty substances may be constituted by an oil or a wax or mixtures thereof. The term "oil" means a compound which is a liquid at ambient temperature. The term "wax" means a compound which is solid or substantially solid at ambient temperature, and has a melting point which is generally more than 35°C.
Oils which may be cited are mineral oils (paraffin) ; vegetable oils (sweet almond oil, macadamia oil, blackcurrant oil, jojoba oil); synthetic oils such as perhydrosqualene, alcohols, fatty amides (such as isopropyl lauroyl sarcosinate sold under the trade name "Eldew SL-205" by Ajinomoto), fatty acids or esters, such as the C12-C15 alcohol benzoate sold under the trade name "Finsolv TN" or "Witconol TN" by WITCO, phenylethyl benzoate sold under the trade name XTEND- 226 by ISP or SPECTRASOL PEB by CP HALL, octyl palmitate, isopropyl lanolate, triglycerides including those of capric/caprylic acids, dicaprylyl carbonate sold under the trade name "Cetiol CC" by Cognis, oxyethylenated or oxypropylenated fatty esters and ethers; silicone (cyclomethicone, polydimethysiloxanes or PDMS) or fluoridated oils, and polyalkylenes .
Waxy compounds which may be cited include paraffin, carnauba wax, beeswax and hydrogenated castor oil.
Organic solvents which may be cited are lower alcohols and polyols. They may be selected from glycols and glycol ethers such as ethylene glycol, propylene glycol, butylene glycol, dipropylene glycol or diethylene glycol.
Hydrophilic thickening agents which may be cited are carboxyvinyl polymers such as Carbopols (carbomers) and Pemulens (acrylate/Cio-C3o-alkylacrylate copolymer) ; polyacrylamides such as the cross-linked copolymers sold under the trade names Sepigel 305 (CTFA name: polyacrylamide/Ci3-Ci4 isoparaffin/Laureth 7) or Simulgel 600 (CTFA name: acrylamide/sodium acryloyldimethyltaurate copolymer/isohexadecane/polysorbate 80) by Seppic; polymers and copolymers of 2-acrylamido 2-methylpropane sulphonic acid, which may be cross-linked and/or neutralized, such as poly (2-acrylamido 2-methylpropane sulphonic acid) sold by Hoechst under the trade name "Hostacerin AMPS" (CTFA name: ammonium polyacryldimethyltauramide) ; cellulosic derivatives such as hydroxyethylcellulose; polysaccharides and in particular gums, such as xanthan gum; and mixtures thereof.
Lipophilic thickening agents which may be cited are synthetic polymers such as poly (C10-C30) alkyl acrylate sold under the trade name "Doresco IPA 13-1" by Landec or modified clays such as hectorite and its derivatives, such as the products sold under the Bentone trade name.
Clearly, the skilled person will take care to select the complementary compound or compounds cited above and/or their quantities in a manner such that the advantageous intrinsic properties of the compositions of the invention are not or are not substantially altered by the envisaged adjuvants.
The compositions of the invention may be prepared using techniques which are well known to the skilled person. In particular, they may be in the form of an emulsion, which may be simple or complex (O/W, W/O, 0/W/O or W/O/W) such as a cream, milk or cream gel; in the form of an aqueous gel; or in the form of a lotion or a stick. They may optionally be packaged as an aerosol and be presented in the form of a foam or spray.
Preferably, the compositions of the invention are presented in the form of an oil-in-water or water-in- oil emulsion.
The emulsions generally contain at least one emulsifying agent selected from amphoteric, anionic, cationic or non-ionic emulsifying agents, used alone or as a mixture. The emulsifying units are selected in an appropriate manner depending on the emulsion to be obtained (W/O or O/W) .
Examples of emulsifying surfactants which may be used to prepare W/O emulsions which may be cited are alkyl esters or ethers of sorbitan, glycerol or sugars; silicone surfactants such as dimethicone copolyols, such as a mixture of cyclomethicone and dimethicone copolyol sold under the trade name "DC 5225C" by Dow Corning, and alkyl-dimethicone copolyols such as Laurylmethicone copolyol sold under the trade name "Dow Corning 5200 Formulation Aid" by Dow Corning; cetyl dimethicone copolyol such as the product sold under the trade name Abil EM 9OR by Goldschmidt and the mixture of cetyl dimethicone copolyol, polyglycerol isostearate (4 moles) and hexyl laurate sold under the trade name ABIL WE 09 by Goldschmidt. It is also possible to add one or more co-emulsifying agents which advantageously may be selected from the group comprising alkylated polyol esters.
Alkylated polyol esters which may be cited include polyethylene glycol esters such as PEG-30 Dipolyhydroxystearate, such as the product sold under the trade name Arlacel P135 by ICI.
Examples of esters of glycerol and/or sorbitan which may be cited include polyglycerol isostearate, such as the product sold under the trade name Isolan GI 34 by Goldschmidt; sorbitan isostearate, such as the product sold under the trade name Arlacel 987 by ICI; sorbitan isostearate and glycerol, such as the product sold under the trade name Arlacel 986 by ICI, and mixtures thereof .
Examples of emulsifying agents for O/W emulsions which may be cited are non-ionic emulsifying agents such as oxyalkylenated (more particularly polyoxyethylenated) esters of fatty acids and glycerol; oxyalkylenated esters of fatty acids and sorbitan; esters of oxyalkylenated (oxyethylenated and/or oxypropylenated) fatty acids such as the PEG-100 Stearate/Glyceryl Stearate mixture sold, for example, by ICI under the trade name Arlacel 165; ethers of oxyalkylenated (oxyethylenated and/or oxypropylenated) fatty alcohols; esters of sugars such as sucrose stearate; ethers of fatty alcohols and sugars, in particular alkylpolyglucosides (APG) such as decylglucoside or laurylglucoside sold, for example, by Henkel under the respective trade names Plantaren 2000 and Plantaren 1200, cetostearylglucoside optionally mixed with cetostearyl alcohol, sold, for example, under the trade name Montanov 68 by Seppic, under the trade name Tegocare CG90 by Goldschmidt and under the trade name Emulgade KE3302 by Henkel, as well as arachidyl glucoside, for example in the form of a mixture of arachidic and behenic alcohols and arachidylglucoside sold under the trade name Montanov 202 by Seppic. In accordance with a particular implementation of the invention, the mixture of alkylpolyglucoside as defined above with the corresponding fatty alcohol may be in the form of a self-emulsifying composition as described, for example, in document WO-A-92/06778.
When it is an emulsion, the aqueous phase thereof may comprise a non-ionic vesicular dispersion prepared using known methods (Bangham, Standish and Watkins. J. MoI. Biol. 13, 238 (1965), FR-2 315 991 and FR-2 416 008) .
The compositions of the invention have applications in a wide variety of treatments, in particular cosmetic, of the skin, lips and hair, including the scalp, especially for the protection and/or care of the skin, lips and/or hair, and or to make up the skin and/or the lips .
Another aspect of the present invention is constituted by the use of the compositions of the invention as defined above for the production of products for the cosmetic treatment of the skin, lips, nails, hair, eyelashes, eyelids and/or scalp, in particular skin care products, sunscreens and makeup products.
The cosmetic compositions of the invention may, for example, be used as a skin care product and/or sunscreen for the face and/or the body with a liquid or semi-liquid consistency, such as lotions, milks, creams of varying oiliness, gels, gel-creams. They may optionally be packaged as an aerosol and be in the form of a foam or spray.
The cosmetic compositions of the invention may, for example, be used as a makeup product. The compositions of the invention in the form of vaporizable fluid lotions in accordance with the invention are applied to the skin or hair in the form of fine particles by dint of pressurization devices. The devices in accordance with the invention are well known to the skilled person and comprise non-aerosol pumps or atomizers, the aerosol receptacles comprising a propellant as well as aerosol pumps using compressed air as a propellant. These latter have been described in patents US-4 077 441 and US-4 850 517 (forming and integral part of the contents of the description) .
Compositions packaged as a aerosol in accordance with the invention generally contain conventional propellants such as hydrofluorinated compounds, dichlorodifluoromethane, difluoroethane, dimethylether, isobutane, n-butane, propane, trichlorofluoromethane .
They are preferably present in quantities of 15% to 50% by weight with respect to the total composition weight.
The compositions of the invention may also include additional cosmetic and dermatological active ingredients .
The additional active ingredients may in particular be selected from moisturizing agents, desquamating agents, agents improving the barrier function, depigmenting agents, antioxidants, dermorelaxing agents, anti- glycation agents, agents stimulating the synthesis of dermal and/or epidermal macromolecules and/or preventing their degradation, agents stimulating the proliferation of fibroblasts or keratinocytes and/or differentiation of keratinocytes, agents promoting the maturation of the cornified envelope, NO-synthase inhibitors, peripheral benzodiazepine receptor (PBR) antagonists, agents increasing the activity of the sebaceous gland, agents stimulating cell energy metabolism, tightening agents, liporestructuring agents, slimming agents, agents promoting cutaneous micro-circulation, soothing agents and/or anti- irritants, sebo-regulators or anti-seborrheic agents, astringent agents, healing agents, antiinflammatories, and anti-acne agents.
The skilled person will select said active ingredient or active ingredients as a function of the desired effect on the skin, hair, eyelids, eyelashes or nails.
To care for and/or makeup aged skin, the skilled person will preferably select at least one active ingredient selected from moisturizing agents, desquamating agents, agents improving the barrier function, depigmenting agents, antioxidants, dermorelaxing agents, anti- glycation agents, agents stimulating the synthesis of dermal and/or epidermal macromolecules and/or preventing their degradation, agents stimulating the proliferation or fibroblasts or keratinocytes and/or the differentiation of keratinocytes, agents promoting maturation of the cornified envelope, NO-synthesis inhibitors, peripheral benzodiazepine receptor (PBR) antagonists, agents increasing the activity of the sebaceous gland, agents stimulating cell energy metabolism, lipo-restructuring agents and agents promoting cutaneous micro-circulation for the contour of the eyes.
The composition may also comprise at least one ingredient such as fillers with a soft-focus effect or agents promoting the natural skin colour, intended to supplement the biological effect of these active ingredients or provide an immediate visual anti-ageing effect .
To care for and/or makeup oily skin, the skilled person will preferably select at least one active ingredient selected from desquamating agents, sebo-regulating or anti-seborrheic agents, and astringent agents. The composition may also comprise at least one additional ingredient intended to supplement the biological effect of said active ingredients or to provide an immediate visual effect; in particular, mattifying agents, fillers with a soft-focus effect, fluorescent agents, agents promoting a natural rosy colour of the skin and abrasive or exfoliating fillers may be cited.
1. Moisturizing or humectant agents
Moisturizing or humectant agents which may be cited include glycerol and its derivatives, urea and its derivatives in particular Hydrovance® sold by National Starch, lactic acids, hyaluronic acid, AHAs, BHAs, sodium pidolate, xylitol, serine, sodium lactate, ectoine and its derivatives, chitosan and its derivatives, collagen, plankton, an imperata cylindra extract sold under the trade name Moist 24® by Sederma, acrylic acid homopolymers such as Lipidure-HM® from NOF Corporation, beta-glucan and in particular sodium carboxymethyl beta-glucan from Mibelle-AG-Biochemistry; a mixture of passiflora, apricot, corn and rice oils sold by Nestle under the trade name NutraLipids®; a C- glycoside derivative such as those described in application WO-02/051828 and in particular C-β-D-xylopyranoside-2-hydroxypropane in the form of a 30% by weight of active substance solution in a water/propylene glycol mixture (60/40% by weight) such as the product produced by CHIMEX under the trade name "MEXORYL SBB®"; a musk rose oil sold by Nestle; an extract from the micro-algae Prophyridium cruentum enriched with zinc sold by Vincience under the trade name Algualane Zinc®; spheres of collagen and chondroitin sulphate of marine origin (Ateocollagen) sold by Engelhard Lyon under the trade name marine filling spheres; hyaluronic acid spheres such as those sold by Engelhard Lyon; and arginine. Preferably, the following are used: a hydrating agent selected from urea and its derivatives, in particular Hydrovance® sold by National Starch, hyaluronic acid, AHAs, BHAs, acrylic acid homopolymers such as Lipidure- HM® from NOF Corporation, beta-glucan and in particular sodium carboxymethyl beta-glucan from Mibelle-AG- Biochemistry; a mixture of passiflora, apricot, corn and rice oils sold by Nestle under the trade name NutraLipids®; a C-glycoside derivative such as those described in application WO-02/051828 and in particular C-β-D-xylopyranoside-2-hydroxy-propane in the form of a 30% by weight of active substance solution in a water/propylene glycol mixture (60/40% by weight) such as the product produced by CHIMEX under the trade name "MEXORYL SBB®"; a musk rose oil sold by Nestle; an extract from the micro-algae Prophyridium cruentum enriched with zinc sold by Vincience under the trade name Algualane Zinc®; spheres of collagen and chondroitin sulphate of marine origin (Ateocollagen) sold by Engelhard Lyon under the trade name marine filling spheres; hyaluronic acid spheres such as those sold by Engelhard Lyon; and arginine.
2. Desquamating agents
The term "desquamating agent" means any compound which is capable of acting:
- either directly on desquamation by promoting exfoliation, such as β-hydroxyacids (BHA) , in particular salicylic acid and its derivatives
(including n-octanoyl 5-salicylic acid, otherwise known under its INCI name of capryloyl salicylic acid) ; α- hydroxyacids (AHA) , such as glycolic, citric, lactic, tartaric, malic or mandelic acids; 8-hexadecene-l, 16- dicarboxylic acid or 9-octadecene dioic acid; urea and its derivatives; gentisic acid and its derivatives; oligofucoses; cinnamic acid; Saphora japonica extract; resveratrol and certain jasmonic acid derivatives; or on the enzymes involved in desquamation or the degradation of corneodesmosomes, glycosidases, stratum corneum chymotryptic enzyme (SCCE) or other proteases (trypsin, chymotrypsin-like) . Aminosulphonic compounds may be cited, in particular 4- (2- hydroxyethyl) piperazine-1-propanesulphonic acid
(HEPES); 2-oxothiazolidine-4-carboxylic acid
(procysteine) and its derivatives; alpha amino acid derivatives of the glycine type (such as those described in EP-O 852 949, as well as sodium methyl glycine diacetate sold by BASF under the trade name TRILON M) ; honey; sugar derivatives such as O-octanoyl- 6-D-maltose and N-acetyl glucosamine.
