OIL-FREE SUNCREEN COMPOSITION

TECHNICAL FIELD

The present invention relates to the field of cosmetics, and especially to the field of sunscreen compositions. BACKGROUND ART

It is known that radiation with wavelengths of between 280 nm and 400 nm permits tanning of the human epidermis and that radiation with wavelengths of between 280 and 320 nm, known as UV-B rays, harms the development of a natural tan. Exposure is also liable to bring about a detrimental change in the biomechanical properties of the epidermis, which is reflected by the appearance of wrinkles, leading to premature ageing of the skin.

It is also known that UV-A rays with wavelengths of between 320 and 400 nm penetrate more deeply into the skin than UV-B rays. UV-A rays cause immediate and persistent browning of the skin. Daily exposure to UVA rays, even of short duration, under normal conditions can result in damage to the collagen fibers and the elastin, which is reflected by a modification in the microrelief of the skin, the appearance of wrinkles and uneven pigmentation (liver spots, lack of uniformity of the complexion). Normal sprayable UV products contain mainly hydrophobic UV filter (or in other words hydrophobic UV-screening agent) in emulsion system. Some of them contain both oil-soluble and water-soluble UV filters and provide white spray mist, while some of them only contain oil-soluble UV filters. But such compositions contain only water-soluble UV filters (or in other words hydrophilic UV-screening agents). Water soluble UV filters provide only limited photoprotection ability. There is need for developing compositions, in particular sunscreen composition, having only water soluble UV filters while presenting a good UV- screening ability.

Due to the presence of high amount of hydrophobic UV filters, the products, as such, have a greasy feeling on the skin. Besides, the mist after spraying is colored (white) and therefore gives an unpleasant feeling on the skin (usually defined as "heavy feeling"), which is not favored by the consumers, especially those who do not prefer makeup products. There is thus need for developing compositions, in particular sunscreen composition, having only water soluble UV filters while presenting good feeling on the skin. There is also need for developing compositions, in particular sunscreen composition, having only water soluble UV filters while being uncolored when applied onto the skin. Anti-sun products provided in spray form are increasingly sought by consumers because of their ease of use and their cosmetic pleasantness. Unlike conventional anti-sun milks and creams, it is particularly difficult to obtain anti-sun compositions in spray form having a high protection index.

AIMS OF THE INVENTION

The present invention aims to provide a composition, in particular a sunscreen composition, having only hydrophilic UV-screening agents while presenting a good UV-screening ability.

The present invention also aims to provide a composition, in particular a sunscreen composition, having only hydrophilic UV-screening agents while presenting good feeling on the skin.

Another aim of the present invention is to provide a composition, in particular a sunscreen composition, having only hydrophilic UV-screening agents while being uncolored when applied onto the skin.

Another aim of the present invention is to provide a sprayable composition, in particular a sprayable sunscreen composition, solving the above mentioned problems.

In more general terms, the invention aims to provide an oil-free sprayable sunscreen composition. More particularly, such composition would be a transparent spray with mist and light texture when applied onto the skin, as appreciated by the user.

DISCLOSURE OF INVENTION

It has been discovered, in accordance to the present invention, that these objectives could be achieved with a composition comprising at least one copolymer of styrene and acrylate, at least one solubilizing agent, solubilizing the copolymer of styrene and acrylate, and one or more UV- screening agents. In fact, the use of at least one copolymer of styrene and acrylate improves the sunblocking or sunscreening effect of a UV-screening composition.

By "improving the sunblocking or sunscreening effect", it is in particular meant the SPF (Sun Protection Factor) and/or PPD (Persistent Pigment Darkening) value of a composition is higher when the copolymer is present in the composition comparatively to substantially the same composition without this copolymer.

SPF is preferably measured according to International standard EN ISO 24444:2010 Cosmetics - Sun protection test methods - In vivo determination of the sun protection factor (SPF). PPD is skin darkening that persists more than 2 h after the end of UVA exposure. It is determined according to ISO 24442:201 1 (en) Cosmetics - Sun protection test methods - In vivo determination of sunscreen UVA protection.

For the purposes of the invention, the term "oil-free" means a composition comprising a single liquid phase which is an aqueous phase (a liquid phase including water). The oil-free composition of the invention does not comprise an oily phase. The term "oily phase" means, according to the invention, a phase that forms a two-phase liquid system with the aqueous phase at 20-25°C and 101325Pa. Such "oily phase" generally comprises at least one oil. The term "oil" means any fatty substance which is in liquid form at room temperature (20 to 25°C) and at atmospheric pressure (760 mmHg). The "fatty substance" comprises at least one hydrocarbon chain, "fat" that is to say a linear hydrocarbon chain of at least 4 carbon atoms, unsaturated or not unsaturated, optionally substituted, and in particular a linear hydrocarbon chain C ₅ -C ₃₀ . The term "oil" does not cover for example water-soluble active ingredients, water- soluble UV-screening agents, and water-soluble glycols (glycol generally comprising no linear hydrocarbon chain of at least 4 carbon atoms, unsaturated or not unsaturated, optionally substituted).

