FR2902652A1 - Cosmetic composition comprises a dibenzoylmethane UV-A filter and an aromatic ester - Google Patents

Abstract

Composition comprising a dibenzoylmethane UV-A filter (I) and an aromatic ester (II) is new. Composition comprising a dibenzoylmethane UV-A filter (I) and an aromatic ester of formula (II) is new. Ar1-[(CH2)m-COO-(CHR2)n-Ar2]b (II) Ar1phenyl or pyridyl substituted with 0-2 of R1; Ar2phenyl substituted with 0-2 of R1; R11-4C alkyl; m : 0-4; R2H or Me; n : 0-4; b : 1 or 2; provided that Ar1 is substituted with 1-2 of R1 and R1 is not methyl when Ar1phenyl, R2 = H, m= 0 and n = 2.

Description

COSMETIC COMPOSITION CONTAINING A DIBENZOYLMETHANE DERIVATIVE AND A

  MONO DERIVATIVE OR ARYLALKYL DIESTER; The present invention relates to a cosmetic composition containing the combination of at least one dibenzoylmethane derivative and at least one particular arylalkyl mono or diester derivative of formula (I) which will be given the definition below.

  It also relates to a photostabilization process with respect to the radiation of at least one dibenzoylmethane derivative by at least one particular arylalkyl mono or diester derivative of formula (I).

  The present invention also relates to the use of said particular arylalkyl mono or diester derivative of formula (I) in a composition comprising, in a cosmetically acceptable support, at least one filter of the dibenzoylmethane derivative type for the purpose of improving the effectiveness of said composition vis-à-vis UV-A.

  It is known that the luminous radiations of wavelengths between 280 nm and 400 nm allow the browning of the human epidermis, and that the wavelength rays more particularly between 280 and 320 nm, known under the name UV -B, cause erythema and skin burns that can affect the development of natural tanning. For these reasons as well as for aesthetic reasons, there is a constant demand for means of control of this natural tan to thereby control the color of the skin; it is therefore necessary to filter this UV-B radiation.

  It is also known that UV-A rays of wavelengths between 320 and 400 nm, which cause browning of the skin, are capable of inducing an alteration thereof, especially in the case of a skin sensitive or skin continuously exposed to solar radiation. UV-A rays cause in particular a loss of elasticity of the skin and the appearance of wrinkles leading to premature cutaneous aging. They promote the triggering of the erythematous reaction or amplify this reaction in some subjects and may even be the cause of phototoxic or photoallergic reactions. Thus, for aesthetic and cosmetic reasons such as the preservation of the natural elasticity of the skin for example, more and more people wish to control the effect of UV-A on their skin. It is therefore desirable to also filter the UV-A radiation.

  In order to ensure protection of the skin and keratin materials against UV radiation, it is generally used antisolar compositions comprising organic filters, active in the UV-A and active in the UV-B. Most of these filters are fat soluble.

  In this respect, a particularly interesting family of UV-A filters currently consists of the dibenzoylmethane derivatives, and in particular 4-tert-butyl-4'-methoxydibenzoylmethane, which in fact have a high intrinsic absorption capacity. These dibenzoylmethane derivatives, which are now products that are well known per se as active filters in UV-A, are described in particular in French patent applications FR-A-2326405 and FR-A-2440933, as well as in European Patent Application EP-A-0114607; 4-tert-butyl-4'-methoxydibenzoyl methane is also currently offered for sale under the trade name PARSOL 1789 by Roche Vitamins.

  Unfortunately, it turns out that the dibenzoylmethane derivatives are relatively sensitive products to ultraviolet radiation (especially UV-A), that is to say, more precisely, that they have an unfortunate tendency to degrade more or less rapidly under the action of the latter. Thus, this substantial lack of photochemical stability of the dibenzoylmethane derivatives against the ultraviolet radiation to which they are inherently intended to be subjected, does not guarantee a constant protection during prolonged exposure to the sun, so that repeated applications at intervals of time Regular and close-ups must be performed by the user to achieve effective protection of the skin against UV rays.

  To solve this problem, it has already been proposed in patent application EP1618870 to use arylalkyl benzoate derivatives, in particular 2-ethylphenyl benzoate, such as the commercial product sold under the name X-TEND 226 8 by the company ISP. However, the level of photostability of the dibenzoylmethane derivative after exposure to UV is still insufficient.

  However, the Applicant has now discovered, surprisingly, that by combining the dibenzoylmethane derivatives mentioned above with an effective amount of a particular arylalkyl mono or diester derivative of formula (I) which will be defined more far in detail, it was possible to improve substantially and remarkably, the photochemical stability (or photostability) of these same dibenzoylmethane derivatives and their effectiveness in UV-A. The compositions containing such an association also lead after application to a more homogeneous distribution of the UV filter.

  These findings are the basis of the present invention.

  Thus, according to one of the objects of the present invention, there is now proposed a composition comprising in a cosmetically acceptable support at least one UV filtering system, characterized in that it comprises at least: (a) at least one UV-A filter of the dibenzoylmethane derivative type and (b) at least one particular arylalkyl mono or diester derivative of formula (I), the definition of which will be given below.

  Another subject of the invention also relates to a process for improving the chemical stability with respect to the UV radiation of at least one UV-A filter of the dibenzoylmethane-derived type comprising associating with said dibenzoylmethane derivative at least one mono derivative Specifically, the present invention also relates to the use of at least one particular arylalkyl mono or diester derivative of formula (I), in which a composition comprising in a cosmetically acceptable support, at least one derivative of dibenzoylmethane in order to improve the effectiveness of said composition vis-à-vis UV-A.

  Other features, aspects and advantages of the invention will appear on reading the detailed description which follows.

  By cosmetically acceptable, is meant compatible with the skin and / or its integuments, which has a pleasant color, smell and feel and which does not generate unacceptable discomfort (tingling, tightness, redness), likely to divert the consumer from use this composition.