Other desquamating agents which may be used in the composition of the invention which may be cited are: oligofructoses, EDTA and its derivatives, laminaria extracts, o-linoleyl-6D-glucose, (3-hydroxy- 2-pentylcyclopentyl) acetic acid, glycerol trilactate, O-octanyl-6' -D-maltose, S-carboxymethyl cysteine, silicon-containing salicylate derivatives, such as those described in EP-O 796 861, oligofucases such as those described in patent EP-O 218 200, 5-acyl salicylic acid salts, active ingredients having effects on transglutaminase, such as those in patent EP- 0 899 330; ficus opuntia indica flower extract such as Exfolactive® from Silab; - 8-hexadecene 1, 16-dicarboxylic acid; esters of glucose and vitamin F; and mixtures thereof.
Preferred desquamating agents which may be cited are beta-hydroxyacids, such as n-octanoyl 5-salicylic acid; urea; glycolic, citric, lactic, tartaric, malic or mandelic acid; 4- (2-hydroxyethyl) piperazine-1- propanesulphonic acid (HEPES); Saphora japonica extract; honey; N-acetyl glucosamine; sodium methyl glycine diacetate, and mixtures thereof.
More preferably, the compositions of the invention will use a desquamating agent selected from n-octanoyl 5- salicylic acid; urea; 4- (2-hydroxyethyl) piperazine-1- propanesulphonic acid (HEPES); Saphora japonica extract; honey; N-acetyl glucosamine; sodium methyl glycine diacetate, and mixtures thereof.
3. Agents improving the barrier function
Particular agents which improve the barrier function which may be cited are arginine, serine, a Thermus thermophilus extract such as Venuceane® from Sederma, a wild yam rhizome extract (dioscorea villosa) such as Actigen Y® from Active Organics, plankton extracts such as omega plancton® from Secma, yeast extracts such as Relipidium® from Coletica, a chestnut extract such as Recoverine® from Silab, a cedar bud extract such as Gatuline Zen® from Gattefosse, sphingosines such as salicyloyl sphingosine sold under the trade name "Phytosphingosine® SLC" by Degussa, a mixture of xylitol, xylityl polyglycoside and xylitan such as Aquaxyl® from Seppic, solanacea extracts such as Lipidessence® from Coletica; unsaturated omega-3 oils such as musk rose oils, and mixtures thereof.
It is also possible to cite ceramides or derivatives, in particular type 2 ceramides (such as N- oleoyldihydrosphingosine) , type 3 ceramides (such as stearoyl-4-hydroxysphinganine, INCI name) and type 5 ceramides (such as N-2- hydroxypalmitoyldihydrosphingosine, with INCI name: hydroxypalmytoyl sphinganine) , compounds based on sphingoids, glycosphingolipids, phospholipids, cholesterol and its derivatives, phytosterols, essential fatty acids, diacylglycerol, 4-chromanone and chromone derivatives, vaseline, lanolin, shea butters, cocoa butter, lanolin, and PCA salts.
Preferred agents having a restructuring effect on the cutaneous barrier which may be cited are a Thermus thermophilus extract, a wild yam rhizome extract
(dioscorea villosa) , a yeast extract, a chestnut extract, a cedar bud extract, arginine, serine, and ceramides, in particular type 3 and 5; and mixtures thereof.
Preferably, serine, aginine or a mixture thereof is used.
4. Depigmenting agents
Depigmenting agents which may in particular be cited include vitamin C and its derivatives, in particular vitamin CG, CP and 3-0 ethyl vitamin C, alpha and beta arbutine, ferulic acid, lucinol and its derivatives, kojic acid, resorcinol and its derivatives, tranexamic acid and its derivatives, gentisic acid, homogentisate, methyl gentisate or homogentisate, dioic acid, D calcium pantheteine sulphonate, lipoic acid, ellagic acid, vitamin B3, linoleic acid and its derivatives, ceramides and their homologues, derivatives for plants such as camomile, bearberry, the aloe family (vera, ferox, bardensis) , mulberry, skullcap; Kiwi fruit water (Actinidia chinensis) sold by Gattefosse, a Paeonia suffructicosa root extract such as that sold by Ichimaru Pharcos under the trade name Botanpi Liquid B®, a brown sugar extract (Saccharum officinarum) , such as the molasses extract sold by Taiyo Kagaku under the trade name Molasses Liquid; this list is not exhaustive.
Preferred depigmenting agents which are used are vitamin C and its derivatives and in particular vitamin CG, CP and 3-0 ethyl vitamin C, alpha and beta arbutine, ferulic acid, kojic acid, resorcinol and its derivatives, D calcium pantheteine sulphonate, lipoic acid, ellagic acid, vitamin B3, Kiwi fruit water
(Actinidia chinensis) sold by Gattefosse, and a Paeonia suffructicosa root extract such as that sold by
Ichimaru Pharcos under the trade name Botanpi Liquid
B® .
5. Antioxidants It is also possible to cite tocopherol and its esters, in particular tocopherol acetate; ascorbic acid and its derivatives, in particular ascorbyl magnesium phosphate and ascorbyl glucoside; ferulic acid; serine; ellagic acid, phloretin, polyphenols, tannins, tannic acid, epoigallocathechins and natural extracts containing them, anthocyans, rosemary extracts, olive leaf extracts such as those from Silab, green tea extracts, resveratrol and its derivatives, ergothineine, N- acetylcysteine, an extract from the brown algae pelvetia canaliculata such as Pelvetiane® from Secma, chlorogenic acid, biotin, chelating agents such as BHT, BHA, N, N' -bis (3, 4 , 5-trimethoxybenzyl) ethylenediamine and its salts; idebenone, plant extracts such as Pronalen Bioprotect TM from Provital; co-enzyme QlO, bioflavonoids, SODs, phytantriol, lignanes, melatonin, pidolates, glutathione, caprylyl glycol, phloretin, Totarol™ or Podocarpus totara extract containing totarol (totara-8, 11, 13-trienol or 2-phenanthrenol, 4b, 5, 6, 7, 8, 8a, 9, 10-octahydro-4b, 8, 8-trimethyl- 1 (1-methylethyl) -; a jasmine extract such as that sold by SILAB under the trade name Helisun®; hesperitine laurate such as Flavagrum PEG® from Engelhard Lyon; a Paeonia suffructicosa root extract such as that sold by Ichimaru Pharcos under the trade name Botanpi Liquid B®; a lychee extact such as the lychee pericarp extract sold by Cognis under the trade name Litchiderm LS 9704®, a pomegranate (Punica Granatum) fruit extract, such as that sold by Draco Natural products. Other anti-ageing agents which may be cited are : DHEA and its derivatives, boswellic acid, rosemary extracts, carotenoids (B carotene, zeaxanthine, luteine) , cysteic acid, copper derivatives, jasmonic acid.
Preferred antioxidants which are used are: ferulic acid; serine; phloretin, a pomegranate extract, biotin, chelating agents such as BHT, BHA, N, N' -bis (3, 4, 5- trimethoxybenzyl) ethylenediamine and its salts, caprylyl glycol, phloretine, Totarol™, a jasmine extract such as that sold by SILAB under the trade name Helisun®; hesperitine laurate such as Flavagrum PEG® from Engelhard Lyon; and a Paeonia suffructicosa root extract such as that sold by Ichimaru Pharcos under the trade name Botanpi Liquid B® .
6. Dermorelaxants
Examples which may be cited are: manganese gluconate and other salts, adenosine, alverine citrate and its salts, glycine, an Iris pallida extract, a hexapeptide
(Argeriline R from Lipotec) or sapogenins such as Wild yam and carbonylated amines described in EP-I 484 052.
Examples of sapogenins which may be cited are those described in patent application WO-02/47650, in particular Wild yam, diosgenin extracted in particular from Dioscorea opposita or any extract comprising one or more sapogenins either naturally or after treatment
(wild yam rhizome, agave leaf which contains hecogenin and tigogenin, liliaceae extract and more particularly
Yacca or smilax containing smilageine and sarsapogenin, or sasparilla root) or Actigen Y from Active Organics; or ginger.
It is also possible to cite DMAE (dimethyl MEA) , criste marine extracts, ciste de Montpellier, curry plant, aniseed, Para cress, Acmella Oleracea extract such as Gatuline® from Gattefosse. Preferred dermorelaxants which may be cited are adenosine, manganese gluconate, wild yam, criste marine, glycine and alverine.
7. Anti-glycation agents
The term "anti-glycation" means a compound preventing and/or reducing the glycation of skin proteins, in particular proteins of the dermis such as collagen.
Anti-glycation agents which may in particular be cited are plant extracts from the Ericaceae family such as an extract from blueberries (Vaccinium angusfifollium, Vaccinium myrtillus) , for example that sold under the trade name "BLUEBERRY HERBASOL EXTRACT PG" by COSMETOCHEM, ergothioneine and its derivatives, hydroxystilbenes and their derivatives, such as resveratrol and 3, 3' , 5, 5' -tetrahydroxystilbene (these anti-glycation agents are described in applications FR- 2 802 425, FR-2 810 548, FR-2 796 278 and FR-2 802 420, respectively) , dihydroxystilbenes and their derivatives, arginines and lysine polypeptides such as that sold under the trade name "AMADORINE®" by SOLABIA, carcinine hydrochloride (sold by Exsymol under the trade name "ALISTIN®») , a Helianthus annuus extract such as Antiglyskin® from Silab, wine extracts such as powdered white wine extract on a maltodextrin support sold under the trade name "Vin blanc deshydrate 2F" by Givaudan, thioctic acid (or alpha lipoic acid) , a mixture of bearberry extract and marine glycogene such as Aglycal LS 8777® from Laboratoires Seriobiologiques, and a black tea extract such as Kombuchka® from Sederma and mixtures thereof.
Preferred anti-glycation agents which may be cited are blueberry extracts (Vaccinium myrtillus) and black tea extract . 8. Agents stimulating the synthesis of dermal and/or epidermal macromolecules and/or preventing their degradation :
Active ingredients which stimulate dermis macromolecules or prevent their degradation which may be cited are those which act:
- either on the synthesis of collagen, such as Centella asiatica extracts, asiaticosides and derivatives; ascorbic acid or vitamin C and its derivatives; synthesized peptides such as iamin, biopeptide CL or palmitoyloligopeptide sold by SEDERMA; peptides extracted from plants, such as soya hydrolysate sold by COLETICA under the trade name Phytokine®; rice peptides such as Nutripeptide® from SILAB, methylsilanol mannuronate such as Algisium C® sold by Exsymol; plant hormones such as auxins and lignans; folic acid; a
Medicago sativa (alfafa) extract such as that sold by SILBA under the trade name Vitanol®; a peptidic hazelnut extract such as that sold by Solabia under the trade name Nuteline C®; and arginine;
or on the inhibition of collagen degradation, in particular agents acting on the inhibition of metalloproteinases (MMP), more particularly MMP 1, 2,
3, 9 . It is possible to cite: retinoids and its derivatives, Medicago sativa extracts such as Vitanol® from Silab, an aphanizomenon flos-aquae (cyanophycea) extract sold under the trade name Lanablue® by Atrium
Biotechnologies, oligopeptides and lipopeptides, lipoaminoacids, malt extract sold by COLETICA under the trade name Collalift®; blueberry or rosemary extracts; lycopene; isoflavones, their derivatives or plant extracts containing them, in particular soya extracts
(sold, for example, by ICHIMARU PHARCOS under the trade name Flavosterone SB®) , red clover, linseed, kakkon; lychee extract such as the lychee pericarp extract sold by Cognis under the trade name Litchiderm LS 9704 13® DIPALMITOYL HYDROXYPROLINE sold by Seppic under the trade name SEPILIFT DPHP®: Baccharis genistelloide or
Baccharine sold by SILAB, an argan tree extract such as
Arganyl LS 9781® from Cognis; the sage extract described in FR-A-2 812 544 from the labia family
(salvia officinalis from Flacksmann) , Rhododendron extract, blueberry extract, a vaccinium myrtillus extract such as those described in FR-A-2 814 950;
- or on the synthesis of molecules belonging to the elastin family (elastin and fibrillin) such as: retinol and its derivatives, in particular retinol palmitate; the Saccharomyces Cerivisiae extract sold by LSN under the trade name Cytovitin®; and the Macrocystis pyrifera algae extract sold by SECMA under the trade name Kelpadelie®; or a peptidic hazelnut extract such as that sold by Solabia under the trade name Nuteline C®;
- or on inhibiting the degradation of elastin such as the peptide extract of Pisum sativum seeds sold by LSN under the trade name Parelastyl®; heparinoids; and the N-acylaminoamide compounds described in application WO- 01/94381, such as {2- [acetyl- (3-trifluoromethyl- phenyl) -amino] -3-methyl-butyrylamino} acetic acid, also denoted N-[N-acetyl, N '- (3-trifluoromethyl) phenyl valyl ] glycine or N-acetyl-N- [3-
(trifluoromethyl) phenyl] valyl-glycine or acetyl trifluoromethyl phenyl valylglycine, or an ester thereof with a Ci-Cβ alcohol; a rice peptides extract such as Colhibin® from Pentapharm, or a Phyllanthus emblica extract such as Emblica® from Rona;
- or on the synthesis of glycosaminoglycans, such as the product from fermenting milk with Lactobacillus vulgaris, sold by BROOKS under the trade name Biomin yogurt®; the brown algae Padina pavonica extract sold by ALBAN MULLER under the trade name HSP3®; the Saccharomyces cerevisiae extract available from SILAB under the trade name Firmalift® or from LSN under the trade name Cytovitin®; a Laminaria ochroleuca extract such as Laminaϊne® from Secma; Mamaku essence from Lucas Meyer, or a cress extract (Odraline® from Silab) ;
- or on the synthesis of fibronectin, such as the Salina zooplankton extract sold by SEPORGA under the trade name GP4G®; the yeast extract available in particular from ALBAN MULLER under the trade name Drieline®; and the palmitoyl pentapeptide sold by SEDERMA under the trade name Matrixil®.
Active ingredients stimulating epidermal macromolecules such as fillagrin and keratins which may be cited are the lupin extract sold by SILAB under the trade name Structurine®; Fagus sylvatica beech bud extract sold by GATTEFOSSE under the trade name Gatuline® RC; and the Salina zooplankton extract sold by SEPORGA under the trade name GP4G®; copper Tripeptide from PROCYTE; and a Voandzeia substerranea extract such as that sold by Laboratoires Serobiologiques under the trade name Filladyn LS 9397®.
Preferably, an active ingredient stimulating the synthesis of dermal and/or epidermal macromolecules and/or preventing their degradation is selected from agents stimulating the synthesis of glycosaminoglycans, agents inhibiting the degradation of elastin, agents stimulating the synthesis of fibronectin, agents stimulating the synthesis of epidermal macromolecules, and mixtures thereof.