The term "sunscreen composition" or "sunscreen agent" means any composition or ingredient that absorbs or scatters at least a part of UV radiations and prevents said UV radiations from reaching the skin, especially deeper layers of the skin (typically the dermis). This term is broadly used to cover sunblocks and sunscreens. The efficacy of such compositions or agents is typically measured by the SPF and/or PPD value.

The term "keratin material" means the skin (of the body, face and around the eyes), hair, eyelashes, eyebrows, bodily hair, nails, lips or mucous membranes.

DETAILED DESCRIPTION OF THE INVENTION The composition according to the present invention relates to an oil-free composition, notably a sunscreen composition, comprising: a) at least one copolymer of styrene and acrylate, b) at least one solubilizing agent, solubilizing the copolymer of styrene and acrylate, wherein said solubilizing agent is selected from the group consisting of polyoxyalkylene ether of alkyl alcohols, polyalkylene glycols of saturated or unsaturated fatty acid, optionally hydrogenated, or a mixture thereof, and c) one or more UV-screening agents. The compositions according to the invention may comprise organic or inorganic sunscreen agents, also known as filtering agents or filters, filtering wavelengths within the UVA and/or UVB ranges, which are hydrophilic or lipophilic or insoluble in routine cosmetic solvents.

The organic filters may be selected from anthranilics; cinnamic derivatives; salicylic derivatives; benzophenone derivatives; phenyl benzotriazole derivatives; benzalmalonate derivatives particularly those cited in the patent US5624663; phenyl benzimidazole derivatives; imidazolines; 4,4-diarylbutadiene derivatives; bis-benzoazolyle derivatives as described in the patents EP669323 and US 2,463,264; p-aminobenzoic acid (PABA) derivatives; methylene bis- (hydroxyphenyl benzotriazole) derivatives as described in the applications US5,237,071 , US 5, 166,355, GB2303549, DE 197 26 184 and EP8931 19; benzoxazole derivatives as described in the patent applications EP0832642, EP1027883, EP1300137 and DE10162844; filter polymers and filter silicones such as those particularly described in the application WO- 93/04665; dimers derived from a-alkylstyrene such as those described in the patent application DE19855649; 4,4-diarylbutadienes as described in the applications EP0967200, DE19746654, DE19755649, EP-A-1008586, EP1 133980 and EP133981 ; merocyanine derivatives such as those described in WO04006878, WO05058269 and WO06032741 and the mixtures thereof.

More preferably the composition comprises one or more hydrophilic UV-screening agents. In a preferred embodiment, said composition comprises only hydrophilic UV-screening agents among UV-screening agents present in the composition. In such a particular embodiment, the composition comprises 0% by weight of hydrophobic UV-screening agent, relative to the total weight of the composition.

The term "hydrophilic UV-screening agent" means any organic or mineral sunscreen agent capable of being fully dissolved in molecular form in a liquid aqueous phase or of being dissolved in colloidal form (for example in micellar form) in a liquid aqueous phase.

The term "hydrophobic UV-screening agent" or "lipophilic screening agent" means any organic or mineral sunscreen agent which can be fully dissolved in molecular state in a liquid fatty phase or which can be dissolved in colloidal form (for example in micellar form) in a liquid fatty phase. Examples of organic UV-screening agents include those referred to hereinafter using the INCI name thereof:

Classification according to UVA and/or UVB radiation wavelength range

1/ Lipophilic UV-A screening agents

Dibenzoylmethane derivatives:

Isopropyl Dibenzoylmethane;

Aminobenzophenones:

n-hexyl 2-(4-diethylamino-2-hydroxybenzoyl)-benzoate particularly sold under the trade name "UVINUL A +" by BASF;

1 , 1 '-(1 ,4-piperazinediyl)bis[1 -[2-[4-(diethylamino)-2-hydroxybenzoyl]phenyl]-methanone

(CAS 919803-06-8)

Anthranilic derivatives:

Menthyl anthranilate particularly sold under the trade name "NEO HELIOPAN MA" by SYMRISE; 4,4-diarylbutadiene derivatives:

1 , 1 -dicarboxy (2,2'-dimethyl-propyl)-4,4-diphenylbutadiene;

Merocyanine derivatives:

Octyl-5-N,N-diethylamino-2-phenysulfonyl-2,4-pentadienoate;

Within the scope of the invention, and according to one particular embodiment, the following lipophilic filters are used:

Butyl Methoxydibenzoylmethane

II/ Hydrophilic UV-A screening agents

The bis-benzoazolyl derivatives as described in the patents EP 669 323, and US 2,463,264 and more specifically the compound Disodium Phenyl Dibenzimidazo tetra-sulfonate sold under the trade name "NEO HELIOPAN AP" by SYMRISE;

The preferred hydrophilic UVA screening agent is Terephthalylidene Dicamphor Sulfonic Acid.