  Among the derivatives of dibenzoylmethane, mention may be made, in a nonlimiting manner: 2-methyldibenzoylmethane, 4-methyldibenzoylmethane, 4-isopropyldibenzoylmethane, 4-tert.-butyldibenzoylmethane, dimethyldibenzoylmethane, 2,5-dimethyldibenzoylmethane, 4,4'-diisopropyldibenzoylmethane, 4,4'-dimethoxydibenzoylmethane, 4-tert-butyl-4'-methoxydibenzoylmethane, 2-methyl-5- isopropyl-4'-methoxydibenzoylmethane, 2-methyl-5-tert-butyl-4'-methoxydibenzoylmethane, 2,4-dimethyl-4'-methoxydibenzoylmethane, 2,6-dimethyl-4-tert- butyl-4'-methoxydibenzoylmethane.

  Among the dibenzoylmethane derivatives mentioned above, use will in particular be made of 4-isopropyl-dibenzoylmethane, sold under the name "Eusolex 8020" by the company Merck, and having the following formula: It is particularly preferred to use the 4- (tert-butyl) -4'-methoxy dibenzoylmethane or Butyl Methoxy Dibenzoylmethane, offered for sale under the trade name "PARSOL 1789" by Roche Vitamins; this filter has the following formula: OMe The dibenzoylmethane derivative (s) may be present in the compositions in accordance with the invention at contents which preferably vary from 0.01 to 10% by weight and more preferably from 0.1 to 10% by weight. at 6% by weight relative to the total weight of the composition. The mono or diester arylalkyl derivatives according to the invention are preferably chosen from those of the following formula (I): ## STR2 ## in which - R 1 is a group C1-C4 alkyl, linear or branched, - a is 0, 1 or 2, - X is CH or N, 10 -m = 0-4, - R2 is independently H or methyl, -p = 0-4 b is 1 or 2, with the proviso that if X = CH, R 2 = H, m = 0, p = 2, then a is different from 0 and R 1 is different from methyl.

  In the formula (I), among the alkyl groups, mention may especially be made of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tert-butyl groups. Among the arylalkyl benzoate derivatives mentioned above, the following products (a) to (f) will be used more particularly: (a) (b) RN = 89291-00-9 RN = 726-26-1 (c) RN = 758717-16-7 (d) o (e) RN = 71653-43-5 The ester derivatives of formulas (I) can be prepared by reaction of the acid derivative of formula (II) with the alcohol of formula (III) ) in the presence of an acid catalyst such as concentrated sulfuric acid in a solvent medium such as toluene 10 according to the following scheme: (f) X 0 (CH 2) m "OH] b + b HO (I) The arylalkyl mono or diester derivative (s) may be present in the compositions at levels which are generally between 0.1% and 40% by weight, and preferably at levels of between 0.1% and 30%. by weight, relative to the total weight of the composition.

  According to the present invention, the compound (s) of formulas (I) and (II) will be used in an amount sufficient to obtain a significant and significant improvement in the photostability of the derivative. dibenzoylmethane in a given composition. This minimum amount of light-stabilizing agent to be used may vary according to the amount of dibenzoylmethane present initially in the composition and according to the nature of the cosmetically acceptable support selected for the composition. It can be determined without any difficulty by means of a conventional photostability measurement test.

  The compositions in accordance with the invention may comprise, in addition, other additional organic UV or inorganic UV screening agents active in water-soluble or fat-soluble UVA and / or UVB or insoluble in the cosmetic solvents commonly used.

  The additional organic photoprotective agents are in particular chosen from anthranilates; cinnamic derivatives; salicylic derivatives, camphor derivatives; benzophenone derivatives; 13,13-diphenylacrylate derivatives; triazine derivatives; benzotriazole derivatives; benzalmalonate derivatives including those cited in US5624663; benzimidazole derivatives; imidazolines; bis-benzoazolyl derivatives as described in patents EP669323 and US 2,463,264; p-aminobenzoic acid derivatives (PABA); methylene bis- (hydroxyphenylbenzotriazole) derivatives as described in US5,237,071, US 5,166,355, GB2303549, DE 197 26 184 and EP893119; benzoxazole derivatives as described in patent applications EP0832642, EP1027883, EP1300137 and DE10162844; filter polymers and silicone filters such as those described in particular in the application WO-93/04665; alkyl-styrene-derived dimers such as those described in patent application DE19855649; 4,4-diarylbutadienes as described in Applications EP0967200, DE19746654, DE19755649, EP-A-1008586, EP1133980 and EP133981 and mixtures thereof.

  As examples of complementary organic photoprotective agents, mention may be made of those designated below under their INCI name: Derivatives of para-aminobenzoic acid: PABA, Ethyl PABA, Ethyl Dihydroxypropyl PABA, Ethylhexyl Dimethyl PABA sold in particular 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 Haarmann and Reimer, Dipropylene glycol salicylate sold under the name DIPSAL by SCHER, TEA Salicylate, sold under the name NEO HELIOPAN TS by Haarmann and Reimer, cinnamic derivatives: Ethylhexyl Methoxycinnamate sold in particular under the trade name Parsol MCX by Hoffmann La Roche, Isopropyl Methoxy Cinnamate, Isoamyl Methoxy Cinnamate sold under the trade name NEO HELIOPAN E 1000 by HAARMANN and REIMER, Cinoxate, DEA Methoxycinnamate, - Diisopropyl Methylcinnamate, Glyceryl Ethylhexanoate Dimethoxycinnamate

  Derivatives of R, 13-diphenylacrylate Octocrylene sold in particular under the trade name UVINUL N539 by BASF, Etocrylene, sold in particular under the trade name UVINUL N35 by BASF,