Still more preferably, an active ingredient stimulating the synthesis of glycosaminoglycans is used which is selected from a brown algae Padina pavonica extract, a Saccharomyces cerevisiae extract, a Laminaria ochroleuca extract, Mamaku essence, a cress extract and mixtures thereof. Preferred active ingredients stimulating the synthesis of dermal and/or epidermal macromolecules and/or impeding their degradation which may be cited are: - synthesized peptides such as iamin, biopeptide CL or palmitoyloligopeptide sold by SEDERMA; peptides extracted from plants, such as the soya hydrolysate sold by COLETICA under the trade name Phytokine®; rice peptides such as Nutripeptide® from SILAB, methylsilanol mannuronate such as Algisium C® sold by Exsymol; folic acid; a Medicago sativa (alfafa) extract such as that sold by SILBA under the trade name Vitanol®; a peptidic hazelnut extract such as that sold by Solabia under the trade name Nuteline C®; arginine; an aphanizomenon flos-aquae (cyanophycea) extract sold under the trade name Lanablue® by Atrium Biotechnologies, malt extract sold by COLETICA under the trade name Collalift®; lycopene; a lychee extract; an argan tree extract such as Arganyl LS 9781® from Cognis; a vaccinium myrtillus extract such as those described in FR-A-2 814 950; retinol and derivatives, in particular retinol palmitate; the Saccharomyces Cerivisiae extract sold by LSN under the trade name Cytovitin®; a peptidic hazelnut extract such as that sold by Solabia under the trade name Nuteline C®; {2- [acetyl- (3-trifluoromethyl-phenyl) -amino] -3-methyl- butyrylamino} acetic acid, also denoted N-[N-acetyl, N '- (3-trifluoromethyl) phenyl valyl] glycine or N-acetyl- N- [ 3- ( trifluoromethyl) phenyl ] valyl-glycine or acetyl trifluoromethyl phenyl valylglycine, or an ester thereof with a Ci-Cβ alcohol; a rice peptides extract such as Colhibin® from Pentapharm, or a Phyllanthus emblica extract such as Emblica® from Rona; the brown algae Padina pavonica extract sold by ALBAN MULLER under the trade name HSP3®; the Saccharomyces cerevisiae extract available in particular from SILAB under the trade name Firmalift® or from LSN under the trade name Cytovitin®; a Laminaria ochroleuca extract such as Laminaϊne® from Secma; Mamaku essence from Lucas Meyer, lupin extract sold by SILAB under the trade name Structurine®; and Fagus sylvatica beech bud extract sold by GATTEFOSSE under the trade name Gatuline® RC.
9. Agents stimulating the proliferation of fibroblasts or keratinocytes and/or differentiation o_f keratinocytes
Examples of agents stimulating the proliferation of fibroblasts which may be used in the composition of the invention may, for example, be selected from plant proteins or polypeptides, in particular extracted from soya (for example a soya extract sold by LSN under the trade name Eleseryl SH-VEG 8® or sold by SILAB under the trade name Raffermine®) ; a hydrolyzed soya protein extract such as RIDULISSE® de SILAB; and plant hormones such as giberrellins and cytokinins; and a peptidic hazelnut extract such as that sold by Solabia under the trade name Nuteline C®.
Preferably, an agent promoting the proliferation and/or differentiation of keratinocytes is used.
Agents stimulating the proliferation of keratinocytes which may be used in the composition of the invention include adenosine; phloroglucinol, hydrangea macrophylla leaf extract such as Amacha liquid E® from
Ichimaru Pharcos, a yeast extract such as Stimoderm® from CLR; Larrea divaricata extract such as Capislow® from Sederma, mixtures of extracts from papaya, olive leaves and lemon such as Xyleine® from Vincience, hydrangea macrophylla leaf extract such as Amacha liquid E® from Ichimaru Pharcos, retinol and its esters including retinyl palmitate, phloroglucinol, walnut shell extracts sold by Gattefosse and solanum tuberosum extracts such as Dermolectine® sold by Sederma.
Examples of agents stimulating the differentiation of keratinocytes include, for example, minerals such as calcium; criste marine, a peptidic lupin extract such as that sold by SILAB under the trade name Structurine®; sodium beta-sitosteryl sulphate such as that sold by SEPORGA under the trade name Phytocohesine®; and a hydrosoluble corn extract such as that sold by SOLABIA under the trade name Phytovityl®; a Voandzeia substerranea extract such as that sold by Laboratoires Serobiologiques under the trade name Filladyn LS 9397®; and lignanes such as secoisolariciresinol, retinol and its esters including retinyl palmitate.
Further agents stimulating the proliferation and/or differentiation of keratinocytes which may be cited are oestrogens such as oestradiol and homologues; and cytokines .
Preferred active ingredients stimulating the proliferation of fibroblasts or keratinocytes and/or the differentiation of keratinocytes which may be cited are plant proteins or polypeptides, extracted primarily from soya (for example a soya extract sold by LSN under the trade name Eleseryl SH-VEG 8® or sold by SILAB under the trade name Raffermine®) ; a hydrolyzed soya protein extract such as RIDULISSE® from SILAB; a peptidic hazelnut extract such as that sold by Solabia under the trade name Nuteline C®; adenosine; phloroglucinol, a yeast extract such as Stimoderm® from CLR; a peptidic lupin extract such as that sold by SILAB under the trade name Structurine®; a hydrosoluble corn extract such as that sold by SOLABIA under the trade name Phytovityl®; a peptidic Voandzeia substerranea extract such as that sold by Laboratoires Serobiologiques under the trade name Filladyn LS 9397®; and retinol and its esters including retinyl palmitate.
10. Agents promoting maturation of the cornified envelope In the compositions of the invention, it is possible to use agents which are involved in maturation of the cornified envelope which changes with age and induces a reduction in transglutaminase activity. Examples which may be cited are urea and its derivatives, in particular Hydrovance® from National Starch and other active ingredients mentioned in L' OREAL λs application FR-2 877 220 (not published) .
11. NO-synthase inhibitors
The agent having an NO synthase inhibiting activity may be selected from PCOs (procyanidolic oligomers) ; plant extracts from the species Vitis vinifera, in particular those sold by Euromed under the trade name Leucocyanidines de raisins extra, or by Indena under the trade name Leucoselect®, or finally by Hansen under the trade name Extrait de marc de raisin; plant extracts from the species Olea europaea, preferably obtained from olive leaves and in particular sold by VINYALS in the dry form, or by Biologia & Technologia under the trade name Eurol® BT; extracts from the species Gingko biloba, preferably a dried aqueous extract from this plant sold by Beaufour under the trade name Ginkgo biloba extrait standard, and mixtures thereof .
12. Peripheral benzodiazepine receptor (PBR) antagonists
Examples which may be cited are 1- (2-chlorophenyl) -N-
( 1-methyl-propyl) -3-isoquinoline carboxamide; the compounds described in applications WO-03/030937,
WO-03/068753, and pyridazino [4, 5-b] indole-1-acetamide derivatives with general formula (VII) such as those described in document WO-00/44384.
13. Agents promoting sebaceous gland activity Examples which may be cited are methyl dehydroj asmonate, hecogenin, hedione, o-linoleyl-6D- glucose and mixtures thereof.
14. Agents stimulating cell energy metabolism
The active ingredient stimulating cell energy metabolism may, for example, be selected from biotin, an extract from Saccharomyces cerevisiae such as Phosphovital® from Sederma, a mixture of sodium, manganese, zinc and magnesium salts of pyrrolidone carboxylic acid such as Physiogenyl® from Solabia, a mixture of zinc, copper and magnesium gluconate such as Sepitonic M3® from Seppic and mixtures thereof; and a beta-glucan derived from Saccharomyces cerevisiae, such as that sold by Mibelle AG Biochemistry.
15. Tightening agents
The term "tightening agent" as used in the context of the invention means compounds which may have a tightening effect, i.e. which may tense the skin.
In general, the term "tightening agent" as used in the context of the invention means any compounds which are soluble in or dispersible in water at a temperature of
25°C to 500C at a concentration of 7% by weight in water or at the maximum concentration at which they form a medium which appears homogeneous and producing at this concentration of 7% or at this maximum concentration in water a retraction of more than 15% in the test described below.
The maximum concentration at which a medium which is homogeneous in appearance is determined to ± 10% and preferably to ± 5%. The term "medium with a homogeneous appearance" means a medium which does not have any aggregates which are visible to the naked eye.
To determine said maximum concentration, the tightening agent is slowly added to water with stirring using a deflocculator at a temperature of 25°C to 500C, then the mixture is stirred for one hour. After 24 hours, observations are made to ascertain whether the mixture which has been prepared has a homogeneous appearance (absence of aggregates which are visible to the naked eye) .
The tightening effect may be characterized by an in-vitro shrinkage test.
A mixture is prepared as described above which is a homogeneous mixture of the tightening agent in water at a concentration of 7% by weight or at the maximum concentration defined above.
30 μl of the homogeneous mixture is deposited on a rectangular specimen (10 x 40 mm, thus with an initial width at LO of 10 mm) of elastomer having an elastic modulus of 20 MPa and a thickness of 100 μm.
After drying for 3 h at 22±3°C and 40+10% relative humidity HR, the elastomer specimen has a retracted width, denoted L3h, due to the tension exerted by the deposited tightening agent.
The tightening effect (TE) of said agent is then quantified as follows: "TE" = (LO - L3h/L0) x 100, as a %; where LO = initial width, 10 mm and L3h = width after drying for 3h.
The tightening agent may be selected from: plant or animal proteins and their hydrolysates; polysaccharides of natural origin; mixed silicates; colloidal particles of inorganic fillers; synthetic polymers; and mixtures thereof.
The skilled person will be capable of selecting, from the chemical categories listed above, the materials which satisfy the tightening test described above.
The following may in particular be cited: (a) proteins and hydrolysates of plant proteins, in particular of corn, rye, wheat, buckwheat, sesame, spelt, pea, broad bean, lentil, soya and lupin; (b) polysaccharides of natural origin, especially (a) polyholosides, for example (i) in the form of starch in particular derived from rice, corn, potato, cassava, pea, wheat, oats, etc; or (ii) in the form of carragheenans, alginates, agars, gellanes, cellulosic polymers and pectins, advantageously in an aqueous dispersion of gel microparticles, and (b) latexes constituted by shellac resin, sandarac gum, dammars, elemi, copals, cellulosic derivatives and mixtures thereof; (c) mixed silicates, especially phyllosilicates and in particular laponites;
(d) colloidal inorganic filler particles with a number average diameter in the range 0.1 to 100 nm, preferably in the range 3 to 30 nm, and selected, for example, from: silica, silica-alumina composites, cerium oxide, zirconium oxide, alumina, calcium carbonate, barium sulphate, calcium sulphate, zinc oxide and titanium dioxide. Examples of composite silica-alumina colloidal particles which may be used in the compositions of the invention which may be cited are those sold by Grace with the names Ludox AM, Ludox AM-X 6021, Ludox HSA and Ludox TMA.
(e) synthetic polymers, such as polyurethane latexes or acrylic-silicone latexes, in particular those described in patent application EP-A-I 038 519, such as a propylthio (polymethyl acrylate) , propylthio (polymethyl methacrylate) or propylthio (polymethacrylic acid) grafted polydimethylsiloxane, or a propylthio (polyisobutyl methacrylate) or propylthio (polymethacrylic acid) grafted polydimethylsiloxane. Such grafted silicone polymers are in particular sold by 3M under the trade names VS 80, VS 70 or LO21 .
The tightening agent is present in the composition in a quantity which is effective to obtain the desired biological effect in accordance with the invention.
As an example, the tightening agent may be included in the composition of the invention in an amount of 0.01% to 30% by weight of active substance, preferably 1% to 30% by weight of active substance, with respect to the total composition weight.
The term "active substance" is intended to exclude the medium in which the tightening agent is optionally dissolved or in dispersion in its commercially available form, for example in the case of dispersions of colloidal particles.
It is also possible to use, in particular to complement and/or potentialize the effect of tightening agents, agents which promote the expression of mechanoreceptors, such as agents promoting the expression of integrins . As an example, a rye seed extract may be cited, such as that sold SILAB under the trade name Coheliss©.
16. Liporestructuring agents
The term "liporestructuring agents" as used in the invention means agents which are capable of stimulating lipogenesis and promoting adipocyte differentiation, thereby avoiding or slowing the melting of fats contained in the skin support tissues, also termed "melting of the skin lipostructure" .
The term "skin lipostructure" means the network of lipid cells which forms volumes on which the skin of the face rests and to which it moulds.
These agents are intended to reduce the loss of skin density and/or melting of the lipostructure of the skin, in particular at the cheeks and the contour of the eye, and/or to avoid sinking and/or hollowing of the curves of the face, a loss of consistency of the skin and/or its support, in particular at the cheeks and the contour of the eye, and/or to improve the supports which subtend the skin of the face and/or the neck, in particular at the cheeks, the outline of the face and the contour of the eye, and/or to improve the density, resilience and support of the skin, in particular at the cheeks, the outline of the face and the contour of the eye, and/or to remodel the lines of the face, in particular the outline of the face.
Examples of liporestructuring agents which may be cited are black tea extract, such as fermented black tea extract sold by Sederma under the trade name Kombuchka®, and an extract of Artemesia abrotanum, such as that sold by Silab under the trade name Pulpactyl®.
17. Slimming agents
Slimming agents (lipolytic agents) which may in particular be cited are caffeine, theophyllin and its derivatives, theobromine, sericosine, asiatic acid, acefylline, aminophylline, chloroethyltheophylline, diprofylline, diniprophylline, etamiphylline and its derivatives, etofylline, proxyphylline; tea, coffee, guarana, mate, cola (Cola Nitida) extracts and in particular dry guarana fruit extract (Paulina sorbilis) containing 8% to 10% of caffeine; extracts of common ivy (Hedera helix) , arnica (Arnica montana L) , rosemary
(Rosmarinus officinalis N) , marigold (Calendula officinalis), sage (Salvia officinalis L), ginseng (Panax ginseng), St John's Wort (Hypericum perforatum), broom (Ruscus aculeatus L) , meadowsweet (Filipendula ulmaria L) , big-flowered Java tea (Orthosiphon stamincus Benth) , birch (Betula alba) , cecropia and argan tree; ginkgo biloba extracts, horsetail extracts, escine extracts , cangzhu extracts, Chrysanthellum indicum extracts, extracts from dioscoria rich in diosgenine or diosgenine or pure hecogenine and their derivatives, Ballote extracts, Guioa extracts, Davallia, Terminalia, Barringtonia, Trema, Antirobia extracts, Seville orange pip extract; coconut shell extract (theobroma cacao) such as that sold by Solabia under the trade name Caobromine®.