Ill/ Lipophilic UV-B screening agents

Para-aminobenzoates: Ethyl PABA;

Ethyl Dihydroxypropyl PABA;

Ethylhexyl Dimethyl PABA (ESCALOL 507 from ISP);

Salicylic derivatives:

Homosalate particularly sold under the name "Eusolex HMS" by Rona/EM Industries;

Ethylhexyl Salicylate particularly sold under the name "NEO HELIOPAN OS" by SYMRISE; Dipropyleneglycol Salicylate particularly sold under the name "DIPSAL" by SCHER;

TEA Salicylate sold under the name "NEO HELIOPAN TS" by SYMRISE;

Cinnamates

Ethylhexyl Methoxycinnamate particularly sold under the trade name "PARSOL MCX" by DSM Nutritional Products, Inc.;

Isopropyl Methoxy cinnamate;

Isoamyl Methoxy cinnamate particularly sold under the trade name "NEO HELIOPAN E 1000" by SYMRISE;

Diisopropyl Methylcinnamate;

Cinnoxate;

Glyceryl Ethylhexanoate Dimethoxycinnamate;

β,β'-diphenylacrylate derivatives:

Etocrylene, particularly sold under the trade name "UVINUL N35" by BASF;

Benzylidene camphor derivatives:

3-Benzylidene camphor manufactured under the name "MEXORYL SD" by CHIMEX;

Methylbenzylidene camphor sold under the name "EUSOLEX 6300" by MERCK;

Polyacrylamidomethyl Benzylidene Camphor manufactured under the name "MEXORYL SW" by CHIMEX;

Triazine derivatives:

Ethylhexyl triazone particularly sold under the trade name "UVINUL T150" by BASF; Diethylhexyl Butamido Triazone particularly sold under the trade name "UVASORB 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(dineopentyl 4'-amino benzalmalonate)-6-(n-butyl 4'-aminobenzoate)-s-triazine;

2,4-bis(n-butyl 4'-amino benzoate)-6-(aminopropyltrisiloxane)-s-triazine;

the symmetrical triazine filters described in the patent US 6,225,467, the 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 (September 20, 2004) particularly 2,4, 6-tris-(biphenyl)-1 ,3,5-triazine (particularly 2,4,6- tris(biphenyl-4-yl-1 ,3,5-triazine) and 2, 4, 6-tris(terphenyl)-1 ,3,5-triazine, the latter two filters being described in the BEIERSDORF applications WO 06/035000, WO 06/034982, WO 06/034991 , WO 06/035007, WO 2006/034992, WO 2006/034985).

Imidazoline derivatives:

Ethylhexyl Dimethoxybenzylidene Dioxoimidazoline Propionate,

Benzalmalonate derivatives:

Polyorganosiloxanes with a benzalmalonate function such as Polysilicone-15 particularly sold under the trade name "PARSOL SLX" by DSM Nutritional Products, Inc.;

Di-neopentyl 4'-methoxybenzalmalonate;

Within the scope of the invention, and according to one particular embodiment, the following lipophilic UV-B filters are used in the composition according to the invention:

Ethylhexylsalicylate;

Octocrylene;

Ethylhexyl triazone.

IV/ Hydrophilic UV-B screening agents

The following p-aminobenzoic acid (PABA) derivatives:

PABA,

Glyceryl PABA and PEG-25 PABA particularly sold under the trade name "UVINUL P25" by BASF.

Phenylbenzimidazole Sulfonic Acid particularly sold under the trade name "EUSOLEX 232" by MERCK,

ferulic acid,

salicylic acid,

DEA methoxycinnamate,

Benzylidene Camphor Sulfonic Acid manufactured under the name "MEXORYL ^® SL" by CHIMEX,

Camphor Benzalkonium Methosulfate manufactured under the name "MEXORYL ^® SO" by CHIMEX,

According to a preferred embodiment, the preferred hydrophilic UVB screening agent is Phenylbenzimidazole Sulfonic Acid.