  Derivatives of benzophenone: Benzophenone-1 sold under the trade name UVINUL 400 by BASF, Benzophenone-2 sold under the trade name UVINUL D50 by BASF 20 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 25 Benzophenone-8 sold under the trade name Spectra-Sorb UV-24 by American Cyanamid Benzophenone-9 sold under the name commercial UVINUL DS-49 by BASF, Benzophenone-12 2- (4-diethylamino-2-hydroxybenzoyl) -benzoate benzoate. Derivatives of benzylidene camphor: 3-Benzylidene camphor manufactured under the name MEXORYL SD by CHIMEX, 4-Methylbenzylidene camphor sold under the name EUSOLEX 6300 by MERCK, Benzylidene Camphor Sulfonic Acid manufactured under the name MEXORYL SL by CHIMEX, Camphor Benzalkonium Methosulfate manufactured under the name MEXORYL SO by CHIMEX, Terephthalylidene Dicamphor Sulfonic Acid manufactured under the name MEXORYL SX by CHIMEX, Polyacrylamidomethyl Benzylidene Camphor manufactured under the name MEXORYL SW by CHIMEX, Derivatives of phenyl benzimidazole: Phenylbenzimidazole Sulfonic Acid sold in particular under the trade name EUSOLEX 232 by MERCK, Disodium Phenyl Dibenzimidazole Tetrasulfonate sold under the trade name 10 commercial NEO HELIOPAN AP by Haarmann and REIMER,

  Derivatives of phenyl benzotriazole: Drometrizole Trisiloxane sold under the name Silatrizole by Rhodia Chimie, methylene bis-benzotriazolyl tetramethylbutylphenol, sold in solid form under the trade name MIXXIM BB / 100 by FAIRMOUNT CHEMICAL or in 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 UVASORB HEB 25 by SIGMA 3V, 2 , 4,6-tris (dineopentyl 4'-amino benzalmalonate) -s-triazine 2,4,6-tris- (4'-amino benzalmalonate diisobutyl) -s-triazine, symmetrical triazine filters described in the patent US6,225,467, WO2004 / 085412 (see compounds 6 and 9) or Symetrical Triazine 30 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-1,3,5-triazine) and 2,4,6-tris (terphenyl) -1,3,5-triazine which are included in patent applications WO06 / 035000, WO06 / 034982, WO06 / 034991, WO06 / 035007, WO2006 / 034992, WO2006 / 034985 Anthranilic derivatives: Menthyl anthranilate sold under the trade name NEO HELIOPAN MA by Haarmann and REIMER, Imidazoline derivatives: Ethylhexyl Dimethoxybenzylidene Dioxoimidazoline Propionate, Derivatives of benzalmalonate: Di-neopentyl 4 methoxybenzalmalonate Benzalmalonate-functional polyorganosiloxane such as Polysilicone-15 sold under the trade name PARSOL SLX by Hoffmann La Roche Derivatives of 4,4-diarylbutadiene: -1,1-dicarboxy (2,2'-dimethylpropyl) -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 of Uvasorb K2A by Sigma 3V and their mixtures.

  The preferred complementary organic photoprotective agents are chosen from ethylhexyl methoxycinnamate homosalate ethylhexyl salicylate, octocrylene, phenylbenzimidazole sulphonic acid, benzophenone-3, benzophenone-4, n-hexyl benzophenone-5, 2- (4-diethylamino-2-hydroxybenzoyl) benzoate . 4-Methylbenzylidene camphor, Terephthalylidene Dicamphor Sulfonic Acid, Disodium Phenyl Dibenzimidazole Tetrasulfonate, Methylene bis-Benzotriazolyl Tetramethylbutylphenol Ethylhexyl Triazone, Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine Diethylhexyl Butamido Triazone, 2,4,6-Tris (4'-amino benzalmalonate Dineopentyl) 2,4,6-tris- (4'-amino benzalmalonate diisobutyl) -s-triazine. 2,4,6-tris (biphenyl-4-yl-1,3,5-triazine) 2,4,6-tris (terphenyl) -1,3,5-triazine Drometrizole Trisiloxane Polysilicone-15 Di-neopentyl 4'-methoxybenzalmalonate 1,1-dicarboxy (2,2'-dimethyl-propyl) -4,4-diphenylbutadiene 2,4-bis- [5-1 (dimethylpropyl) benzoxazol-2-yl- (4-phenyl) - imino] -6 (2-ethylhexyl) imino-1,3,5-triazine and mixtures thereof.

  The inorganic photoprotective agents are chosen from coated or uncoated metal oxide pigments (average size of the primary particles: generally between 5 nm and 100 nm, preferably between 10 nm and 50 nm), for example titanium oxide pigments. (Amorphous or crystallized in rutile and / or anatase form), iron, zinc, zirconium or cerium which are all UV photoprotective agents well known per se.

  The pigments can be coated or uncoated.

  The coated pigments are pigments which have undergone one or more surface treatments of a chemical, electronic, mechanochemical and / or mechanical nature with compounds as described, for example, in Cosmetics & Toiletries, February 1990, Vol. 105, p. 53-64, such as amino acids, beeswax, fatty acids, fatty alcohols, anionic surfactants, lecithins, sodium, potassium, zinc, iron or aluminum salts of fatty acids, metal alkoxides (titanium or aluminum), polyethylene, silicones, proteins (collagen, elastin), alkanolamines, silicon oxides, metal oxides or sodium hexametaphosphate.

  In a known manner, the silicones are organosilicon polymers or oligomers with a linear or cyclic, branched or crosslinked structure, of variable molecular weight, obtained by polymerization and / or polycondensation of suitably functionalized silanes, and essentially constituted by a repetition of main units in which the silicon atoms are connected to each other by oxygen atoms (siloxane bond), optionally substituted hydrocarbon radicals being directly bonded via a carbon atom to said silicon atoms.

  The term "silicones" also includes the silanes necessary for their preparation, in particular alkyl silanes.