18. Agents promoting cutaneous microcirculation
The active ingredient acting on cutaneous microcirculation may be used to avoid fading of the skin and/or to improve the appearance of the eye contour, and in particular to reduce blemishes. It may, for example, be selected from a maritime pine bark extract such as Pycnogenol® from Biolandes, manganese gluconate (Givobio GMn® from Seppic) , an extract of Ammi visnaga such as Visnadine from Indena, lupin extract (Eclaline® from Silab) , hydrolyzed wheat protein/ palmitic acid coupled with palmitic acid such as Epaline 100 from Laboratoires Carilene, Seville orange flower extract (Remoduline® from Silab) , vitamin P and its derivatives such as sodium methyl-4 esculetol mono-ethanoate sold under the trade name Permethol® by Sephytal, ruscus extracts, horse chestnut extracts, ivy extract, ginseng extract and melilot extract, caffeine, nicotinate and its derivatives, lysine and its derivatives such as Asparlyne® from Solabia, a black tea extract such as Kombuchka from Sederma; rutine salts: an extract of corallina officinalis algae such as that sold by CODIF; and mixtures thereof.
Preferred agents promoting cutaneous microcirculation which may be cited are, caffeine, Seville orange flower extract, black tea extract, rutine salts, and corallina officinalis algae extract.
19. Soothing agents or anti-irritants
The term "soothing agent" means a compound which can reduce the sensation of tingling, itching or pulling of the skin.
Examples of soothing agents which may be used in the composition of the invention which may be cited are: procyannidolic oligomers, vitamins E, C, B5, B3, caffeine and its derivatives, pentacyclic triterpenes and extracts from plants containing them, β- glycyrrhetinic acid and its salts or derivatives
(stearyl glycyrrhetate, 3-stearoyloxy glycyrrhetic acid, glycyrrhetinic acid monoglucuronide) as well as plants containing them (for example: Glycyrrhiza glabra) , oleanolic acid and its salts, ursolic acid and its salts, boswellic acid and its salts, betulinic acid and its salts, a Paeonia suffruticosa and/or lactiflora extract, a Laminaria saccharina extract, Centella asiatica extracts, Canola oil, bisabolol, the phosphoric diester of vitamin E and C such as Sepivital EPC® from Seppic, camomile extracts, allantoin, omega-3 unsaturated oils such as musk rose oil, blackcurrant, Ecchium oil, fish oil, calophilum oil, plankton extracts, capryloyl glycine, a mixture of water lily flower oil and palmitoylproline such as that sold under the trade name "Seppicalm VG®" by Seppic, a Boswellia serrata extract, a Centipeda cunnighami extract such as that sold under the trade name "Cehami PF®" by TRI-K Industries, a sunflower seed extract, in particular Helioxine® from Silab, a Linum usitatissimum seed extract such as Sensiline® from Silab, tocotrienols, piperonal, an Epilobium angustifolium extract such as that sold under the trade name "Canadian Willowherb Extract" by FYTOKEM PRODUCTS, aloe vera, phytosterols, blueberry water, rose water, mint extract, in particular from mint leaves such as Calmiskin® from Silab, anis derivatives, filamentous bacteria such as Vitreoscilla filiformis as described in EP-O 761 204 and sold by Chimex under the trade name Mexoryl SBG®, a rose petal extract such as Rose Flower Herbasol ® extract from Cosmetochem, shea butter oil, a mixture of the wax fraction of barley grain obtained using supercritical CO2, shea butter and argan tree oil, such as "Stimu-tex AS®" from Pentapharm, salts of alkaline earths such as strontium, a fermented extract from Alteromonas sold under the trade name ABYSSINE® by Atrium Biotechnologies; thermal water from the Vichy basin, such as water deriving from the Celestins, Chomel, Grande-Grille, Hδpital, Lucas and Pare sources, and preferably water from the Lucas source; an Eperua falcata bark extract such as that sold by COGNIS under the trade name Eperuline®; a Paeonia suffructicosa root extract such as that sold by Ichimaru Pharcos under the trade name Botanpi Liquid B®; and mixtures thereof.
Preferred soothing agents used in accordance with the invention are: β-glycyrrhetinic acid and its salts or derivatives (stearyl glycyrrhetate, 3-stearoyloxy glycyrrhetic acid, glycyrrhetinic acid monoglucuronide) and plants containing them (for example: Glycyrrhiza glabra); ursolic acid and its salts; Centella asiatica extracts, Canola oil, bisabolol; camomile extracts, allantoin; a mixture of water lily flower extract and palmitoylproline such as that sold under the trade name "Seppicalm VG®" by Seppic; aloe vera, rose water, mint extract, in particular from mint leaves such as Calmiskin® from Silab, filamentous bacteria such as Vitreoscilla filiformis as described in patent EP-O 761 204 and sold by Chimex under the trade name Mexoryl SBG®, a rose petal extract such as Rose Flower Herbasol® extract from Cosmetochem, shea butter oil, a fermented extract from Alteromonas sold under the trade name ABYSSINE® by Atrium Biotechnologies; thermal water from the Vichy basin such as that from the Celestins, Chomel, Grande-Grille, Hδpital, Lucas and Pare sources, and preferably water from the Lucas source; an Eperua falcata bark extract such as that sold by COGNIS under the trade name Eperuline®; and a Paeonia suffructicosa root extract such as that sold by Ichimaru Pharcos under the trade name Botanpi Liquid B®; and mixtures thereof .
20. Sebo-regulating or anti-seborrheic agents
The terms "sebo-regulating or anti-seborrheic agent" means agents which are capable of regulating the activity of sebaceous glands.
The following may in particular be cited:
- retinoic acid, benzoyl peroxide, sulphur, vitamin B6 (or pyridoxine) , selenium chloride, criste marine;
- mixtures of cinnamon, tea and octanoylglycine extract such as Sepicontrol A5 TEA® from Seppic;
- mixture of cinnamon, sarcosine and octanoylglycine, sold by SEPPIC under the trade name Sepicontrol A5®;
- zinc salts such as zinc gluconate, zinc pyrrolidone carboxylate (or zinc pidolate) , zinc lactate, zinc aspartate, zinc carboxylate, zinc salicylate, zinc cysteate; copper derivatives, and in particular copper pidolate, such as Cuivridone® from Solabia; plant extracts from the species Arnica montana, Cinchona succirubra, Eugenia caryophyllata, Humulus lupulus, Hypericum perforatum, Mentha piperita,
Rosmarinus officinalis, Salvia oficinalis and Thymus vulgaris, all sold, for example, by MARUZEN; - European meadowsweet extracts (spiraea ulamaria) such as that sold under the trade name Sebonormine® by Silab; laminaria saccharina algae extracts, such as that sold under the trade name Phlorogine® by Biotechmarine; mixtures of pimpernel root (sanguisorba officinalis/poterium officinale) , ginger rhizomes
(zingiber officinalis) and cinnamon bark (cinnamomum cassia) such as that sold under the trade name Sebustop® by Solabia;
- linseed extracts such as that sold under the trade name Linumine® by Lucas Meyer;
- Phellodendron extracts such as those sold under the trade name Phellodendron extract BG by Maruzen or Oubaku liquid B by Ichimaru Pharcos;
- mixtures of argan tree oil, serenoa serrulata (saw palmetto) extract and sesame seed extract, such as that sold under the trade name Regu SEB® by Pentapharm;
- mixtures of epilobe, terminalia chebula, capucine and bioavailable zinc (microalgae) extracts such as that sold under the trade name Seborilys® by green tech;
- extracts of Pygeum afrianum such as that sold under the trade name Pygeum afrianum sterolic lipid extract by Euromed; - serenoa serrulata extracts such as those sold under the trade name Viapure Sabal by Actives International, or those sold by Euromed;
- mixtures of extracts of plantain, berberis aquifolium and sodium salicylate such as that sold under the trade name Seboclear® by Rahn;
- clove extracts such as that sold under the trade name Clove extract Powder by Maruzen;
- argan tree oil such as that sold under the trade name Lipofructyl® by Laboratoires Serobiologiques; - lactic protein filtrates such as that sold under the trade name Normaseb® by Sederma;
- laminaria algae extracts, such as that sold under the trade name Laminarghane® by Biotechmarine; - oligosaccharides from the algae laminaria digitata such as that sold under the trade name Phycosaccharide AC by Codif;
- cane sugar extracts such as that sold under the trade name Policosanol® by Sabinsa;
- sulphonated schist oil, such as that sold under the trade name Ichtyol Pale® by Ichthyol; extracts of meadowsweet (spiraea ulmaria) such as that sold under the trade name Cytobiol® Meadowsweet by Libiol;
- sebacic acid, in particular sold in the form of a sodium polyacrylate gel under the trade name Sebosoft® by Sederma; glucomannans extracted from konjac tubers and modified by alkylsulphonate chains such as that sold under the trade name Biopol Beta by Arch Chemical;
- extracts of Sophora angustifolia, such as those sold under the trade name Sophora powder or Sophora extract by Bioland; - extracts of cinchona succirubra bark such as that sold under the trade name Red bark HS by Alban Muller; extracts of quillaja saponaria such as that sold under the trade name Panama wood HS by Alban Muller;
- glycine grafted onto an undecylenic chain, such as that sold under the trade name Lipacid UG OR by Seppic; the mixture of oleanolic acid and nordihydroguaiaretic acid, such as that sold in the form of a gel under the trade name AC. Net by Sederma;
- phthalimidoperoxyhexanoic acid; - (C12-C13) trialkyl citrate sold under the trade name COSMACOL® ECI by Sasol; (Ci4-Ci5) trialkyl citrate sold under the trade name COSMACOL® ECL by Sasol;
- 10-hydroxydecanoic acid, and in particular mixtures of 10-hydroxydecanoic acid, sebacic acid and 1,10- decandiol such as that sold under the trade name Acnacidol® BG by Vincience; and
- mixtures thereof. Preferred anti-seborrheic agents which may be cited are :
- benzoyl peroxide, vitamin B6 (or pyridoxine) ;
- zinc salts such as zinc gluconate, zinc pyrrolidone carboxylate (or zinc pidolate) , zinc lactate, zinc aspartate, zinc carboxylate, zinc salicylate, zinc cysteate;
- extracts of European meadowsweet (spiraea ulamaria) such as that sold under the trade name Sebonormine® by Silab;
- extracts of laminaria saccharina algae such as that sold under the trade name Phlorogine® by Biotechmarine;
- mixtures of extracts of pimpernel root (sanguisorba officinalis/poterium officinale) , ginger rhizomes (zingiber officinalis) and cinnamon bark (cinnamomum cassia) such as that sold under the trade name Sebustop® by Solabia;
- clove extract such as that sold under the trade name Clove extract Powder by Maruzen; - lactic protein filtrates such as that sold under the trade name Normaseb® by Sederma;
- meadowsweet (spiraea ulmaria) extracts such as that sold under the trade name Cytobiol® Meadowsweet by Libiol ; - sebacic acid, in particular sold in the form of a sodium polyacrylate gel under the trade name Sebosoft® by Sederma; glycine grafted onto an undecylenic chain such as that sold under the trade name Lipacid UG OR by Seppic; - (C12-C13) trialkyl citrate sold under the trade name COSMACOL® ECI by Sasol; (Ci4-Ci5) trialkyl citrate sold under the trade name COSMACOL® ECL by Sasol;
- 10-hydroxydecanoic acid, and in particular mixtures of 10-hydroxydecanoic acid, sebacic acid and 1,10- decandiol such as that sold under the trade name Acnacidol® BG by Vincience;
- and mixtures thereof.
Preferably, the anti-seborrheic agent is selected from: - zinc salts such as zinc gluconate, zinc pyrrolidone carboxylate (or zinc pidolate) , zinc lactate, zinc aspartate, zinc carboxylate, zinc salicylate, zinc cysteate; and preferably zinc pyrrolidone carboxylate (or zinc pidolate) or zinc salicylate;
- clove extract such as that sold under the trade name Clove extract Powder by Maruzen;
- glycine grafted onto an undecylenic chain, such as that sold under the trade name Lipacid UG OR by Seppic; - (C12-C13) trialkyl citrate sold under the trade name COSMACOL® ECI by Sasol; (Ci4-Ci5) trialkyl citrate sold under the trade name COSMACOL® ECL by Sasol;
- and mixtures thereof.
The anti-seborrheic agent is, for example, present in an amount of 0.1% to 10% by weight, preferably 0.1% to 5% by weight, and preferably 0.5% to 3% by weight, with respect to the total composition weight.
21. Astringent agents
The term "astringent agents" as used in the invention means agents which can combat the dilation of sebaceous follicles .
Astringent agents which may be used in the composition of the invention which may be cited are extracts from mushroom pulp (polyporus officinalis) such as "Laricyl LS8865®" from Cognis, extracts from Terminalia catappa and sambucus nigra such as Phytofirm LS9120® from Cognis, nut gall extracts such as Tanlex VE® from Ichimaru Pharcos, aluminium hydroxychloride, extracts of centella (for example Plantactiv centella from Cognis), dicetyl dimethyl ammonium chloride such as Varisoft 432 CG® from Degussa, extracts of horse chestnut, extracts of mallow, Hammamelis extracts, sweet almond extracts, extracts from marsh mallows and from linseed such as Almondermin LS 3380® from Cognis, extracts of bardane, nettle extracts, birch extracts, horsetail extracts, camomile extracts such as those sold under the trade name Extrapone 9 special® by
Symrise, Scutellaria extracts, Meadowsweet extracts
(for example Cytobiol Meadowsweet de Libiol) , a mixture of extracts of white ginger, horsetail, nettle, rosemary, yucca such as Herb extract B1348® from Bell flavors & fragrances, acacia extracts, elm, white willow, cinnamon, birch, European meadowsweet, panama sapogenins, zinc phenolsulphonate from Interchemical, extracts from gentian, cucumber, walnut, a mixture of extracts of Ratanhia, grapefruit, grindelia and oak apple such as Epilami® from Alban Muller.
Preferred astringent agents for use in the invention are extracts of Scutellaria, extracts of meadowsweet, extracts of European meadowsweet, extracts of gentian, extracts of bardane and mixtures thereof.
22. Healing agents
Particular examples of healing agents which may be cited are: allantoin, urea, certain amino acids such as hydroxyproline, arginine, serine, and also white lily extracts (such as Phytelene Lys 37EG 16295 from Indena) , a yeast extract such as the LS LO/7225B healing agent from Laboratoires Seriobiologiques) , tamanu oil, saccharomyces cerevisiae extract such as Biodynes® TRF® from Arch Chemical, oat extracts, chitosan and derivatives such as chitosan glutamate, carrot extracts, artemia extract such as GP4G® from Vincience, sodium acexamate, lavender extracts, propolis extracts, ximeninic acid and its salts, rosa rugosa oil, extracts from marigold such as Marigold Ami® Liposoluble from Alban Muller, extracts from horsetail, lemon peel extracts such as Herbasol® lemon from Cosmetochem, curry plant extracts, extracts from yarrow, and folic acid. Preferred healing agents which may be used in the invention are arginine, serine, folic acid, tamanu oil, sodium acexamate, extracts from horsetail, curry plant extracts, and mixtures thereof.