V/ Combined lipophilic UVA and UVB screening agents

Benzophenone derivatives

Benzophenone-1 particularly sold under the trade name "UVINUL 400" by BASF;

Benzophenone-2 particularly sold under the trade name "UVINUL D50" by BASF;

Benzophenone-3 or Oxybenzone particularly sold under the trade name "UVINUL M40" by BASF;

Benzophenone-6 particularly sold under the trade name "Helisorb 1 1 " by Norquay;

Benzophenone-8 particularly sold under the trade name "Spectra-Sorb UV-24" by American Cyanamid;

Benzophenone-10;

Benzophenone-1 1 ;

Benzophenone-12;

Phenyl benzotriazole derivatives:

Drometrizole Trisiloxane particularly sold under the name "Silatrizole" by RHODIA CHIMIE or manufactured under the name "Meroxyl XL" by CHIMEX; Methylene bis-Benzotriazolyl Tetramethylbutylphenol, sold in solid form particularly under the trade name "MIXXIM BB/100" by FAIRMOUNT CHEMICAL or in micronized form in aqueous dispersion particularly under the trade name "TINOSORB M" by CIBA SPECIALTY CHEMICALS;

Benzoxazole derivatives:

2,4-bis-[5-1 (dimethylpropyl)benzoxazol-2-yl-(4-phenyl)-imino]-6-(2-ethyl hexyl)-imino-1 ,3,5- triazine particularly sold under the name Uvasorb K2A by Sigma 3V.

The preferential lipophilic organic UVA and UVB filters are selected from:

Drometrizole Trisiloxane;

Methylene bis-Benzotriazolyl Tetramethylbutylphenol;

Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine.

VI/ Combined hydrophilic UVA and UVB screening agents

Benzophenone derivatives comprising at least one sulfonic radical such as

Benzophenone-4 particularly sold under the trade name "UVINUL MS 40" by BASF,

Benzophenone-5 and

Benzophenone-9.The composition according to the invention may also comprise mineral filters which are pigments. The pigments may be coated or uncoated.

The coated pigments are pigments which have undergone one or a plurality of chemical, electronic, mechanochemical and/or mechanical surface treatments 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 (titanium or aluminum) alkoxides, polyethylene, silicones, proteins (collagen, elastin), alkanolamines, silicon oxides, metal oxides or sodium hexametaphosphate.

According to the prior art, the silicones are organosilicate polymers or oligomers with a linear or cyclic, branched or cross-linked structure, with a variable molecular weight, obtained by polymerization and/or polycondensation of suitably functionalized silanes, and essentially consisting of a repetition of primary structural units wherein the silicon atoms are interconnected by oxygen atoms (siloxane bond), optionally substituted hydrocarbon radicals being directly bound via a carbon atom on said silicon atoms.

The term "silicones" also covers the silanes required for the preparation thereof, particularly, alkyl silanes.

The silicones used for coating pigments suitable for the present invention are preferably selected from the group containing alkyl silanes, polydialkylsiloxanes, and polyalkylhydrogen siloxanes. More preferentially, the silicones are selected from the group containing octyl trimethyl silane, polydimethylsiloxanes and polymethylhydrogen siloxanes.

Obviously, prior to the treatment thereof with silicone, the metal oxide pigments may have been treated with other surface agents, particularly cerium oxide, alumina, silica, aluminum compounds, silicon compounds, or mixtures thereof.

The coated pigments are, for example, titanium oxides coated with:

- silica such as the product "SUNVEIL" from IKEDA and the product "Eusolex T-AVO" from MERCK

- silica and iron oxide such as the product "SUNVEIL F" from IKEDA,

- silica and alumina such as the products "MICROTITANIUM DIOXIDE MT 500 SA" and "MICROTITANIUM DIOXIDE MT 100 SA" from TAYCA, "TIOVEIL" from 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 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 UNIQEMA,

- silica, alumina and alginic acid such as the product "MT-100 AQ" from TAYCA,

- alumina and aluminum laurate such as the product "MICROTITANIUM DIOXIDE 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 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,

- silica and treated with a silicone such as the product "UV-TITAN X 195" from KEMIRA, or the product SMT-100 WRS from TAYCA.- alumina and treated with a silicone such as the products "TIPAQUE TTO-55 (S)" from ISHIHARA, or "UV TITAN M 262" from KEMIRA,

triethanolamine such as the product "STT-65-S" from TITAN KOGYO,

- stearic acid such as the product "TIPAQUE TTO-55 (C)" from ISHIHARA,

- sodium hexametaphosphate such as the product "MICROTITANIUM DIOXIDE MT 150 W" from TAYCA.

Further titanium oxide pigments treated with a silicone are for example Ti0 ₂ treated with octyl trimethyl silane such as that sold under the trade name "T 805" by DEGUSSA SILICES, Ti0 ₂ treated with a polydimethylsiloxane such as that sold under the trade name "70250 Cardre UF Ti02SI3" by CARDRE, anatase/rutile Ti0 ₂ treated with a polydimethylhydrogen siloxane such as that sold under the trade name "MICRO TITANIUM DIOXYDE USP GRADE HYDROPHOBIC" by COLOR TECHNIQUES.