  The silicones used for coating the pigments suitable for the present invention are preferably chosen from the group containing alkyl silanes, polydialkylsiloxanes, and polyalkylhydrogensiloxanes. Even more preferentially, the silicones are chosen from the group containing octyl trimethyl silane, polydimethylsiloxanes and polymethylhydro-genosiloxanes.

  Of course, the metal oxide pigments before their treatment with silicones, may have been treated with other surfactants, in particular with cerium oxide, alumina, silica, aluminum, silicon compounds, or mixtures thereof.

  The coated pigments are more particularly titanium oxides coated with: - silica such as the product "Sunveil" from the company IKEDA and the product "Eusolex TAVO" from the company MERCK - silica and iron oxide such as the product "SUNVEIL F" from the IKEDA company, - silica and alumina such as the products "MICROTITANIUM DIOXIDE MT 500 SA" and "MICROTITANIUM DIOXIDE MT 100 SA" from the company TAYCA, "TIOVEIL" from the company TIOXIDE, and Mirasun TiW 60 from Rhodia-Alumina, such as the products "TIPAQUE TTO-55 (B)" and "TIPAQUE TTO-55 (A)" from ISHIHARA, and "UVT 14/4" from the company KEMIRA, alumina and aluminum stearate such as the product "MICROTITANIUM DIOXIDE MT 100 TV, MT 100 TX, MT 100 Z, MT-01 from TAYCA, the products" Solaveil CT-10 W "," Solaveil CT 100 "and" Solaveil CT 200 "from the company UNIQEMA, silica, alumina and alginic acid such as the product" MT-100 AQ "from the company TAYCA, - alumina and aluminum laurate such as the product "MICROTITANIUM DIOXIDE 30 MT 100 S" from TAYCA, - iron oxide and iron stearate such as the product "MICROTITANIUM DIOXIDE MT 100 F" from TAYCA, - zinc oxide and zinc stearate such as the product "BR351" from the company TAYCA, -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, silica, alumina, aluminum stearate and treated with a silicone such as the product "STT-30-DS" from TITAN KOGYO, - of silica and treated with a silicone such as the product "UV-TITAN X 195" Kemira company, or the product SMT-100 WRS TAYCA society. of alumina and treated with a silicone such as the products "TIPAQUE TTO-55 (S)" from ISHIHARA, or "UV TITAN M 262" from KEMIRA, of triethanolamine such as the product "STT-65- S "of the company TITAN KOGYO, - stearic acid such as the product" TIPAQUE TTO-55 (C) "from the company ISHIHARA, - sodium hexametaphosphate such as the product" MICROTITANIUM DIOXIDE MT 150 W "of the TAYCA company.

  Other titanium oxide pigments treated with a silicone are preferably TiO 2 treated with octyl trimethyl silane and whose average elementary particle size is between 25 and 40 nm, such as that sold under the trade name "T 805 "by the company Degussa Silices, the TiO 2 treated with a polydimethylsiloxane and whose average elementary particle size is 21 nm, such as that sold under the trade name" 70250 Cardre UF TiO2S13 "by CARDRE, TiO2 anatase / rutile treated with a polydimethylhydrogensiloxane and whose average elementary particle size is 25 nm, such as that sold under the trade name "MICRO TITANIUM DIOXIDE USP GRADE HYDROPHOBIC" by the company COLOR TECHNIQUES.

  Uncoated titanium oxide pigments are for example sold by the company Tayca under the trade names "MICROTITANIUM DIOXIDE MT 500 B" or "MICROTITANIUM DIOXIDE MT600 B", by the company DEGUSSA under the name "P 25", by the WACKHER company under the name "transparent titanium oxide PW", by MIYOSHI KASEI under the name "UFTR", by TOMEN under the name "ITS" and by the company TIOXIDE under the name "TIOVEIL AQ".

  The uncoated zinc oxide pigments are, for example, those marketed under the name "Z-cote" by the company Sunsmart; those marketed under the name "Nanox" by the company Elementis; those marketed under the name "Nanogard WCD 2025" by Nanophase Technologies;

  The coated zinc oxide pigments are, for example, those marketed under the name Z-COTE HP1 by Sunsmart (dimethicone-coated ZnO); those marketed under the name "Zinc Oxide CS-5" by the company Toshibi (ZnO coated with polymethylhydrogenosiloxane); those marketed under the name "Nanogard Zinc Oxide FN" by Nanophase Technologies (as a 40% dispersion in Finsolv TN, C12-C15 alcohol benzoate); -Those sold under the name "DAITOPERSION ZN-30" and "DAITOPERSION Zn-50" by the company Daito (dispersions in cyclopolymethylsiloxane / polydimethylsiloxane oxyethylenated, containing 30% or 50% of zinc nano-oxides coated with silica and polymethylhydrogensiloxane ); those marketed under the name "NFD Ultrafine ZnO" by the company Daikin (ZnO coated with perfluoroalkyl phosphate and a copolymer based on perfluoroalkylethyl dispersed in cyclopentasiloxane); those marketed under the name "SPD-Z1" by Shin-Etsu (ZnO coated with silicone-grafted acrylic polymer, dispersed in cyclodimethylsiloxane); those marketed under the name "Escalol Z100" by the company ISP (ZnO treated alumina and dispersed in the mixture methoxycinnamate ethylhexyl / copolymer PVP-hexadecene / methicone); those marketed under the name "Fuji ZnO-SMS-10" by the company Fuji Pigment (ZnO coated with silica and polymethylsilsesquioxane); those marketed under the name "Nanox Gel TN" by Elementis (ZnO dispersed at 55% in C12-C15 alcohols benzoate with hydroxystearic acid polycondensate).