23. Anti-inflammatories
Particular anti-inflammatories which may be used in accordance with the invention which may be cited are cortisone, hydrocortisone, indomethacine, betamethasone, azealic acid, acetominophene, diclofenac, clobetasol propionate, folic acid; an Eperua falcata bark extract such as that sold by COGNIS under the trade name Eperuline®; a Paeonia suffructicosa root extract such as that sold by Ichimaru Pharcos under the trade name Botanpi Liquid B®; and mixtures thereof.
Preferred anti-inflammatories which may be cited are azelaic acid, folic acid, Eperua falcata bark extract such as that sold by COGNIS under the trade name Eperuline®; a Paeonia suffructicosa root extract such as that sold by Ichimaru Pharcos under the trade name Botanpi Liquid B®; and mixtures thereof.
24. Anti-acne agents
In an advantageous aspect of the invention, the composition may also comprise at least one anti-acne agent.
The term "anti-acne agent" means any active ingredient which has effects on the specific flora of oily skin, such as Propionibacterium acnes (P acnes), for example.
These effects may be bactericidal.
Anti-bactericidal agents which may in particular be cited are as follows: the active ingredients and preservatives with an anti-microbial activity cited in application DE-103 24 567, hereby incorporated into the present invention by reference; - asiatic acid; the monoethanolamine salt of l-hydroxy-4-methyl 6- trimethylpentyl 2-pyridone (INCI name: piroctone olamine) , in particular that sold under the trade name Octopirox® by Clariant; - citronellic acid, perillic acid (or 4- isopropenylcyclohex-1-enecarboxylic acid) ; glycerol 2-ethyl hexyl ether (INCI name: ethylhexylglycerine) , for example that sold under the trade name Sensiva SC 50® by Shulke & Mayr; - glyceryl caprylate/caprate, for example that sold under the trade name Capmul MCM® by ABITEC; calcium and sodium phosphosilicate, in particular that sold under the trade names Bioactive glasspowder® and Actysse Premier BG® by Schott Glass; - silver-based particles, for example that sold under the trade name Metashine ME 2025 PS® by Nippon Sheet Glass; hop (Humulus Lupulus) extract obtained by supercritical CO2 extraction, such as that sold under the trade name HOP CO2-TO extract® by Flavex Naturextrakte,
- extract of Millepertius obtained by supercritical CO2 extraction, such as that sold under the trade name St John's Wort CO2-TO extract® by Flavex Naturextrakte; - the mixture of Scutellaria baicalensis, paeonia suffruticosa and glycyrrhiza glabra root extracts, such as that sold under the trade name BMB - CF® by Naturogin; argan tree extract such as Argapure LS9710 from COGNIS;
- bearberry leaf extracts such as that sold under the trade name "Melfade-J" by Pentapharm;
- 10-hydroxy-2 decanoic acid such as Acnacidol P® from Vincience, sodium ursolate, azelaic acid, di-iodo- methyl p-tolylsulphone such as Amical Flowable® from
Angus, malachite powder, zinc oxide such as Zincare ® from Elementis GmbH, octadecenedioic acid such as
Arlatone dioic DCA® from Uniqema; ellagic acid; 2,4,4'- trichloro-2' -hydroxy diphenyl ether (or triclosan) , 1-
(3' , 4 ' -dichlorophenyl) -3- (4 ' -chlorophenyl) urea (or triclocarban) , 3, 4, 4' -trichlorocarbanilide, 3', 4', 5'- trichlorosalicylanilide, phenoxyethanol, phenoxypropanol, phenoxyisopropanol, hexamidine isethionate, metronidazole and its salts, miconazole and its salts, itraconazole, terconazole, econazole, ketoconazole, saperconazole, fluconazole, clotrimazole, butoconazole, oxiconazole, sulphaconazole, sulconazole, terbinafine, ciclopirox, ciclopiroxolamine, undecylenic acid and its salts, benzoyl peroxide, 3-hydroxy benzoic acid, 4-hydroxy benzoic acid, phytic acid, N-acetyl-L- cysteine, lipoic acid, azelaic acid and its salts, arachidonic acid, resorcinol, 3,4,4'- trichlorocarbanalide, octoxyglycerine or octoglycerine, octanoylglycine such as Lipacid C8G® from Seppic, caprylyl glycol, lO-hydroxy-2-decanoic acid, dichlorophenyl imidazole dioxolan and its derivatives described in patent application WO-93/18743, iodopropynyl butylcarbamate, 3, 7, 11-trimethyldodeca- 2, 5, 10-trienol or farnesol, phytosphingosines; quaternary ammonium salts such as cetyltrimethylammonium salts, or cetylpyridinium salts, and - mixtures thereof.
It is also possible to cite certain surfactants with an antimicrobial effect, such as sodium cocoamphoacetate or disodium diacetate such as Miranol C2M CONC NP, betaines such as cocoyl betaine Genagen KB from Clariant, sodium lauryl ether sulphate such as Emal 270 D from Kao, decyl glucoside such as Plantacare 2000 UP, branched C12-C13 dialcohol malates such as Cosmacol EMI, propylene glycol monoesters such as propylene glycol monolaurate, monocaprylate, monocaprate, lauryl dimethylamine betaine such as Empigen BB/LS as well as quaternary polyammoniums such as Quaternium-24 or Bardac 2050 from Lonza and those described in FR 0 108 283, and mixtures thereof.
Preferred antimicrobial agents which may be used in the compositions of the invention are agents selected from octoglycerine and octoxyglycerine, 10-hydroxy-2- decanoic acid, and mixtures thereof.
Other additional anti-acne agents may be added to the anti-acne agents cited above.
In particular, it is possible to cite agents having bacterial anti-adhesion effects or which act on the bacterial biofilm to prevent them from multiplying.
Particular agents preventing and/or reducing the adhesion of micro-organisms which may be cited are: phytanetriol and its derivatives as described in patent application EP-I 529 523, vegetable oils such as wheat germ oil, calendula oil, castor oil, olive oil, avocado oil, sweet almond oil, peanut oil, jojoba oil, sesame seed oil, apricot kernel oil, sunflower seed oil, or macadamia nut oil described in patent EP-I 133 979, or certain surfactants such as disodium cocoamphodiacetate, oxyethylenated (7 OE) glyceryl cocoate, hexadecenylsuccinate 18, octoxyglyceryl palmitate, octoxyglyceryl behenate, dioctyl adipate, PPG-15 stearyl ether, branched Ci2-Ci3 di-alcohol tartrate described in patent EP-I 129 694, and mixtures thereof .
Regarding the propagation of P acne in particular, or as active ingredients acting on the bacterial biofilm to prevent their proliferation, the following may be cited : pentylene glycol, nylon-66 (fibres of polyamide 66) , castor oil, polyvinyl alcohol such as Celvol 540 PV alcohol® from Celanese Chemical, rapeseed oil such as Akorex L® from Karlshamns, and fructose derivatives and mixtures thereof.
The active ingredient countering acne may be present in an amount of 0.01% to 10% by weight, preferably 0.05% to 5% by weight with respect to the total composition weight .
Depending on the nature and/or solubility of the active ingredients cited above, the skilled person will select the implementation which is most adapted to the invention .
Lipophilic active ingredients which may be used in the kit or in at least one of the compositions of the invention which may in particular be cited are D-α- tocopherol, DL-α-tocopherol, D-α-tocopherol acetate, DL-α-tocopherol acetate, ascorbyl palmitate, vitamin F glycerides, the vitamin D group, vitamin D2, vitamin D3, retinol, retinol esters, retinol palmitate, retinol propionate, carotenes including β carotene, D- panthenol, farnesol, farnesyl acetate, salicylic acid and its derivatives such as n-octanoyl-5 salicylic acid, α-hydroxyacid alkyl esters such as citric acid, lactic acid, glycolic acid, asiatic acid, madecassic acid, asiaticoside, centella asiatica total extract, β- glycyrrhetinic acid, α-bisabolol, ceramides such as 2- oleoylamino-1, 3-octadecane, phytanetriol, phospholipids of marine origin rich in essential polyunsaturated fatty acids, ethoxyquine, rosemary extract, melissa extract, quercetin, dry microalgae extracts, essential bergamot oil, octylmethoxycinnamate, butylmethoxydibenzoylmethane, octyl triazone, 3,5-di- tertiobutyl-4 -hydroxy-3-benzylidene camphor, antibiotics, antifungals, anaesthetics, analgesics, antiseptics, antivirals, pesticides, herbicides, and mixtures thereof. The cosmetic and/or dermatological agents are present in the kit or one of the compositions of the invention in an amount of 0.001% to 20% by weight with respect to the total composition weight, preferably in the range 0.01% to 10%, more preferably in the range 0.5% to 5% and still more preferably in the range 0.1% to 1% by weight with respect to the total composition weight.
For peeling applications, the amounts of cosmetic and/or dermatological agents may be from 1% to 50% by weight with respect to the total composition weight, preferably 1% to 30% by weight with respect to the total composition weight.
Peeling is a well known method for improving the appearance and/or texture of the skin and/or scalp, in particular of improving radiance and homogeneity of the skin and/or of reducing visible and/or tactile irregularities in the skin, and in particular of improving the surface appearance of the skin surface, to reduce actinic lentigo, acne or chicken pox scars and to prevent, reduce or combat the signs of skin ageing, and in particular to smooth out irregularities in the texture of the skin such as wrinkles and fine lines.
They remove a surface portion of the skin to be treated (epidermis and possibly a superficial layer of the dermis) using chemical methods.
OTHER ADDITIONAL INGREDIENTS
In order to supplement and/or optimize the effects endowed on the keratinous materials by the cosmetic and/or dermatological agents cited above, it may be advantageous to integrate other additional ingredients into the compositions of the invention. In particular, these additional ingredients may provide an immediate visual effect which will be relayed by the biological effect of the active ingredients cited above. They may also, via a mechanical action (for example: abrasive fillers) amplify the effect of the biological agents cited above.
Thus, the composition of the invention may also comprise at least one agent selected from mattifying agents, fillers with a soft-focus effect, fluorescent agents, agents promoting the natural pink colour of the skin, abrasive fillers or exfoliating agents and mixtures thereof.
Mattifying agents
The term "mattifying agent" means agents which are intended to render the skin visibly more matt, and less shiny.
The mattifying effect of the agent and/or the composition containing it may in particular be evaluated using a gonioreflectometer, by measuring the ratio R between the specular reflection and the diffuse reflection. A value for R of 2 or less is generally considered to be a mattifying effect.
The mattifying agent may in particular be selected from a rice starch or corn starch, kaolinite, talc, a pumpkin seed extract, cellulose microbeads, plant fibres, synthetic fibres, in particular polyamides, microspheres of expanded acrylic copolymers, polyamide powders, silica powders, polytetrafluoroethylene powders, silicone resin powders, acrylic polymer powders, powdered waxes, polyethylene powders, cross- linked organopolysiloxane elastomer powders coated with silicone resin, composite talc/titanium dioxide/alumina/silica powders, mixed amorphous silicate powders, silicate particles in particular of mixed silicates, and mixtures thereof.
Particular examples of mattifying agents which may be cited are: rice or corn starch, in particular an octenyl succinate aluminium starch sold under the trade name Dry Flo® by National Starch;
- kaolinite; - silicas;
- talc;
- a pumpkin seed extract such as that sold under the trade name Curbilene® by Indena; cellulose microbeads such as those described in patent application EP-I 562 562; fibres, such as silk, cotton, wool, linseed, cellulose extracted from wood in particular, plant or algae fibres, polyamide (Nylon®) , modified cellulose, poly-p-phenylene terephthamide, acrylic, polyolefin, glass, silica, aramide, carbon, Teflon®, insoluble collagen, polyesters, polyvinyl or vinylidene chloride, polyvinyl alcohol, polyacrylonitrile, chitosan, polyurethane, polyethylene phthalate, fibres formed from a mixture of polymers, resorbable synthetic fibres, and mixtures thereof described in patent application EP-I 151 742;
- microspheres of expanded acrylic copolymers such as those sold by EXPANCEL under the trade name EXPANCEL 551®; - fillers with an optical effect, such as those described in patent application FR-2 869 796, in particular : polyamide powders (Nylon®) such as, for example,
Nylon 12 particles of the Orgasol Arkema type with a mean dimension of 10 microns and a refractive index of
1.54;
- silica powders, for example SB150 Silica beads from Miyoshi with a mean dimension of 5 microns and a refractive index of 1.45; polytetrafluoroethylene powders, such as PTFE Ceridust 9205F from Clariant with a mean dimension of 8 microns and a refractive index of 1.36;
- silicon resin powders such as Silicon resin Tospearl 145A from GE Silicone with a mean dimension of 4.5 microns and a refractive index of 1.41,
- acrylic copolymer powders, especially of polymethyl methacrylate, such as PMMA Jurymer MBI particles from Nihon Junyoki with a mean dimension of 8 microns and a refractive index of 1.49, or Micropearl M100® and F 80 ED® particles from Matsumoto Yushi-Seiyaku;
- powdered waxes such as Paraffin wax microease 114S from Micropowders with a mean dimension of 7 microns and a refractive index of 1.54; - polyethylene powders, especially comprising at least one ethylene/acrylic acid copolymer, in particular constituted by ethylene/acrylic acid copolymers such as Flobeads EA 209 particles from Sumitomo (with a mean dimension of 10 microns and a refractive index of 1.48);
- elastomeric cross-linked organopolysiloxane powders coated with silicone resin, in particular with silsesquioxane resin as described, for example, in patent US-5 538 793. Such elastomer powders are sold under the trade names "KSP-100", "KSP-101", "KSP-102", "KSP-103", "KSP-104", "KSP-105" by SHIN ETSU; and composite talc/titanium dioxide/alumina/silica powders such as those sold under the trade name Coverleaf® AR-80 by Catalyst & chemicals; - mixtures thereof; sebum-absorbing and/or adsorbing compounds as described in patent application FR-2 869 796. The following may in particular be cited: silica powders, such as the porous silica microspheres sold under the trade name "SILICA BEADS
SB-700" sold by MYOSHI, "SUNSPHERE® H51", "SUNSPHERE
H33" , "SUNSPHERE® H53" sold by ASAHI GLASS; amorphous silica microspheres coated with polydimethylsiloxane sold under the trade name "SA SUNSPHERE® H-33" and "SA SUNSPHERE® H-53" sold by ASAHI GLASS; amorphous mixed silicate powders, especially of aluminium and magnesium such as, for example, that sold under the trade name "NEUSILIN UFL2" by Sumitomo; polyamide powders (Nylon®) such as, for example, "ORGASOL® 4000" sold by Arkema; and
- acrylic polymer powders, in particular of polymethyl methacrylate such as, for example, "COVABEAD® LH85" sold by WACKER; polymethyl methacrylate/ ethylene glycol dimethacrylate such as, for example, "DOW CORNING 5640 MICROSPONGE® SKIN OIL ADSORBER" sold by DOW CORNING, or "GANZPEARL® GMP-0820" sold by GANZ CHEMICAL; allyl polymethacrylate/ethylene glycol dimethacrylate, such as, for example, "POLY-PORE® L200" or "POLY-PORE® E200" sold by AMCOL; ethylene glycol dimethacrylate/lauryl methacrylate copolymer, such as, for example, "POLYTRAP® 6603" sold by DOW CORNING;
- silicate particles, such as alumina silicate; - mixed silicate particles, such as:
- particles of aluminium and magnesium silicate, such as magnesium saponite or silicate and aluminium hydrate with sodium sulphate sold under the trade name Sumecton® by Kunimine; - the complex of magnesium silicate, hydroxyethylcellulose, black cumin oil, gourd oil and phospholipids or Matipure® from Lucas Meyer; and
- mixtures thereof.