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

The uncoated zinc oxide pigments are for example

- those marketed under the name "Z-cote" by Sunsmart;

- those marketed under the name "Nanox" by 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 (ZnO coated with dimethicone); - those marketed under the name "CS-5 zinc oxide" by Toshibi (ZnO coated with polymethylhydrogen siloxane);

- those marketed under the name "Nanogard Zinc Oxide FN" by Nanophase Technologies (in 40% dispersion in Finsolv TN, C12-C15 alcohol benzoate);

- those marketed under the name "DAITOPERSION ZN-30" and "DAITOPERSION Zn-50" by Daito (dispersions in cyclopolymethylsiloxane/oxyethylenated polydimethylsiloxane, containing 30% or 50% zinc oxides coated with silica and polymethylhydrogen siloxane);

- those marketed under the name "NFD Ultrafine ZnO" by Daikin (ZnO coated perfluoroalkyl phosphate and perfluoroalkylethyl-based copolymer in dispersion 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 ISP (ZnO treated with alumina and dispersed in the ethylhexyl methoxycinnamate / PVP-hexadecene copolymer / methicone mixture);

- those marketed under the name "Fuji ZnO-SMS-10" by Fuji Pigment (ZnO coated with silica and polymethylsilsesquioxane);

- those marketed under the name "Nanox Gel TN" by Elementis (ZnO in 55% dispersion in C ₁₂ - C ₁₅ alcohol benzoate with hydroxystearic acid polycondensate).

The uncoated cerium oxide pigments are sold for example under the name "COLLOIDAL CERIUM OXIDE" by RHONE POULENC.

The uncoated iron oxide pigments 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 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 BASF under the name "TRANSPARENT IRON OXIDE".

It is also possible to cite metal oxide mixtures, particularly 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 name "SUNVEIL A", and 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 glycerin such as the product "M 21 1 " sold by KEMIRA.

The pigments may be introduced into the compositions according to the invention as is or in pigment paste form, i.e. in a mixture with a dispersion agent, as described for example in the document GB-A-2206339.

According to a particular embodiment, the composition does not comprise hydrophobic UV- screening agents.

According to a particular embodiment, said UV-screening agent is selected from the group consisting of sulfonic acid based hydrophilic UV-screening agents. In a specific embodiment, the composition of the invention comprises phenylbenzimidazole sulfonic acid and/or terephtalylidene dicamphor sulfonic acid.

In general the composition of the invention comprises from 3% to 40% by weight, more preferably from 5% to 30% by weight, and even more preferably from 8 to 20% by weight, relative to the total weight of the composition, of one or more UV-screening agents. In particular, the composition of the invention comprises from 3% to 40% by weight, more preferably from 5% to 30% by weight, and even more preferably from 8 to 20% by weight, relative to the total weight of the composition, of hydrophilic UV-screening agents.

The composition of the present invention comprises at least one copolymer of styrene and acrylates. According to one embodiment the styrene/acrylates copolymer is a polymer of styrene and a monomer consisting of acrylic acid, methacrylic acid or one of their simple esters.

According to one embodiment said copolymer of styrene and acrylate is an anionic polymer of styrene and acrylate, preferably a sodium polymer of styrene and acrylate.

Suitable Styrene/Acrylates Copolymers include styrene/acrylate copolymers like Opulyn ^™ 301 from Rohm and Haas.

Such copolymer is in general in the form of particles, but is solubilized in the composition of the invention by a solubilizing agent. In one embodiment, the composition comprises from 0.001 % to 10% by weight, preferably from 0.001 % to 5% by weight, more preferably from 0.1 % to 3% by weight, of copolymer of styrene and acrylate, relative to the total weight of the composition.

The composition of the present invention comprises at least one solubilizing agent. In one embodiment, the solubilizing agent is selected from the group consisting of polyoxyalkylene ether of alkyl alcohols, polyalkylene glycols of saturated or unsaturated fatty acid, optionally hydrogenated, and any mixture thereof.

More specifically, the polyoxylakylene etherof alkyl alcohols may be chosen from polyoxyethylene ether and/or polyoxypropylene ether of alkyl alcohols, or a mixture thereof. In one embodiment, the solubilizing agent is preferably polyoxyethylene ether and/or polyoxypropylene ether of C C ₁₂ , more preferably C C ₈ , even more preferably C ₄ alcohol, or a mixture thereof.

Mentions may be made of, for example, oxypropylenated (26 PO) oxyethylenated (26 EO) butyl alcohols. The solubilizing agents of the present invention may also be chosen from polyalkylene glycols of saturated or unsaturated fatty acid, optionally hydrogenated, or its mixture.

In one embodiment, the solubilizing agent is a polyalkylene glocols of castor oil, optionally hydrogenated, or its mixture.