  Uncoated cerium oxide pigments are sold for example under the name "COLLOIDAL CERIUM OXIDE" by the company RHONE POULENC. Uncoated iron oxide nanopigments are for example sold by ARNAUD under the names "NANOGARD WCD 2002 (FE 45B)", "NANOGARD IRON FE 45 BL AQ", "NANOGARD FE 45R AQ," NANOGARD WCD 2006 ( FE 45R) ", or by the company MITSUBISHI under the name" TY-220 ".

  The coated iron oxide pigments are for example sold by ARNAUD under the names "NANOGARD WCD 2008" (FE 45B FN) "," NANOGARD WCD 2009 (FE 45B 556) "," NANOGARD FE 45 BL 345 "," NANOGARD FE 45 BL ", or by the company BASF under the name" OXIDE OF CLEAR IRON ".

  Mention may also be made of mixtures of metal oxides, in particular titanium dioxide and cerium dioxide, including the titanium dioxide / silica-coated cerium-aluminum alloy mixture sold by the company IKEDA under the 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 that the product "M 211" sold by KEMIRA.

  The additional photoprotective agents are generally present in the compositions according to the invention in proportions ranging from 0.01% to 20% by weight relative to the total weight of the composition, and preferably ranging from 0.1% to 10% by weight relative to the total weight of the composition. relative to the total weight of the composition.

  The compositions according to the invention may also contain agents for artificial tanning and / or browning of the skin (self-tanning agents), and more particularly dihydroxyacetone (DHA). They are preferably present in amounts ranging from 0.1 to 10% by weight relative to the total weight of the composition.

  The aqueous compositions in accordance with the present invention may also comprise conventional cosmetic adjuvants, chosen in particular from fatty substances, organic solvents, ionic or nonionic thickeners, hydrophilic or lipophilic thickeners, softeners, humectants, opacifiers, stabilizers, emollients, silicones, anti-foam agents, perfumes, preservatives, anionic, cationic, nonionic, zwitterionic or amphoteric surfactants, actives, fillers, polymers, propellants, basifying or acidifying agents or any another ingredient usually used in the cosmetic and / or dermatological field.

  The fatty substances may consist of an oil or a wax other than the apolar waxes as defined above or mixtures thereof. By oil is meant a liquid compound at room temperature. By wax is meant a compound which is solid or substantially solid at ambient temperature and whose melting point is generally greater than 35 C.

  As oils, mention may be made of mineral oils (paraffin); vegetable (sweet almond oil, macadamia oil, blackcurrant seed oil, jojoba oil); synthetic such as perhydrosqualene, alcohols, fatty amides (such as isopropyl lauroyl sarcosinate sold under the name of Eldew SL-205 by the company Ajinomoto), fatty acids or esters (such as C12 alcohols benzoate). C15 sold under the trade name Finsolv TN or Witconol TN by WITCO, octyl palmitate, isopropyl lanolate, triglycerides including those of capric / caprylic acids, dicaprylyl carbonate sold under the name Cetiol CC by the company Cognis), oxyethylenated or oxypropylene fatty esters and ethers; silicone oils (cyclomethicone, polydimethylsiloxane or PDMS) or fluorinated oils, polyalkylenes.

  As waxy compounds, mention may be made of carnauba wax, beeswax, hydrogenated castor oil, polyethylene waxes and polymethylene waxes, such as that sold under the name Cirebelle 303 by the company SASOL.

  Among the organic solvents, mention may be made of lower alcohols and polyols. These can be selected from glycols and glycol ethers such as ethylene glycol, propylene glycol, butylene glycol, dipropylene glycol or diethylene glycol.

  As hydrophilic thickeners, mention may be made of carboxyvinyl polymers such as Carbopols (Carbomers) and Pemulen (acrylate / C10-C30-alkylacrylate copolymer); polyacrylamides, for example crosslinked copolymers sold under the names Sepigel 305 (CTFA name: polyacrylamide / C13-14 isoparaffin / Laureth 7) or Simulgel 600 (CTFA name: acrylamide / sodium acryloyldimethyltaurate copolymer / isohexadecane / polysorbate 80) by the company Seppic ; polymers and copolymers of 2-acrylamido-2-methylpropanesulphonic acid, optionally cross-linked and / or neutralized, such as poly (2-acrylamido-2-methylpropanesulphonic acid) marketed by Hoechst under the trademark Hostacerin AMPS (CTFA name: ammonium polyacryloyldimethyl taurate or SIMULGEL 800 sold by the company SEPPIC (CTFA name: sodium polyacryolyldimethyl taurate / polysorbate 80 / sorbitan oleate); copolymers of 2-acrylamido-2-methylpropanesulphonic acid and hydroxyethyl acrylate such as SIMULGEL NS and SEPINOV EMT 10 sold by the company SEPPIC, cellulosic derivatives such as hydroxyethylcellulose, polysaccharides and in particular gums such as Xanthan gum, and mixtures thereof.

  As lipophilic thickeners, mention may be made of synthetic polymers such as poly C 10 -C 30 alkyl acrylates sold under the name INTELIMER IPA 13-1 and INTELIMER IPA 13-6 by the company Landec, or modified clays such as hectorite and its derivatives. derivatives, such as the products marketed under the names of Bentone.

  Among the active ingredients, mention may be made of: vitamins (A, C, E, K, PP) and their derivatives or precursors, alone or in mixtures, anti-pollution agents and / or anti-radical agents; depigmenting agents and / or pro-pigmenting agents; anti-glycation agents; the soothing agents; the NO-synthase inhibitors; agents stimulating the synthesis of dermal or epidermal macromolecules and / or preventing their degradation; agents stimulating the proliferation of fibroblasts; agents stimulating the proliferation of keratinocytes; - muscle relaxants; tensing agents, mattifying agents, keratolytic agents, desquamating agents; the moisturizing agents; anti-inflammatory agents; agents acting on the energetic metabolism of cells; insect repellents; antagonists of substances P or CRGP. - anti-hair loss and / or hair regrowth agents - anti-wrinkle agents.

