EP4221671A1

EP4221671A1 - Aqueous gel cosmetic sunscreen composition, process for manufacturing the aqueous gel cosmetic sunscreen composition and the use of the aqueous gel cosmetic sunscreen composition

Info

Publication number: EP4221671A1
Application number: EP20788702.7A
Authority: EP
Inventors: Beatriz TAVARES FERREIRA; Pedro Tupinamba Werneck BARROSO; José Mario BARCELOS
Original assignee: LOreal SA
Current assignee: LOreal SA
Priority date: 2020-09-30
Filing date: 2020-09-30
Publication date: 2023-08-09
Also published as: FR3114503A1; BR112023005311A2; WO2022067402A1

Abstract

The present invention is directed to an aqueous gel cosmetic sunscreen composition comprising (a) a hydrophilic UV filter system; (b) a solubilizing agent; and (c) a polymer, selected from carbomer. The present invention is also related to a process for manufacturing the aqueous gel cosmetic sunscreen composition, and to the use of the aqueous gel cosmetic sunscreen composition for the manufacture of a product to be used as a sunscreen daily product.

Description

AQUEOUS GEL COSMETIC SUNSCREEN COMPOSITION, PROCESS FOR MANUFACTURING THE AQUEOUS GEL COSMETIC SUNSCREEN COMPOSITION AND THE USE OF THE AQUEOUS GEL COSMETIC SUNSCREEN COMPOSITION FIELD OF THE INVENTION

The present invention is directed to an aqueous gel cosmetic sunscreen composition comprising (a) a hydrophilic UV filter system; (b) a solubilizing agent selected from PPG-26-BUTETH-26 (and) PEG-40 hydrogenated castor oil; and (c) a polymer, selected from carbomer and acrylates/C -30 alkyl acrylate crosspolymer, and mixtures thereof. The present invention is also related to a process of manufacturing the aqueous gel cosmetic sunscreen composition and the use of the aqueous gel cosmetic sunscreen composition.

BACKGROUND OF THE INVENTION

The photoprotection of keratinous materials, including both skin and hair, is considered of great importance in order to protect from sun-damage, sunburn, photoaging, as well as to decrease the chances of skin cancer development caused by exposure to ultraviolet (“UV”) radiation. There are typically two types of UVA/UVB cosmetic compositions used to accomplish photoprotection, namely, inorganic UV filters and organic UV filters.

The degree of UV protection afforded by a cosmetic composition is directly related to the amount and type of UV filters contained therein. The higher the amount of UV filters, the greater the degree of UV protection (UVA/UVB). Particularly, cosmetic compositions must provide good protection against the sun, a measure of which is the Sun Protection Factor (SPF) value, yet have satisfactory sensory perception, such as a smooth but not greasy feel upon application.

Usually, sunscreen products may be in the form of lotions, milks, creams, gels, gel creams, foams, sprays and sticks. Such products can be anhydrous or in the form of emulsions, generally containing sunscreen actives that are solubilized, emulsified, or dispersed in a vehicle, which is topically applied onto the skin. The sunscreen actives, typically through the aid of polymers and other ingredients included in the vehicle, form a thin, protective, and often water-resistant layer on the skin.

The inventors have identified a need for aqueous gel cosmetic sunscreen compositions, which are presented as a transparent composition, having soft and matte effect, in order to enhance the aesthetic appeal. The challenge of achieving the aqueous gel cosmetic sunscreen composition with the desired features is preserving the stability of the water-based composition due to the combination of the ingredients.

Considering the current drawbacks of the state of the art and the difficulties to overcome them, the inventors formulated an aqueous gel cosmetic sunscreen surprisingly showing great stability in a transparent water-based composition, as well as with high SPF.

Additionally, the inventors were able to develop an aqueous gel cosmetic composition that is capable to achieve the desired results by the vehiculation of hydrophobic ingredients due to polarity characteristics. The aqueous gel cosmetic sunscreen composition according to the present invention is sufficiently robust to support electrolytes in high concentrations without stability issues and sensorial losses.

SUMMARY OF THE INVENTION

The present invention is directed to an aqueous gel cosmetic sunscreen composition comprising (a) a hydrophilic UV filter system; (b) a solubilizing agent selected from PPG-26-BUTETH-26 (and) PEG-40 hydrogenated castor oil; and (c) a polymer, selected from carbomer and acrylates/C 10-30 alkyl acrylate crosspolymer, and mixtures thereof . The present invention is also related to a process of manufacturing the aqueous gel cosmetic sunscreen composition and the use of the aqueous gel cosmetic sunscreen composition.