Mentions may be made of oxyethylenated castor oils such as PEG-40 castor oil, PEG-60 castor oil, preferably hydrogenated, or a mixture thereof.

According to one embodiment, mentions can be made of the solubilizing agents, such as oxyethylenated (40 EO) hydrogenated castor oil sold as a mixture with oxypropylenated (26 PO) oxyethylenated (26 EO) butyl alcohol in water under the reference Solubilisant LRI by LCW, the polyoxyl 40 hydrogenated castor oil sold under the name Cremophore RH 40, the PEG-60 hydrogenated castor oil sold under the name Eumulgin Co 60 by the company Cognis (BASF), or a mixture thereof.

In one embodiment, the composition comprises from 0.001 % to 20% by weight, preferably from 0.01 % to 10% by weight, more preferably from 0.1 % to 5% by weight, of said solubilizing agent, relative to the total weight of the composition. According to one embodiment, the composition of the invention is oil-free.

In one embodiment, the composition according to the invention is an aqueous solution.

In one embodiment, the composition according to the invention comprises a continuous aqueous phase optionally with solid particles dispersed therein. The continuous aqueous phase comprises water.

In one embodiment, the continuous aqueous phase may comprise at least one C C ₄ alcohol, preferably in an amount of 0.1 % to 20% by weight, relative to the total weight of the composition.

An alcohol according to the present invention may preferably be chosen from linear or branched, saturated or unsaturated alcohols with at least one hydroxyl group, or dialkylene alcohols with at least one hydroxyl group. Preferably the alcohol of the present invention is chosen from linear C C ₄ hydroxyalkyls, C C ₄ dialkylene alcohols, or a mixture thereof.

In one embodiment, the composition of the invention comprises from 0.1 % to 20% by weight, relative to the total weight of the composition, of at least one C C ₄ alcohol with at least one hydroxyl group, linear or branched, saturated or unsaturated. Preferably the alcohol of the present invention is chosen from ethanols, ethylene glycols, dipropylene glycols, or a mixture thereof.

According to an even preferred embodiment, the C C ₄ alcohol of the present invention is ethanol, dipropylene glycol, or a mixture thereof.

In particular, the composition of the present invention comprises from 0.5% to 15% by weight, more preferably from 1 % to 10% by weight of the C C ₄ alcohol, relative to the total weight of the composition.

The continuous aqueous phase may also comprise water-miscible organic solvents (at room temperature of 20-25°C), for instance polyols especially containing from 2 to 20 carbon atoms, preferably containing from 2 to 10 carbon atoms and preferentially containing from 2 to 6 carbon atoms, such as glycerol, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, dipropylene glycol or diethylene glycol; glycol ethers (especially containing from 3 to 16 carbon atoms) such as mono-, di- or tripropylene glycol (C C ₄ )alkyl ethers, mono-, di- or triethylene glycol (C C ₄ )alkyl ethers, and mixtures thereof. In one embodiment, the composition of the invention comprises at least one glycol, preferably selected from the group consisting of glycol alkylene, for example C C ₁₂ alkylene glycol, a dialkylene glycol, for example Ci.Cs dialkylene glycol, and any mixture thereof.

The aqueous phase may also comprise stabilizers, for example sodium chloride, magnesium dichloride or magnesium sulfate.

Additives

The compositions in accordance with the present invention may also comprise conventional cosmetic additives soluble in the aqueous phase of the composition of the invention chosen in particular from organic solvents, ionic or nonionic thickeners, softeners, humectants, additional opacifiers, stabilizers, emollients, silicones, antifoams, fragrances, preserving agents, anionic, cationic, nonionic, zwitterionic or amphoteric surfactants, active agents, fillers, polymers, propellants, acidifying or basifying agents or any other ingredient commonly used in the cosmetic and/or dermatological field.

Among the organic solvents that may be mentioned are alcohols and in particular the short chain C ₂ -C ₈ polyols, for instance glycerol, diols for instance caprylyl glycol, 1 ,2-pentanediol, propanediol, butanediol, glycols and glycol ethers, for instance ethylene glycol, propylene glycol, butylene glycol, dipropylene glycol or diethylene glycol.