  Of course, those skilled in the art will take care to choose the optional additional compound (s) mentioned above and / or their amounts in such a way that the advantageous properties intrinsically attached to the compositions in accordance with the invention are not, or substantially, not, altered by the addition or additions envisaged.

  The compositions according to the invention can be prepared according to the techniques well known to those skilled in the art. They may be in particular in the form of an emulsion, simple or complex (O / W, W / O, O / W / H or W / O / W) such as cream, milk or cream gel ; in the form of an aqueous gel; in the form of a lotion. They may optionally be packaged in aerosol and be in the form of foam or spray.

  Preferably, the compositions according to the invention are in the form of an oil-in-water or water-in-oil emulsion.

  The emulsions generally contain at least one emulsifier chosen from amphoteric, anionic, cationic or nonionic emulsifiers, used alone or as a mixture. The emulsifiers are suitably selected according to the emulsion to be obtained (W / O or O / W). The emulsions may also contain other types of stabilizers, for example fillers, gelling or thickening polymers.

  As emulsifying surfactants that may be used for the preparation of W / O emulsions, mention may be made, for example, of alkyl esters or ethers of sorbitan, of glycerol or of sugars; silicone surfactants such as dimethicone copolyols such as the mixture of cyclomethicone and dimethicone copolyol, sold under the name DC 5225 C by Dow Corning, and alkyl dimethicone copolyols such as Laurylmethicone copolyol sold under the name Dow Corning 5200 Formulation Aid "by Dow Corning; cetyl dimethicone copolyol such as the product sold under the name Abil EM 90R by Goldschmidt and the mixture of cetyl dimethicone copolyol, polyglycerol isostearate (4 moles) and hexyl laurate sold under the name ABIL WE 09 by the company Goldschmidt. One or more coemulsifiers may also be added, which advantageously may be selected from the group consisting of alkylated polyol esters.

  Polyol alkyl esters that may especially be mentioned include polyethylene glycol esters such as PEG-30 dipolyhydroxystearate, such as the product marketed under the name Arlacel P135 by the company ICI; Examples of glycerol and / or sorbitan esters that may be mentioned are polyglycerol isostearate, such as the product sold under the name Isolan GI 34 by the company Goldschmidt; sorbitan isostearate, such as the product sold under the name Arlacel 987 by the company ICI; sorbitan isostearate and glycerol, such as the product sold under the name Arlacel 986 by the company ICI, and mixtures thereof.

  For O / W emulsions, mention may be made, for example, as emulsifiers, of nonionic emulsifiers such as oxyalkylenated (more particularly polyoxyethylenated) fatty acid esters of glycerol; oxyalkylenated fatty acid and sorbitan esters; oxyalkylenated fatty acid esters (oxyethylenated and / or oxypropylenated) such as the PEG-100 Stearate / Glyceryl Stearate mixture marketed for example by the company ICI under the name Arlacel 165; oxyalkylenated fatty alcohol ethers (oxyethylenated and / or oxypropylenated); sugar esters such as sucrose stearate; fatty alcohol and sugar ethers, in particular alkylpolyglucosides (APG) such as decylglucoside and laurylglucoside sold, for example, by Henkel under the respective names Plantaren 2000 and Plantaren 1200, cetostearylglucoside optionally mixed with cetostearyl alcohol; , marketed for example under the name Montanov 68 by the company Seppic, under the name Tegocare CG90 by Goldschmidt and under the name Emulgade KE3302 by Henkel, and arachidyl glucoside, for example in the form of a mixture of arachidic and behenic alcohols and arachidylglucoside sold under the name Montanov 202 by the company Seppic. According to one particular embodiment of the invention, the mixture of the alkylpolyglucoside as defined above with the corresponding fatty alcohol may be in the form of a self-emulsifying composition, as described, for example, in WO- A-92/06778.

  Among the other emulsion stabilizers, the polymers of isophthalic acid or sulfoisophthalic acid, and in particular the phthalate / sulphoisophthalate / glycol copolymers, for example the diethylene glycol / phthalate / isophthalate / 1,4-diol copolymer, will be used more particularly. cyclohexane-dimethanol (INCI name: Polyester-5) sold under the names "Eastman AQ polymer" (AQ35S, AQ38S, AQ55S, AQ48 Ultra) by the company Eastman Chemical.

  In the case of an emulsion, the aqueous phase thereof may comprise a nonionic vesicular dispersion prepared according to known methods (Bangham, Standish and Watkins, J. Mol Biol 13, 238 (1965)). FR 2 315 991 and FR 2 416 008).

  The compositions according to the invention find their application in a large number of treatments, in particular cosmetics, of the skin, lips and hair, including the scalp, in particular for the protection and / or care of the skin, lips and / or hair, and / or for makeup of the skin and / or lips.

  Another object of the present invention is constituted by the use of the compositions according to the invention as defined above for the manufacture of products for the cosmetic treatment of the skin, lips, nails, hair, eyelashes, eyebrows and / or scalp, including skincare products, sunscreen products and make-up products.

  The cosmetic compositions according to the invention may for example be used as a makeup product.

  The cosmetic compositions according to the invention may for example be used as a skincare and / or sun protection product for the face and / or the body of liquid to semi-liquid consistency, such as milks, more or less unctuous creams, gel-creams, pasta. They may optionally be packaged in aerosol and be in the form of foam or spray.

  The compositions according to the invention in the form of vaporizable fluid lotions according to the invention are applied to the skin or the hair in the form of fine particles by means of pressurizing devices. The devices according to the invention are well known to those skilled in the art and include non-aerosol pumps or "atomizers", aerosol containers comprising a propellant and aerosol pumps using compressed air as a propellant. These are described in US Pat. Nos. 4,077,441 and 4,850,517 (which forms an integral part of the content of the description).