Preferred mattifying agents which may be used in accordance with the invention are an extract of pumpkin seeds, a rice or corn starch, kaolinite, silicas, talc, polyamide powders, polyethylene powders, acrylic copolymer powders, microspheres of expanded acrylic copolymers, silicone resin microbeads, mixed silicate particles and mixtures thereof.
Fillers with a soft-focus effect These fillers may be any material which is capable of modifying wrinkles by its intrinsic physical properties and of masking them. These fillers may in particular modify wrinkles by a tightening effect, a camouflage effect or a soft-focus effect.
Examples of compounds which may be used as fillers are as follows :
- porous silica microparticules such as, for example, Silica Beads® SB 150 and SB 700 from Myochi with a mean dimension of 5 μm and SUNSPHERES® series H from Asahi Glass such as H33, H51 with respective dimensions of 3.5 and 5 μm; hollow hemispherical particles of silicone resins such as NLK 500®, NLK 506® and NLK 510® from Takemoto Oil and Fat, in particular as described in EP-A-I 579 849;
- silicone resin powders such as, for example, SILICON Resin Tospearl® 145 A DE GE silicone with a mean dimension of 4.5 μm; acrylic copolymer powders, in particular of polymethyl methacrylate such as, for example, PMMA Jurimer MBI® particles from Nihon Junyoki with a mean dimension of 8 μm, hollow PMMA spheres sold under the trade name COVABEAD® LH 85 by Wacker and expanded vinylidene/acrylonitrile/methyl methacrylate microspheres sold under the trade name Expancel®;
- powdered wax such as Paraffin wax microloase® 114S particles from Micropowders with a mean dimension of 7 μm;
- polyethylene powders, especially those comprising at least one ethylene/acrylic acid copolymer such as, for example, FLOBEADS® EA 209 E from Sumimoto with a mean dimension of 10 μm; - cross-linked elastomeric organopolysiloxane powders coated with silicone resin, especially with silsesquioxane under the trade name KSP 100®, KSP IOI3 KSP 102®, KSP 103®, KSP 104® and KSP 105® by Shin Etsu; composite talc/titanium dioxide/alumina/silica powders such as, for example, Coverleaf AR 80® from Catalyst & Chemical; talc, mica, kaolin, lauryl glycine, starch powders cross-linked with octeanyl succinate anhydride, boron nitride, polytetrafluoroethylene powders, precipitated calcium carbonate, magnesium hydrocarbonate carbonate, barium sulphate, hydroxyapatite, calcium silicate, cerium dioxide and glass or ceramic microcapsules. - synthetic or natural, mineral or organic hydrophilic or hydrophobic fibres, such as silk, cotton, wool, linseed, cellulose extracted in particular from wood, vegetable or algae fibres, polyamide (Nylon®) , modified cellulose, poly-p-phenylene terephthamide, acrylic, polyolefin, glass, silica, aramid, carbon, polytetrafluoroethylene (Teflon®) , insoluble collagen, polyesters, polyvinyl or vinylidene chloride, polyvinyl alcohol, polyacrylonitrile, chitosan, polyurethane, polyethylene phthalate, fibres formed from a mixture of polymers, resorbable synthetic fibres, and mixtures thereof described in patent application EP-I 151 742; - spherical cross-linked elastomeric silicones such as Trefil E-505C® or E-506 C® from Dow Corning; abrasive filers which mechanically smooth of the cutaneous microrelief, such as abrasive silica, such as, for example, Abrasif SP® from Semanez or powdered nuts or shells (apricot, hazelnuts, for example from Cosmetochem) .
Particular fillers having an effect on the signs of ageing are selected from porous silica microparticles, hollow hemispherical silicone particles, silicone resin powders, acrylic copolymer powders, polyethylene powders, cross-linked elastomeric organopolysiloxane powders coated with silicone resin, composite talc/titanium dioxide/alumina/silica powders, precipitated calcium carbonate, magnesium hydrocarbonate carbonate, barium sulphate, hydroxyapatite, calcium silicate, cerium dioxide and glass or ceramic microcapsules, silk fibres, cotton fibres, and mixtures thereof.
The filler may be a "soft-focus" filler.
The term "soft-focus" means a filler which in addition provides the skin with both transparency and a soft- focussed effect. Preferably, soft-focus fillers have a mean particle size of 15 microns or less. These particles may have any shape, and in particular they may be spherical or non-spherical. Preferably again, these fillers are non-spherical.
Soft-focus fillers may be selected from powdered silica and silicates, in particular of alumina, powders of the polymethyl methacrylate (PMMA) type, talc, silica/Tic^ composites or silica/zinc oxide composites, polyethylene powders, starch powders, polyamide powders, styrene/acrylic copolymer powders, silicone elastomers, and mixtures thereof.
In particular, it is possible to cite talc with a number average dimension of 3 microns or less, for example talc with a number average dimension of 1.8 microns and in particular that sold under the trade name Talc P3® by Nippon Talc, Nylon® 12 powder, in particular that sold under the trade name Orgasol 2002 Extra D Nat Cos® by Atochem, silica particles surface treated with a 1% to 2% mineral wax (INCI name: hydrated silica (and) paraffin) , such as those sold by Degussa, amorphous silica microspheres such as those sold under the trade name Sunsphere, for example with reference H-53® from Asahi Glass, and silica micro- beads such as those sold under the trade name SB-700® or SB-150® by Miyoshi; this list is not limiting.
The concentration of these fillers having an effect on the signs of ageing in the compositions of the invention may be in the range 0.1% to 40%, or even in the range 0.1% to 20% by weight with respect to the total composition weight.
Fluorescent agents
The term "fluorescent agent" means a substance which, under the effect of ultraviolet radiation and/or visible light, re-emits in the visible the portion of light which it has absorbed with the same colour as that which it naturally reflects. The naturally reflected colour is thus reinforced by the re-emitted colour and appears extremely bright.
Examples which may be cited are coloured resins of polyamide and/or formaldehyde/benzoguanamine and/or melamine/formaldehyde/sulphonamide, from coloured aminotriazine/formaldehyde/sulphonamide co-condensates and/or from metallized polyester flakes and/or mixtures thereof. These fluorescent pigments may also be in the form of aqueous dispersions of fluorescent pigments.
It is also possible to cite the fluorescent pink coloured aminotriazine/formaldehyde/sulphonamide co- condensate with a mean particle dimension of 3-4 microns sold under the trade name "Fiesta Astral Pink FEX-I" and the blue-coloured fluorescent aminotriazine/formaldehyde/sulphonamide co-condensate with a mean particle size of 3-4.5 microns sold under the trade name "Fiesta Comet Blue FTX-60" by Swada or the yellow-coloured benzoguanamine/formaldehyde resin coated with formaldehyde/urea resin sold under the trade name "FB-205 Yellow" and the red-coloured benzoguanamine/formaldehyde resin coated with formaldehyde/urea resin sold under the trade name "FB- 400 Orange Red" by UK SEUNG CHEMICAL, and the orange- coloured polyamide resin sold under the trade name "Flare 911 Orange 4" by Sterling Industrial Colors. The fluorescent substances are preferably present in the composition in an amount of 0.1% to 20%, preferably 0.1% to 15%, more preferably 0.5% to 3% by weight with respect to the total composition weight.
When the organic fluorescent substances are white, they may also be termed optical brighteners .
The optical brightener intensifies the radiance and enlivens the colours of cosmetic compositions comprising them when applied to the skin.
More particular optical brighteners which may be cited are stilbene derivatives, in particular polystyrylstilbenes and triazinstilbenes, coumarin derivatives, in particular hydroxycoumarins and les aminocoumarins, oxazole, benzoxazole, imidazole, triazole, pyrazoline derivatives, pyrene derivatives and derivatives of porphyrin and/or mixtures thereof.
Such compounds are, for example, available under the trade names Tinopal SOP® and Uvitex OB® from CIBA GEIGY.
Preferred optical brighteners which may be used are sodium 4 , 4 ' -bis [ (4 , 6-dianilino-l , 3, 5-triazin-2- yl) amino] stilbene-2, 2 ' -disulphonate, 2, 5-thiophene di- yl bis (5-ter-butyl-l, 3-benzoxazole) , disodium di- styryl-4, 4' -biphenyl sulphonate and/or mixtures thereof.
Agents promoting the natural pink colour of the skin
The following may in particular be cited: - a self-tanning agent, i.e. an agent which, when applied to the skin, in particular to the face, can produce a tanned effect which bears a reasonable similarity to that which can result from prolonged exposure to the sun (natural tanning) or under a UV 1 amp ; an additional colouring agent, i.e. any compound having a particular affinity for the skin which can endow it with a durable colour, and with no coverage
(i.e. has no tendency to opacify the skin) and which is not eliminated with water or with a solvent, and which resists both rubbing and washing with a solution containing surfactants. Such a durable colour is thus distinguished from the superficial, momentary colour provided, for example, by a makeup pigment; and mixtures thereof.
Particular self-tanning agents which may be cited are: dihydroxyacetone (DHA) ; erythrulose; and a catalytic system combination formed by: manganese and/or zinc salts and oxides; and alkali or alkaline-earth bicarbonates .
The self-tanning agents are generally selected from mono- or polycarbonylated compounds such as, for example, isatine, alloxane, ninhydrin, glyceraldehyde, mesotartaric aldehyde, glutaraldehyde, erythrulose, pyrazolin-4, 5-dione derivatives such as those described in FR-2 466 492 and WO-97/35842, dihydroxyacetone (DHA) , 4, 4-dihydroxypyrazolin-5-one derivatives such as those described in patent application EP-O 903 342. Preferably, DHA is used.
The DHA may be used in the free and/or encapsulated form, for example in lipid vesicles such as liposomes, described in particular in application WO-97/25970.
In general, the self-tanning agent is present in a quantity of 0.01% to 20% by weight, preferably in a quantity in the range 0.1% to 10% of the total composition weight. - I A -
It is also possible to use other dyes which can modify the colour produced by the self-tanning agent.
Said dyes may be selected from direct synthetic or natural dyes.
Said dyes may, for example, be selected from red or orange fluorane type dyes such as those described in patent application FR-2 840 806. The following dyes may, for example, be cited :
- tetrabromofluoroscein or eosine with the CTFA name: CI 45380 or Red 21;
- phloxine B with the CTFA name: CI 45410 or Red 27;
- diiodofluorescein with the CTFA name : CI 45425 or Orange 10;
- dibromofluorescein with the CTFA name: CI 45370 or Orange 5; the sodium salt of tetrabromofluoroscein with the CTFA name: CI 45380 (Na salt) or Red 22; - the sodium salt of phloxine B with the CTFA name: CI 45410 (Na salt) or Red 28;
- the sodium salt of diiodofluorescein with the CTFA name: CI 45425 (Na salt) or Orange 11;
- erythrosine with the CTFA name: CI 45430 or Acid Red 51;
- phloxine with the CTFA name: CI 45405 or Acid Red 98.
These dyes may also be selected from anthraquinones, caramel, carmine, carbon black, azulene blues, methoxalene, trioxalene, guajazulene, chamuzulene, bengal rose, cosine 1OB, cyanosine, and daphinine.
These dyes may also be selected from indole derivatives such as monohydroxyindoles for example those described in FR-2 651 126 (i.e.: 4-, 5-, 6- or 7-hydroxyindole) or di-hydroxyindoles such as those described in EP-B-O 425 324 (i.e.: 5, 6-dihydroxyindole, 2-methyl 5,6- dihydroxyindole, 3-methyl 5, 6-dihydroxyindole, 2,3- dimethyl 5, 6-dihydroxyindole) . Abrasive fillers or exfoliating agents
Exfoliating agents which may be used in rinsing compositions of the invention which may, for example, be cited are exfoliating or buffing particles of mineral, vegetable or organic origin. Thus, for example, polyethylene beads or powder may be used, also nylon powder, polyvinyl chloride powder, pumice stone, ground apricot kernels or hazelnut shells, sawdust, glass beads, alumina and mixtures thereof.
It is also possible to cite Exfogreen® from Solabia (bamboo extract) , extracts from strawberry seeds (Akenes de fraise from Greentech) , powdered peach kernel, powdered apricot kernel, and finally in the field of vegetable powders with an abrasive effect, we can cite cranberry seed powder.
Preferred abrasive fillers or exfoliating agents of the invention which may be cited are peach kernel powder, apricot kernel powder, cranberry seed powder, extracts from strawberry seeds, and bamboo extracts.
The following examples serve to illustrate the invention without in any way being limiting in nature. In these examples, the quantities of the ingredients in the compositions are given as a % by weight with respect to the total composition weight.
EXAMPLE 1 : Preparation of 2, 4-bis- (neopentyl 4'- aminobenzalmalonate)-6-[ (3-{l, 3, 3, 3-tetramethyl-l- [ (trimethylsilyl) oxy] disiloxanyl}propyl) amino] -1,3,5- triazine :
Figure imgf000077_0001
First step: Preparation of 2, 4-dichloro-6- { [1, 3, 3, 3- tetramethyl-1- [ (trimethylsilyl) oxy] disiloxanyl ] propyl- 3-ylamino }-s-triazine:
To a solution of cyanuryl chloride (25 g, 0.135 mole) in 250 ml of acetone, amino-1 [ 1, 3, 3, 3-tetramethyl-l-
[ (trimethylsilyl) oxy] disiloxanyl] -3-propane (41.7 g, 0.149 mole) and a solution of sodium bicarbonate (11.4 g, 0.135 mole) in 120 ml of water were added dropwise at 00C so that the pH was in the range 3 to 6.5. At the end of introduction, the pH was 6.5. Stirring was maintained for 1 hour 30 minutes at 100C, then left at laboratory temperature. The precipitate formed was filtered, washed with water, drained and dried. 55.2 g
(yield: 95%) of the expected derivative was obtained in the form of a white powder (MP: 59°C) .