Thickeners that may be mentioned include the carboxyvinyl polymers such as the Carbopol ^® products (Carbomers) and the Pemulen products, for instance Pemulen TR1 ^® and Pemulen TR2 ^® (acrylate/C ₁₀ -C ₃ o alkyl acrylate copolymer); polyacrylamides, for instance the crosslinked copolymers sold under the names Sepigel 305 ^® (CTFA name: polyacrylamide/C ₁₃ - ₁₄ isoparaffin/laureth 7) or Simulgel 600 (CTFA name: acrylamide/sodium acryloyldimethyltaurate copolymer/isohexadecane/polysorbate 80) by the company SEPPIC; 2-acrylamido-2- methylpropanesulfonic acid polymers and copolymers, optionally crosslinked and/or neutralized, for instance poly(2-acrylamido-2-methylpropanesulfonic acid) sold by the company Hoechst under the trade name "Hostacerin AMPS ^® " (INCI name: ammonium polyacryloyldimethyl taurate, made with AMPS ^® monomer (2-acrylamido-2-methylpropanesulfonic acid from LUBRIZOL), or Simulgel 800 ^® sold by the company SEPPIC (CTFA name: sodium polyacryolyldimethyl taurate/polysorbate 80/sorbitan oleate); copolymers of 2-acrylamido-2-methylpropanesulfonic acid and of hydroxyethyl acrylate, for instance Simulgel NS ^® and Sepinov EMT 10 ^® sold by the company SEPPIC; cellulose derivatives such as hydroxyethylcellulose; polysaccharides and especially gums such as xanthan gum; water-soluble or water-dispersible silicone derivatives, for instance acrylic silicones, polyether silicones and cationic silicones, and mixtures thereof.

Among the acidifying agents, examples that may be mentioned include mineral or organic acids, for instance hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids, for instance acetic acid, tartaric acid, citric acid or lactic acid, and sulfonic acids.

Among the basifying agents, examples that may be mentioned include aqueous ammonia, alkali metal carbonates, alkanolamines such as monoethanolamine, diethanolamine and triethanolamine, and also derivatives thereof, sodium hydroxide and potassium hydroxide.

Preferably, the cosmetic composition comprises one or more basifying agents chosen from alkanolamines, in particular triethanolamine, and sodium hydroxide.

In the case of a aqueous solution, the pH of the composition in accordance with the invention is generally between 3 and 12 approximately, preferably between 5 and 1 1 approximately and even more particularly from 6.5 to 8.5.

Among the active agents for caring for keratin materials such as the skin, the lips, the scalp, the hair, the eyelashes or the nails, examples that may be mentioned include:

- vitamins and derivatives or precursors thereof, alone or as mixtures;

- antioxidants;

- free-radical scavengers;

- antipollution agents; - self-tanning agents;

- antiglycation agents;

- calmatives;

- deodorants;

- essential oils;

- NO-synthase inhibitors; - agents for stimulating the synthesis of dermal or epidermal macromolecules and/or which prevent their decomposition;

- agents for stimulating the proliferation of fibroblasts;

- agents for stimulating the proliferation of keratinocytes;

- muscle relaxants;

- refreshing agents;

- tensioning agents;

- mattifying agents;

- depigmenting agents;

- propigmenting agents;

- keratolytic agents;

- desquamating agents;

- moisturizers;

- antiinflammatory agents;

- antimicrobial agents;

- slimming agents;

- agents acting on the energy metabolism of cells;

- insect repellents;

- substance P or CGRP antagonists;

- hair-loss counteractants;

- antiwrinkle agents;

- antiageing agents. A person skilled in the art will select the said active principle(s) according to the effect desired on the skin, the hair, the eyelashes, the eyebrows or the nails.

Needless to say, a person skilled in the art will take care to select the abovementioned optional compound(s) and/or the amounts thereof such that the advantageous properties intrinsically associated with the compositions in accordance with the invention are not, or are not substantially, adversely affected by the envisaged addition(s).

If one or more oils are present as additives their total amount should satisfy the invention's requirement (i.e. being soluble in the aqueous phase of the composition).

In one embodiment, the composition of the invention comprises: (i) from 0.001 % to 10%, preferably from 0.001 % to 5%, more preferably from 0.1 % to 3%, of copolymer of styrene and acrylate; (ii) from 0.001 to 20%, preferably from 0.01 to 10%, more preferably from 0.1 to 5%, of said solubilizing agent; and (iii) from 3 to 40% of one or more UV-screening agents, wherein % are expressed by weight relative to the total weight of the composition.

The composition of the present invention is sprayable or, in other words, capable of being dispensed in the form of fine particles.

This means that the composition may be dispensed using a dispenser having a spray nozzle.

Accordingly, the present invention also relates to a device comprising a container and a spray nozzle, wherein said container contains the composition of the invention. In one preferred embodiment the composition is translucent, or even transparent. The compositions of the invention may be applied with any device having spraying means, including suitable aerosol or non-aerosol spray devices. Non-aerosol spray devices are preferred, and include for example, spray pumps such as the following: Eurogel Spray Pump (available from Seqquist Perfect, Cary III.), P1 spray pump (available from Precision, Ajax, Canada), Calmar Spray Pumps, Calmar, Inc., City of Industry, Calif, and Mitani Mist Pumps (available from MITANI VALVE CO., LTD).

The composition of the present invention is transparent or translucent, preferably translucent.