  The aerosol-conditioned compositions in accordance with the invention generally contain conventional propellants such as, for example, hydrofluorinated compounds, dichlorodifluoromethane, difluoroethane, dimethyl ether, isobutane, n-butane, propane and trichlorofluoromethane. They are present preferably in amounts ranging from 15 to 50% by weight relative to the total weight of the composition.

  Concrete but non-limiting examples illustrating the invention will now be given. EXAMPLES OF SYNTHESIS EXAMPLE 1 Preparation of 2-phenylethyl 3,4-dimethylbenzoate A mixture of 3,4-dimethyl benzoic acid (16.53 g, 0.11 mol) 2-phenyl ethanol (15.8 mL, 0.132 mole) and 98% sulfuric acid (0.6 mL, 0.011 mole) in 170 mL toluene. The brown reaction mixture is washed with water. After separation of the organic phase, the solvent is evaporated under reduced pressure. The residue is taken up in a Heptane / AcOEt 97: 3 mixture and is filtered on a silica bed. After isolation of the clean fractions and after evaporation of the solvent, 20.2 g (yield: 72%) of the compound of Example 1 are obtained in the form of a pale yellow oil. EXAMPLE 2 Preparation of bis (2-phenylethyl) pyridine-2,4-dicarboxylate: (a) (f) The mixture of 2,4-pyridine dicarboxylic acid (6 g, 0.0359 mol), 2-phenylethanol (10.16 ml, 0.085 mol) and 0.6 ml of concentrated sulfuric acid dissolved in 60 ml of toluene. After evaporation of the solvents under reduced pressure, the viscous yellow oil obtained is solubilized in dichloromethane and is purified on a silica bed. After evaporation of the solvent, 5.8 g (yield: 43%) of the clean fractions of the product of Example 2 are obtained in the form of a white solid.

EXAMPLES OF FORMULATION 3 to 5

  The following compositions were carried out and the photostability of 4-Tertiobutyl-4'-methoxy-Dibenzoylmethane was evaluated for each of them. EX3 EX4 EX5 Compositions (Comparative) Poly Dimethylsiloxane 0.5 0.5 0.5 Preservatives 1 1 1 Stearic acid 1.5 1.5 1.5 Mixture of glyceryl monostearate / 1 1 1 PEG stearate (100 0E) (ARLACEL P165- UNIQUEMA) Deionized water 73.35 73.35 73.35 Sequesterant 0.1 0 , 1 0.1 2-Ethylphenylbenzoate (X-TEND 226 8 -ISP) Mono or arylalkyl diester (compound a) Mono or arylalkyl diester (compound d) 4-Tertiobutyl-4'-methoxy - 2 2 2 Dibenzoylmethane (PARSOL 1789 DSM NUTRITIONAL PRODUCTS) Glycerol 5 5 5 Xanthan Gum 0.2 0.2 0.2 Potassium Cetyl Phosphate (AMPHISOL 1 1 1 K ûDSM NUTRITIONAL PRODUCTS) Iso-Hexadecane 1 1 1 Copolymer Acrylic Acid 0.22 0.2 stearyl methacrylate (PEMULEN TR 1- NOVEON) Cetyl alcohol 0.5 0.5 0.5 Triethanolamine 0.65 0.65 0.65 Mixture of cetylstearyl glucoside and 2 2 2 d 'alco cetyl and stearyl ols (MONTANOV 68 ûSEPPIC) 22 15 20 25 Measuring method

  For each formula, 3 test samples and 3 control samples were prepared. 2 mg / cm.sup.2 of the formula are deposited by spatula on plates of polymethylmethacrylate. The test plates are exposed for 38 minutes to the SUN TEST HERAUS equipped with a Xenon lamp having a UV-A flux of 9.51. 10-3 W / cm2 and a UV-B flux of 5.43 10-4 W / cm2. The control plates are stored for the same time and at the same temperature (38-40 ° C) in the dark. At the end of this time, the filters are extracted by immersing each plate in 50 g of methanol and sonicating them for 15 minutes to ensure good extraction. The solutions obtained are analyzed by HPLC and UV spectrophotometry.

  For each formula tested, the level of residual 4-tert-butyl-4'-methoxy-dibenzoylmethane after exposure is given in the ratio of its optical density (OD) in the sample exposed to its unexposed optical density (OD). The maximum absorption corresponding to butylimethoxy-dibenzoylmethane is Xmax = 358 nm.

  The results obtained are summarized in the following table: Compositions 0/0 residual of di-benzoylmethane after exposure 1 hour UVA Formula 1 52 0/0 Formula 2 74% Formula 3 65 0/0 There is a significant improvement in the photostability of dibenzoylmethane in the presence of arylalkyl mono or diester (compounds (a) and (d)) relative to 2-ethylphenyl benzoate (X-TEND 226 8 - ISP) 235

Claims (20)