Second step: Preparation of dineopentyl malonate:
In a reactor surmounted by a Dean Stark apparatus, malonic acid (40 g, 0.38 mole) and neopentyl alcohol (77.5 g, 0.88 mole) in 110 ml of toluene was heated under reflux for 3 hours in the presence of 0.2 ml of concentrated sulphuric acid. The water formed was eliminated by azeotropy. The organic phase was washed 3 times with water and dried over sodium sulphate.
After filtering and evaporating off the solvent under vacuum, 88 g (94% yield) of dineopentyl malonate was obtained in the form of a colourless oil and used as is for the next step.
Third step : Preparation of dineopentyl 4^ nitrobenzalmalonate :
p-nitro benzaldehyde (49.5 g, 0.33 mole) and dineopentyl malonate (80 g, 0.33 mole) in 200 ml of toluene were placed in a flask provided with a Dean Stark apparatus surmounted by a cooling apparatus and with a nitrogen bubble-through. The pre-prepared catalyst, acetic acid (2 ml) and piperidine (3.3 ml) in suspension in 2 ml of toluene, was added, the mixture was heated under reflux with stirring for 5 hours and the water formed was eliminated by means of the Dean Stark apparatus. It was necessary to add the same quantity of catalyst two more times.
The cooled reaction mixture was poured into water and extracted with dichloromethane . The organic phase was washed with water then dried and concentrated under reduced pressure to a volume of 150 ml. 50 ml of isopropanol was added and it was allowed to crystallize. The solid obtained was filtered and re- crystallized in isopropanol. 68 g (55% yield) of dineopentyl 4-nitrobenzalmalonate in the form of pale beige crystals was obtained and used, as is, in the next step. Fourth step : Preparation of dineopentyl 4^ aminobenzalmalonate :
The derivative from the preceding step (67 g, 0.178 mole) in 80 ml of acetic acid was dispersed with stirring and with a nitrogen bubble-through. 120 ml of water was added. The mixture was heated to 500C. Iron
(107 g) was added in portions without exceeding a temperature of 55°C (introduction period 1 hour) . Next, acetic acid (120 ml) was added dropwise without exceeding a temperature of 55°C (introduction period 2 hours) . It was heated for 4 more hours at 55°C. It was cooled, water was added and then extracted with dichloromethane . The organic phase was washed with water, with a saturated sodium bicarbonate solution, with water and then was dried over sodium sulphate. After concentrating under reduced pressure, a yellow solid was obtained. It was recrystallized from a mixture of heptane and 1, 2-dichloroethane . 43 g (69% yield) of dineopentyl 4-aminobenzalmalonate was obtained in the form of fibrous yellow crystals and used, as is, in the next step.
Fifth step: Preparation of derivative of Example 1:
A mixture of the derivative from the first step (2 g,
0.005 mole) and the derivative from the preceding step
(3.6 g, 0.01 mole) in suspension in 15 ml of toluene was heated under reflux for 3 hours. It was cooled and dichloromethane was added. The organic phase was washed with a saturated sodium bicarbonate solution then with water. The organic phase was washed then concentrated under reduced pressure. The orangey oil obtained was separated on a silica column (eluent: heptane/EtOAc, 80:20) . Clean fractions were recovered in the form of a pale yellow solid of the derivative of Example 1 (2.8 g, 53% yield) : UV (Ethanol) λmax = 355 nm , E1% = 680. EXAMPLE 2 : Preparation of 2 , 4-bis- ( 4-methyl-2-pentanyl 4 / -aminobenzalmalonate) -6- [ (3- { l , 3 , 3 , 3-tetramethyl-l- [ (trimethylsilyl) oxy] disiloxanyl }propyl) amino] -1 , 3 , 5- triazine :
Figure imgf000080_0001
First step: Preparation of 1, 3-dimethylbutyl malonate:
Malonic acid (72.8 g, 0.7 mole) and the alcohol 2- methyl-4-pentanol (286 g, 2.8 mole) in 200 ml of toluene were heated under reflux for 2 hours in a reactor surmounted by a Dean Stark apparatus in the presence of 1.8 ml of concentrated sulphuric acid. The water formed was eliminated azeotropically . The organic phase was washed 3 times with water and dried over sodium sulphate. It was filtered and the solvent was evaporated off. The product obtained distilled at 147°C at 20 hPa. 160 g (79% yield) of 1,3- dimethylbutyl malonate was obtained in the form of a colourless oil which was used as is in the next step.
Second step: Preparation of 1, 3-dimethylbutyl 4- acetamido benzalmalonate :
p-acetamido benzaldehyde (6 g, 0.367 mole) and 1,3- dimethylbutyl malonate (10 g, 0.0367 mole) in 50 ml of toluene were placed in a flask provided with a Dean Stark apparatus surmounted by a cooling apparatus and with a nitrogen bubble-through. The pre-prepared catalyst, acetic acid (0.63 ml) and piperidine (1.1 ml) in suspension in 4 ml of toluene, was added. The mixture was heated under reflux with stirring for 3 hours and the water formed was eliminated by means of the Dean Stark apparatus. The cooled reaction mixture was poured into water and extracted with dichloromethane . The organic phase was washed with water then dried and concentrated under reduced pressure. The orangey yellow oil obtained was chromatographed on a silica column (eluent: heptane/EtOAc, 97:3) . 11.5 g (75% yield) of clean fractions of 1, 3-dimethylbutyl 4-acetamido benzalmalonate was obtained in the form of a yellow oil and used, as is, in the next step.
Third step: Preparation of 1, 3-dimethylbutyl 4- aminobenzalmalonate
The derivative from the preceding step (11.46 g, 0.0243 mole) was dissolved in 100 ml of isopropanol with stirring and a nitrogen bubble-through. 40 ml of a 2N HCl solution was added thereto. The mixture was heated under reflux for 12 hours. After cooling, the reaction mixture was extracted with 2 x 100 ml of dichloromethane. The organic phase was washed twice with a saturated sodium bicarbonate solution, then with water and then was dried over sodium sulphate. After concentrating under reduced pressure, an orangey brown oil was obtained which was purified by passage over a silica column (eluent: CH2Cl2) . 5.9 g (64% yield) of clean fractions of 1, 3-dimethylbutyl 4- aminobenzalmalonate was recovered in the form of an orangey yellow oil and used, as is, in the next step.
Fourth step: Preparation of derivative from Example 2:
A mixture of the derivative from the first step of Example 1 (3.43 g, 0.0082 mole) and the derivative from the preceding step (5.9 g, 0.0165 mole) in suspension in 125 ml of toluene was heated under reflux with an argon bubble-through for 4 hours. It was cooled and dichloromethane was added. The organic phase was dried with a saturated sodium bicarbonate solution then with water. The organic phase was washed then concentrated under reduced pressure. The viscous yellow oil obtained was separated on a silica column (eluent : heptane/EtOAc, 80:20) . Clean fractions were recovered in the form of a pale yellow solid of the derivative of Example 2 (2.73 g, 30% yield) : UV (Ethanol) λmax = 354 nm , E1% = 646.
EXAMPLE 3: Preparation of 2, 4-bis- (isopropyl-4' - aminobenzalmalonate)-6-[ (3-{l, 3, 3, 3-tetramethyl-l- [ (trimethylsilyl) oxy] disiloxanyl}propyl) amino] -1,3,5- triazine :
Figure imgf000082_0001
(6)
First step: Preparation of isopropyl 4-acetamido benzalmalonate :
p-acetamido benzaldehyde (8.67 g, 0.053 mole) and isopropyl malonate (10 g, 0.053 mole) in 100 ml of toluene were placed in a flask provided with a Dean Stark apparatus surmounted by a cooling apparatus and with a nitrogen bubble-through. The catalyst prepared in advance, acetic acid (0.304 ml) and piperidine
(0.526 ml) in suspension in 4 ml of toluene, was added.
The mixture was heated under reflux with stirring for 12 hours and the water formed was eliminated via the Dean Stark apparatus. The cooled reaction mixture was poured into water and extracted with dichloromethane . The organic phase was washed with water, then dried and concentrated under reduced pressure. The orangey solid obtained was recrystallized in isopropanol/heptane mixture in a ratio of 2:15 by volume. 8.8 g (49% yield) of isopropyl 4-acetamido benzalmalonate was recovered in the form of a yellow powder and used, as is, in the next step.
Second step : Preparation of isopropyl 4^ aminobenzalmalonate :
The derivative from the preceding step (8.5 g, 0.0255 mole) was dissolved in 80 ml of isopropanol with stirring and a nitrogen bubble-through. 50 ml of a 2N HCl solution was added thereto. The mixture was heated under reflux for 24 hours. After cooling, the reaction mixture was extracted with 2 x 100 ml of dichloromethane. The organic phase was washed twice with a saturated sodium bicarbonate solution, then with water and then was dried over sodium sulphate. After concentration under reduced pressure, a brown oil was obtained which was purified by passing over a silica column (eluent: CH2CI2) . 3.83 g (51% yield) of clean fractions of isopropyl 4-aminobenzalmalonate was recovered in the form of an orangey yellow oil and used, as is, in the next step.
Third step: Preparation of derivative of Example 3:
A mixture of the derivative from the first step of Example 1 (3.8 g, 0.013 mole) and the derivative from the preceding step (2.84 g, 0.0065 mole) in suspension in 85 ml of toluene was heated under reflux with an argon bubble-through for 5 hours. It was cooled and dichloromethane was added. The organic phase was washed with a saturated sodium bicarbonate solution then with water. The organic phase was washed, then concentrated under reduced pressure. The yellow oil obtained was separated on a silica column (eluent : heptane/EtOAc, 80:20) . Clean fractions were recovered in the form of a pale yellow solid of the derivative of Example 3 (3 g, 50% yield) : UV (Ethanol) λmax = 356 nm , E1% = 760.
EXAMPLE 4: Preparation of tetrakis (cyclohexylmethyl) 2 , 2 ' - [ { 6- [ (3-{ 1 , 3 , 3 , 3-tetramethyl-l- [ (trimethylsilyl) - oxy] disiloxanyl}propyl) amino] -1,3, 5-triazine-2, 4-diyl}- bis (iminobenzene-4, 1-diylmethylidene) ] dipropanedioate :
Figure imgf000084_0001
First step: Preparation of bis (cyclohexylmethyl) malonate :
Malonic acid (5.47 g, 0.052 mole) and cyclohexyl- methanol (24 g, 0.208 mole) in 30 ml of toluene in the presence of 0.2 ml of concentrated sulphuric acid are brought to reflux for 16 hours in a reactor surmounted by Dean Stark apparatus. After cooling, the organic phase is washed three times with water and is dried over sodium sulphate. After filtering and evaporating the solvent under vacuum, the crude oil obtained is subjected to distillation under vacuum (1700C under 0.2 mbar) so as to remove the volatile components. The distillation residue obtained (14 g, yield 90%) is bis (cyclohexylmethyl) malonate in the form of a colourless oil used as is in the following step. Second step: Preparation of bis (cyclohexylmethyl) 4-acetamidobenzalmalonate :
p-Acetamidobenzaldehyde (7.12 g, 0.436 mole) and bis (cyclohexylmethyl) malonate (12.93 g, 0.436 mole) in 120 ml of toluene are brought to reflux in a reactor surmounted by Dean Stark apparatus while sparging with nitrogen. The preprepared catalyst, acetic acid (0.249 ml) and piperidine (0.432 ml) in suspension in 4 ml of toluene, is added thereto. The mixture is brought to reflux with stirring for 12 hours and the water formed is removed via the Dean Stark apparatus. The cooled reaction mixture is poured into water and extracted with dichloromethane . The organic phase is washed with water and then dried and concentrated under reduced pressure. The yellow solid obtained is recrystallized from toluene. 16.45 g (yield 85%) of bis (cyclohexylmethyl) 4-acetamidobenzalmalonate are thus recovered in the form of a pale yellow powder used as is in the following step.
Third step: Preparation of bis (cyclohexylmethyl) 4-aminobenzalmalonate :
The derivative from the preceding step (15.5 g, 0.0255 mole) is dissolved in 120 ml of isopropanol with stirring and sparging with nitrogen. 35 ml of 5N HCl solution are added thereto. The mixture is heated at reflux for 12 hours. After cooling, the reaction mixture is extracted with 2 x 100 ml of dichloromethane. The organic phase is washed twice with a saturated sodium bicarbonate solution and with water and is then dried over sodium sulphate. After concentrating under reduced pressure, a yellow gum is obtained and is purified by passing through a silica column (eluent: CH2Cl2) . 4.74 g (yield 33%) of clean bis (cyclohexylmethyl) 4-aminobenzalmalonate fractions are recovered in the form of a yellow powder used as is in the following step. Fourth step: Preparation of the derivative of Example 4 :
A mixture of the derivative from the first step of Example 1 (2.4 g, 0.0056 mole) and of the derivative from the preceding step (4.5 g, 0.00113 mole) in suspension in 90 ml of toluene is heated at reflux for 4 hours while sparging with nitrogen. The mixture is cooled and dichloromethane is added. The organic phase is washed with a saturated sodium bicarbonate solution and then with water. The organic phase is dried and then concentrated under reduced pressure. The yellow oil obtained is subjected to separation on a silica column (eluent: heptane/EtOAc, gradient from 90:10 to 80:20) . Clean fractions are recovered in the form of a pale yellow powder of the derivative of Example 4 (1.27 g, yield 20%) : UV (Ethanol) : λmax = 355 nm, E1% = 607.
EXAMPLE 5: Preparation of tetracyclohexyl 2, 2' - [ {6- [ (3- {1, 3, 3, 3-tetramethyl-l- [ (trimethylsilyl) oxy] di- siloxanyl}propyl) amino] -1,3, 5-triazine-2, 4-diyl}bis- (iminobenzene-4, 1-diylmethylidene) ] dipropanedioate :
Figure imgf000086_0001
First step: Preparation of biscyclohexyl malonate:
Malonic acid (6.15 g, 0.059 mole) and cyclohexanol (23.675 g, 0.236 mole) in 30 ml of toluene in the presence of 0.2 ml of concentrated sulphuric acid are brought to reflux over 16 hours in a reactor surmounted by Dean Stark apparatus. After cooling, the organic phase is washed three times with water and is dried over sodium sulphate. After filtering and evaporating the solvent under vacuum, the crude oil obtained is subjected to distillation under vacuum (1700C under 0.2 mbar) , so as to remove the volatile components. The distillation residue obtained (12.4 g, yield 78%) is biscyclohexyl malonate in the form of a yellow oil used as is in the following step.