The term "translucent" means that allows light to pass through without making it possible to distinguish alphanumeric characters using 5 mm thick sample. The term "transparent" means "which allows light to pass through, and makes it possible to distinguish alphanumeric characters using 5 mm thick sample.

Preferably, the viscosity of the aqueous solution according to the invention is inferior or equal to 50 UD (Mobile 1) by Rheomat at 25°C, preferably inferior or equal to 40 UD. The viscosity is generally measured at 25°C with a viscosimeter PRORHEO RM R180 with Mobile 1 adapted to the viscosity of the product to be tested (mobile is chosen for having a measure between 20 and 80 for UD Unit Deviation), the measure being made after 10mn rotating the mobile inside the composition, with a shear rate from 200s ^"1 . The UD values may then be converted in Poises (1 Poise= 0.1 Pa. s) with a correspondence table.

Method and use

The composition of the present invention can be used for a non-theraputic process, such as a cosmetic process or method, for making up/caring for the keratin materials, such as the skin, in particular the face and the lips, by being applied to the skin, especially the face and the lips. The present invention also relates to a use of the composition according to the present invention, as it is or in cosmetic product for making up/caring for/cleansing/make up removing products for the skin, especially for the face and the lips.

The invention relates to the use of at least one copolymer of styrene and acrylate for improving the sunblocking or sun screening effect of a UV-screening composition. The present invention relates to a non-therapeutic cosmetic process for caring for and/or making up a keratin material, comprising the application, to the surface of the said keratin material, of at least one composition of the invention.

The present invention relates to a non-therapeutic cosmetic process for limiting the darkening of the skin and/or improving the colour and/or uniformity of the complexion, comprising the application, to the surface of the skin, of at least one composition as defined in any one of the preceding claims.

The present invention relates to a non-therapeutic cosmetic process for preventing and/or treating the signs of ageing of a keratin material, comprising the application, to the surface of the keratin material, of at least one composition as defined in any one of the preceding claims The examples that follow are aimed at illustrating the compositions and processes according to this invention, but are not in any way a limitation of the scope of the invention.

EXAMPLES

Example 1 : formulation example Water-soluble UV filters were neutralized and added in water. Then styrene/acrylates copolymer was introduced in formula and stabilized by the solubilizing agent.

Table 1

Example 2: Example of formulation Two UV filters were neutralized by TRIETHANOLAMINE to pH around 7.0 in water, at 25 °C. They were then added to the water phase which contained other water soluble functional components such as preservatives (PHENOXYETHANOL and CAPRYLYL GLYCOL), alcohol, glycerin, and other glycols (DIPROPYLENE GLYCOL, PROPYLENE GLYCOL), at 25 °C. Then STYRENE/ACRYLATES COPOLYMER or POLYSTYRENE, when present, was introduced to the formula together with the solubilizing agent.

All the amounts in the table below are by active matters and in weight percent relative to the total weight of the composition.

PROPYLENE GLYCOL 6 6 3 3

CAPRYLYL GLYCOL 0.1 0.1 0.1 0.1

PHENYLBENZIMIDAZOL

4 4 4 4 E SULFONIC ACID

TEREPHTHALYLIDENE DICAMPHOR SULFONIC 5 5 5 5 ACID

PEG-60

HYDROGENATED 0 0 1 .5 3 CASTOR OIL

PPG-26-BUTETH-26

(and) PEG-40

0.1 0.1 0.1 0.1 HYDROGENATED CASTOR OIL

14.1 ±

In vivo SPF value 4.9 ± 1 .3 4.2 ± 0.3 18.9±2.7

2.0

In vivo PPD value 2.6 ± 0.5 3.2 ± 0.3 3.1 ± 0.5 5.0±0.8

SPF: Sun Protection Factor

PPD: Persistent Pigment Darkening

Comparative composition n°1 does not contain any polymers, and therefore has no boosting effect on UV protection, with a SPF in-vivo result of 4.9 ± 1 .3. Comparative composition n°2 comprising POLYSTYRENE (Commercial Name MODAREZ OS- 197 - supplier: SYNTHRON) instead of STYRENE/ACRYLATES COPOLYMER, shows almost not boosting effect, with a SPF in-vivo result of 4.2 ± 0.3.

In vivo SPF value of the composition of the invention is of 14.1 ± 2.0 (Invention n°1 ) or 18.9±2.7 (Invention n°2), and in vivo PPD value of the composition of the invention is of 3.1 ± 0.5 (Invention n°1 ) or 5.0±0.8 (Invention n°2). Therefore, we see that the composition according the invention is more effective than the other compositions.

The invention n°1 and n°2 are both translucent sprayable sunscreen compositions.

They present a good feeling on the skin.

In addition users feel a mist and light texture of the composition of the invention when applied onto the skin, according to their own appreciation.