  1. Composition containing in a cosmetically acceptable medium at least one UV-A filter of the dibenzoylmethane derivative type and at least one arylalkyl mono or diester derivative of the following formula (I): ## STR2 ## Wherein R 1 is a linear or branched C 1 -C 4 alkyl group, a is 0, 1 or 2, X is CH or N, m is an integer of 0 to 4, - R2 independently is H or methyl, - n is an integer from 0 to 4, - b is 1 or 2, with the following condition: if X = CH, R2 = H, m = 0, n = 2 then a is different from 0 and R1 different from methyl.   2. Composition according to claim 1, wherein the compound of formula (I) is chosen from the following products (a) to (f): RN = 89291-00-9 RN = 726-26-1 (a) (b) (c) RN = 758717-16-7 (d) o (e) RN = 71653-43-5 (f)   3. Composition according to any one of the preceding claims, wherein the arylalkyl mono or diester derivative (s) are present in the compositions at contents ranging from 0.1% to 40% by weight, and preferably at levels vary from 0.1% to 30% by weight, relative to the total weight of the composition.   4. Composition according to any one of the preceding claims, wherein the dibenzoylmethane derivative is chosen from: 2-methyldibenzoylmethane, 4-methyldibenzoylmethane, 4-isopropyldibenzoylmethane, 4-tert-butyldibenzoylmethane, 2,4-dimethyldibenzoylmethane, 2,5-dimethyldibenzoylmethane, 4,4'-diisopropyldibenzoylmethane, 4,4'-dimethoxydibenzoylmethane, 4-tert-butyl-4'-methoxydibenzoylmethane, 2-methyl 5-isopropyl-4'-methoxydibenzoylmethane, 2-methyl-5-tert-butyl-4'-methoxydibenzoylmethane, 2,4-dimethyl-4'-methoxydibenzoylmethane, 2,6-dimethyl-4- tert-butyl-4'-methoxydibenzoylmethane.   5. Composition according to claim 4, wherein the dibenzoylmethane derivative is 4-isopropyl-dibenzoylmethane corresponding to the following formula:   6. Composition according to claim 4, wherein the dibenzoylmethane derivative is 4- (tert-butyl) -4'-methoxy dibenzoylmethane or butyl methoxy dibenzoylmethane of the following formula:   7. Composition according to any one of the preceding claims, wherein the dibenzoylmethane derivative (s) are present at levels which vary from 0.01 to 10% by weight and more preferably from 0.1 to 6% by weight relative to total weight of the composition.   8. Composition according to any one of the preceding claims, characterized in that it contains in addition to other organic or inorganic agents active in the UV-A and / or UV-B water-soluble or fat-soluble or insoluble in commonly used cosmetic solvents. 20   9. Composition according to claim 8, wherein the complementary organic photoprotective agents are chosen from anthranilates; cinnamic derivatives; salicylic derivatives, camphor derivatives; benzophenone derivatives; 13,13-diphenylacrylate derivatives; triazine derivatives; benzotriazole derivatives; Benzalmalonate derivatives; benzimidazole derivatives; imidazolines; bis-benzoazolyl derivatives; p-aminobenzoic acid derivatives (PABA); methylene bis (hydroxyphenyl benzotriazole) derivatives; benzoxazole derivatives; filter polymers and silicone filters; dimers derived from α-alkylstyrene; 4,4-diarylbutadienes and mixtures thereof. 10 15 OMe 30   10. Composition according to Claim 9, characterized in that the organic UV screening agent (s) is (are) chosen from the following compounds: Ethylhexyl Methoxycinnamate Homosalate Ethylhexyl Salicylate, Octocrylene, Phenylbenzimidazole Sulfonic Acid, Benzophenone-3, Benzophenone-4, Benzophenone-5, N-hexyl 2- (4-diethylamino-2-hydroxybenzoyl) benzoate. 4-Methylbenzylidene camphor, Terephthalylidene Dicamphor Sulfonic Acid, Disodium Phenyl Dibenzimidazole Tetrasulfonate, Methylene bis-Benzotriazolyl Tetramethylbutylphenol Ethylhexyl Triazone, Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine Diethylhexyl Butamido Triazone, 2,4,6-Tris (4'-amino benzalmalonate Dineopentyl) 2,4,6-tris- (4'-amino benzalmalonate diisobutyl) -s-triazine. 2,4,6-tris (biphenyl-4-yl-1,3,5-triazine) 2,4,6-tris (terphenyl) -1,3,5-triazine Drometrizole Trisiloxane Polysilicone-15 Di-neopentyl 4'-methoxybenzalmalonate 1,1-dicarboxy (2,2'-dimethyl-propyl) -4,4-diphenylbutadiene 2,4-bis- [5-1 (dimethylpropyl) benzoxazol-2-yl- (4-phenyl) - imino] -6 (2-ethylhexyl) imino-1,3,5-triazine and mixtures thereof.   11. Composition according to claim 8, characterized in that the complementary inorganic photoprotective agents are metal oxide pigments, treated or not.   12. Composition according to claim 11, characterized in that said pigments are selected from titanium oxides, zinc, iron, zirconium, cerium and mixtures thereof, treated or not.   13. Composition according to any one of claims 1 to 12, characterized in that it further comprises at least one agent for tanning and / or artificial browning of the skin.   14. Composition according to any one of claims 1 to 13, characterized in that it further comprises at least one adjuvant selected from fatty substances, organic solvents, ionic or nonionic thickeners, hydrophilic or lipophilic, softeners, humectants, opacifiers, stabilizers, emollients, silicones, anti-foam agents, perfumes, preservatives, anionic, cationic, nonionic, zwitterionic or amphoteric surfactants, actives, fillers, polymers, propellants, alkalizing or acidifying agents   15. Composition according to any one of claims 1 to 14, characterized in that it is in the form of an oil-in-water or water-in-oil emulsion.   16. Use of a composition as defined in any one of claims 1 to 15 for the manufacture of products for the cosmetic treatment of skin, lips, nails, hair, eyelashes, eyebrows and / or scalp   17. Use of a composition as defined in any one of claims 1 to 15 for the manufacture of care products for the skin, lips, nails, hair and / or scalp. 25   18. Use of a composition as defined in any one of claims 1 to 15 for the manufacture of makeup products.   19. Process for improving the chemical stability with respect to the UV radiation of at least one UV-A filter of the dibenzoylmethane derivative type as defined in any one of the preceding claims, characterized by the fact that associates with said dibenzoylmethane derivative at least one mono or diester arylalkyl derivative of formula (I) as defined in the preceding claims.   20. Use of at least one arylalkyl mono or diester derivative of formula (I) as defined in the preceding claims in a composition comprising, in a cosmetically acceptable support, at least one dibenzoylmethane derivative as defined in US Pat. any of the preceding claims for the purpose of improving the effectiveness of said composition vis-à-vis UV-A. 20