Second step: Preparation of biscyclohexyl 4-acetamido- benzalmalonate :
p-Acetamidobenzaldehyde (6.9 g, 0.4233 mole) and biscyclohexyl malonate (11.35 g, 0.423 mole) in 110 ml of toluene are brought to reflux in a reactor surmounted by Dean Stark apparatus while sparging with nitrogen. The preprepared catalyst, acetic acid (0.242 ml) and piperidine (0.419 ml) in suspension in 3 ml of toluene, is added thereto. The mixture is brought to reflux with stirring for 12 hours and the water formed is removed via the Dean Stark apparatus. The cooled reaction mixture is poured into water and extracted with dichloromethane . The organic phase is washed with water and then dried and concentrated under reduced pressure. The yellow solid obtained is recrystallized from toluene. 12.77 g (yield 73%) of biscyclohexyl 4-acetamidobenzalmalonate are thus recovered in the form of a pale yellow powder used as is in the following step.
Third step: Preparation of biscyclohexyl 4-aminobenzal- malonate :
The derivative from the preceding step (11.55 g, 0.0278 mole) is dissolved in 90 ml of isopropanol with stirring and sparging with nitrogen. 35 ml of 5N HCl solution are added thereto. The mixture is heated at reflux for 12 hours. After cooling, the reaction mixture is extracted with 2 x 100 ml of dichloromethane . The organic phase is washed twice with a saturated sodium bicarbonate solution and with water and is then dried over sodium sulphate. After concentrating under reduced pressure, a brown gum is obtained and is purified by passing through a silica column (eluent: CH2CI2) . 3.73 g (yield 36%) of the clean biscyclohexyl 4-aminobenzalmalonate fractions are recovered in the form of a yellow powder used as is in the following step.
Fourth step: Preparation of the derivative of
Example 5 :
A mixture of the derivative from the first step of Example 1 (1.81 g, 0.0042 mole) and of the derivative from the preceding step (3.14 g, 0.0084 mole) in suspension in 60 ml of toluene is heated at reflux for
4 hours while sparging with nitrogen. The mixture is cooled and dichloromethane is added. The organic phase is washed with a saturated sodium bicarbonate solution and then with water. The organic phase is dried and then concentrated under reduced pressure. The yellow oil obtained is subjected to separation on a silica column (eluent: heptane/EtOAc, gradient from 90:10 to 80:20) . Clean fractions are recovered in the form of a pale yellow powder of the derivative of Example 5
(1.35 g, yield 29%) :
UV (Ethanol) : λmax = 355 nm, E1% = 622.
Formulation Example 6 :
Figure imgf000088_0001
Figure imgf000089_0001
Photostability of prior art compound compared with compound in accordance with the invention of EXAMPLE 1.
Test products: 2, 4-bis- (isobutyl-4' -aminobenzalmalonate) -6- [ (3- {1,3,3, 3-tetramethyl-l- [ (trimethylsilyl) oxy] di- siloxanyl jpropyl) amino] -1, 3, 5-triazine = Example 5 of patent EP-O 841 341:
Figure imgf000090_0001
2, 4-bis- (neopentyl 4' -aminobenzalmalonate) -6- [ (3- {1,3,3, 3-tetramethyl-l- [ (trimethylsilyl) oxy] di- siloxanyl jpropyl) amino] -1, 3, 5-triazine = compound with formula (1) in accordance with the invention:
Figure imgf000090_0002
The two products were dissolved at 2% by weight in Miglyol 812 oil. Approximately 10 mg of the Miglyol 812 solution was spread onto 10 cm2 of the surface of a hollow ground glass disc; the quantity was determined by weighing.
The films obtained were exposed to 50 J/cm2 of UV-A using an ORIEL solar simulator (UV-A = 15.6 mW/cm2, UV- B = 0.48 mW/cm2) , then extracted with 10 ml of ethanol/5 min ultrasound.
The products were quantified by HPLC of the extracts. HPLC Conditions: column: UPWOD-15QS; Eluent: 98% methanol + 2% water; flow rate: 1 ml/min; Injected volume: 10 μl; Detection: Diode arrays; Rt = 4.1 min for the prior art compound and 5.0 min for the compound of Example 1.
The losses were determined by comparing the quantities of product present in the irradiated samples and in the non-irradiated controls prepared simultaneously and treated in the same manner (mean over 3 samples; S = surface/mg of solution) : % loss = 100 x (So - Sirr)/So.
PHOTOSTABILITY RESULTS
Figure imgf000091_0001
SOLUBILITIES COMPARED BETWEEN A COMPOUND OF THE PRIOR ART AND THE COMPOUNDS ACCORDING TO THE INVENTION OF EXAMPLES 1, 3, 4, 5 and 6
Products tested:
2, 4-bis (isobutyl 4' -aminobenzalmalonate) -6- [ (3- {1,3,3, 3-tetramethyl-l- [ (trimethylsilyl) oxy]di- siloxanyl jpropyl) amino] -1, 3, 5-triazine = Example 5 of Patent EP 0 841 341:
Figure imgf000092_0001
Compounds of formulae (1), (3), (4] !5) and (6; according to the invention;
Oil chosen: Capric/Caprylic Triglycerides (Miglyol 812) :
X mg of product are introduced into Y mg of the oil; with gentle heating (<40°C) and the use of an ultrasound generator for 1 minute, the solution obtained is left at laboratory temperature for 2 weeks; the condition of this solution is observed; if no crystal or oily deposit is visible, the solubility of the product is regarded as greater than X x 100/ (X + Y) as weight/weight.
SOLUBILITY RESULTS
Figure imgf000092_0002

Claims

PATENT CLAIMS
1. s-Triazine compound with general formula (I' below or one of its tautomeric forms:
Figure imgf000093_0001
in which
• radicals (X) , which may be identical or different, represent a linear or branched C1-C30 alkyl radical, optionally halogenated or unsaturated, a C6-C12 aryl radical, a C1-C10 alkoxy radical or the trimethylsilyloxy group;
• a = 1 to 3;
• group (D) designates an s-triazine compound with the following formula (II) :
Figure imgf000093_0002
in which:
• radicals R, which may be identical or different, designate a group with formula (III) :
Figure imgf000093_0003
in which: Ri and R2, which may be identical or different, represent a linear or branched Ci-Cs alkyl group; Ri and R2 may form a C5-Cs cycle, optionally substituted with 1, 2 or 3 linear or branched C1-C4 alkyl groups; R3, R4 and R5, which may be identical or different, represent a hydrogen atom or a linear or branched Ci-C4 alkyl group; n is 0 or 1; m is 0 or 1; provided that:
(i) when n = 1 and R4 designates hydrogen, then m = 0 and R3 is different from hydrogen; (ii) when Ri and R2 form a Ci-Cs cycle, then the sum n + m is different from 2; • A is a divalent radical with the following formula :
(Z)-CH-CH2-
W
in which:
• (Z) is a linear or branched, saturated or unsaturated C1-C10 alkylene diradical, optionally substituted with a hydroxy radical or oxygens and which may optionally contain an amino group; • W represents a hydrogen atom, a hydroxy radical or a linear or branched Ci-Cs alkyl radical.
2. Compound according to Claim 1 in which, in addition to units with formula -(Si) (X) a (O) (3-a) /2, the organosiloxane may comprise units with formula -(X)b-(Si) (O) <4-b)/2 in which:
(X) has the same meaning as in formula (I) ; b = 1-3.
3. Compound according to Claim 1 or Claim 2, having one of the following formulae (Ia) or (Ib) :
Figure imgf000095_0001
R6 R6
(Ib) R. (D)
in which:
(D) has formula (II) as defined in Claim 1 ; R6, which may be identical or different, are selected from linear or branched C1-C20 alkyl, phenyl, 3, 3, 3-trifluoropropyl and trimethylsilyloxy radicals, at least 80% by number of radicals R6 being methyl;
(B) , which may be identical or different, are selected from radicals R6 and radical (D) , r is a whole number in the range 0 to 200 inclusive; s is a whole number from 0 to 50 and if s = 0, at least one of the two symbols (B) designates (D) ; u is a whole number from 1 to 10; t is a whole number from 0 to 10, given that t + u is 3 or more.
4. Compound according to Claim 3, selected from those with formula (Ia) .
5. Compound according to Claim 3 or Claim 4, characterized in that it is a random oligomer or polymer having at least one and more preferably all of the following characteristics:
• Re is alkyl; more preferably, it is methyl; • (B) is preferably methyl.
6. Compound according to any one of Claims 1 to 5, in which (X) is the methyl radical and A is the propyl di-radical .
7. Compound according to any one of Claims 1 to 6, in which the following two conditions are combined:
(a) n = m = 0 ; and
(b) Ri, R2 and R3 designate a Ci-C4 alkyl and more particularly methyl, or R3 designates hydrogen and Ri and R2 form a C5-Cs cycle, optionally substituted with 1 or two alkyl radicals, more particularly cyclohexyl.
8. Compound according to any one of Claims 1 to 6, in which the following two conditions are combined:
(a) n = 1 and R4 designates an alkyl, in particular methyl, or m = 1 and R5 designates an alkyl, in particular methyl; and
(b) Ri and R2 designate a Ci-C4 alkyl, more particularly methyl.
9. Compound according to any one of Claims 1 to 8, selected from the following formulae (1) to (10) :
Figure imgf000096_0001
(1) (2)
Figure imgf000097_0001
(3) (4)
Figure imgf000097_0002
(5) (6)
Figure imgf000097_0003
(7)
(8)
Figure imgf000098_0001
where r = 8.1
Figure imgf000098_0002
(10)
where r = s = 6.
10. Cosmetic or dermatological composition, intended for the photoprotection of keratinous materials containing at least one compound with formula (I) as defined in any one of Claims 1 to 9 in a cosmetically acceptable medium.
11. Composition according to Claim 10, further comprising at least one complementary mineral UV filter and/or at least one organic UV filter.
12. Composition according to Claim 11, in which the complementary organic UV filters are selected from cinnamic derivatives; anthranilates; salicylic derivatives, dibenzoylmethane derivatives, camphor derivatives; benzophenone derivatives; β/β~ diphenylacrylate derivatives; triazine derivatives; benzotriazole derivatives; benzalmalonate derivatives; benzimidazole derivatives; imidazolines; bis- benzoazolyl derivatives; p-aminobenzoic acid (PABA) derivatives; methylene bis- (hydroxyphenyl benzotriazole) derivatives; benzoxazole derivatives; polymer filters and silicone filters; dimers derived from α-alkylstyrene; 4, 4-diarylbutadienes; merocyanine derivatives, and mixtures thereof.
13. Composition according to Claim 11, in which the inorganic filter or filters are metal oxide pigments, which may or may not be coated, having a mean elementary particle size of 500 nm or less, more preferably in the range 5 nm to 500 nm, and still more preferably in the range 10 nm to 100 nm, preferably in the range 15 nm to 50 nm.
14. Composition according to Claim 13, in which the metal oxide pigments are selected from oxides of titanium, zinc, iron, zirconium, cerium and mixtures thereof, and more particularly titanium oxides.
15. Use of at least one s-triazine compound containing one aminosiloxane group and two grafted para-aminobenzalmalonate groups with formula (I) as defined in any one of Claims 1 to 9 in a cosmetic composition as a UV-A radiation filtering agent.
PCT/EP2008/065115 2007-12-12 2008-11-07 S-triazine compounds containing one aminosiloxane group and two particular para-aminobenzalmalonate groups; cosmetic compositions containing said derivatives; uses of said s-triazine derivatives WO2009074409A1 (en)

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FR07/59785 2007-12-12
US1376407P 2007-12-14 2007-12-14
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011012002A (en) * 2009-07-01 2011-01-20 Shin-Etsu Chemical Co Ltd Melamine-functional organosilicon compound and method for producing the same
WO2011061864A1 (en) * 2009-11-20 2011-05-26 L'oreal A cosmetic or dermatological composition with low stickiness, containing a lipophilic active ingredient
FR2957251A1 (en) * 2010-03-15 2011-09-16 Oreal Composition, useful for the cosmetic treatment of e.g. skin, comprises silicon-s-triazine substituted by at least two groups of alkylaminobenzoates, and hydrophilic or water soluble merocyanine UV filter, in a medium of UV filter system
WO2011141111A2 (en) 2010-05-12 2011-11-17 Merck Patent Gmbh Triazines as reaction accelerators
CN109777741A (en) * 2019-01-15 2019-05-21 昆明理工大学 A kind of method that walnut shell efficiently utilizes
US11357713B2 (en) 2015-07-14 2022-06-14 Conopco, Inc. Antimicrobial composition

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EP0841341A1 (en) * 1996-11-08 1998-05-13 L'oreal Sunscreen agents, and cosmetic compositions containing them

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EP0841341A1 (en) * 1996-11-08 1998-05-13 L'oreal Sunscreen agents, and cosmetic compositions containing them

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011012002A (en) * 2009-07-01 2011-01-20 Shin-Etsu Chemical Co Ltd Melamine-functional organosilicon compound and method for producing the same
US8263766B2 (en) 2009-07-01 2012-09-11 Shin-Etsu Chemical Co., Ltd. Melamine-functional organosilicon compound and making method
WO2011061864A1 (en) * 2009-11-20 2011-05-26 L'oreal A cosmetic or dermatological composition with low stickiness, containing a lipophilic active ingredient
CN102655839B (en) * 2009-11-20 2014-11-12 莱雅公司 A cosmetic or dermatological composition with low stickiness, containing a lipophilic active ingredient
FR2957251A1 (en) * 2010-03-15 2011-09-16 Oreal Composition, useful for the cosmetic treatment of e.g. skin, comprises silicon-s-triazine substituted by at least two groups of alkylaminobenzoates, and hydrophilic or water soluble merocyanine UV filter, in a medium of UV filter system
WO2011141111A2 (en) 2010-05-12 2011-11-17 Merck Patent Gmbh Triazines as reaction accelerators
US11357713B2 (en) 2015-07-14 2022-06-14 Conopco, Inc. Antimicrobial composition
CN109777741A (en) * 2019-01-15 2019-05-21 昆明理工大学 A kind of method that walnut shell efficiently utilizes
CN109777741B (en) * 2019-01-15 2022-01-04 昆明理工大学 Method for efficiently utilizing walnut shells

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