Particularly, the present invention relates to the use of the aqueous gel cosmetic sunscreen composition for the manufacture of a product to be used as a sunscreen daily product.

Other features and advantages of the present invention will be apparent from the following more detailed description of the desirable embodiments which illustrates, by way of example, the principles of the invention.

DETAILED DESCRIPTION OF THE INVENTION

The aqueous gel cosmetic sunscreen composition of the present invention can comprise, consist of, or consist essentially of the essential elements and limitations of the present invention described herein, as well as any of the additional or optional ingredients, components, or limitations described herein.

All ranges and values disclosed herein are inclusive and combinable. For examples, any value or point described herein that falls within a range described herein can serve as a minimum or maximum value to derive a sub-range, etc.

In an embodiment, the aqueous gel cosmetic sunscreen composition of the present invention comprises:

(a) from about 5.0 % to about 25.0 % by weight, based on the total weight of the composition, of a hydrophilic UV filter system,

(b) from about 0.5 % to about 10.0 % by weight, based on the total weight of the composition, of a solubilizing agent selected from PPG-26-BUTETH-26 (and) PEG-40 hydrogenated castor oil, and

(c) from about 0.2 % to about 2.0 % by weight, based on the total weight of the composition, of a polymer, selected from carbomer and acrylates/C10-30 alkyl acrylate crosspolymer, and mixtures thereof.

The aqueous gel cosmetic sunscreen composition according to the invention presents enhanced anti-oiliness properties, high SPF values, dry touch to the skin after application combined with matt effect.

In a preferred embodiment, the aqueous gel cosmetic sunscreen composition of the present invention comprises from about 5.0 % to about 25.0 % by weight, preferably from about 15.0 % to about 20.0 % by weight, from about 16.0 % to about 18.0 % by weight of the hydrophilic UV filter system, based on the total weight of the composition. In a preferred embodiment, the hydrophilic UV system comprises one or more filters selected from the group of phenylbenzimidazole sulfonic acid, terephthalylidene dicamphor sulfonic acid, and combinations thereof.

In a preferred embodiment, the aqueous gel cosmetic sunscreen composition of the present invention comprises from about 0.5 % to about 10.0 % by weight, preferably from about 0.75 to about 8.0 % be weight, from about 1 .0 from about 5.0 % by weigh of the solubilizing agent, based on the total weight of the composition.

In a preferred embodiment, the aqueous gel cosmetic sunscreen composition of the present invention comprises from about 0.2 % to about 2.0 % by weight, preferably from about 0.5 % to about 1 .2 % by weight, from 0.6 % to 1 .0 % by weight of the polymer, based on the total weight of the composition.

In a further preferred embodiment, the aqueous gel cosmetic sunscreen composition of the present invention comprises, additionally, one or more polyol, ranging from about 5.0 % to about 15.0 % by weight, preferably from about 8.0 % to about 12.0 % by weight, from 9.0 % to 10.5 % by weight of the one or more polyol, based on the total weight of the composition. Preferably, the one or more polyol is selected from glycols, preferably propylene glycol. The present composition may further comprise additional liquid oil UV filters, preferably selected from the group of octocrylene, homosalate, ethylhexyl salicilate, and mixtures thereof.

In a preferred embodiment, the aqueous gel cosmetic sunscreen composition of the present invention presents dry touch to the skin after application combined with matt effect, and, to improve these properties, it is usually used silica aerogel.

However, when the aqueous gel cosmetic sunscreen composition of the present invention further comprises silica aerogel, there is an additional formulation challenge since the maximum concentration of silica in standard cosmetic sunscreens compositions is limited, due to its highly hydrophobic properties, thereby rendering the composition instable when high concentrations of silica are applied; considering a completely aqueous system, the technical challenge of having a highly hydrophobic raw material is even more complex.. In this sense, cosmetic sunscreen compositions are usually limited to have about 0.5% by weight of silica, relative to the total weight of the composition.

Thus, in a further embodiment, the aqueous gel cosmetic sunscreen composition according to the present invention may further comprise silica aerogel, preferably silica silylate.

If present, the amount of silica aerogel is ranging from about 0.2 % to about 2.0 % by weight, preferably from about 0.4 % to about 1 .8 % by weight, from about 0.6 % to about 1 .0 % by weight, more preferably from about 0.5 % to about 1 .2 % by weight of silica silylate, based on the total weight of the composition.

In another preferred embodiment, the aqueous gel cosmetic sunscreen composition according to the present invention may further comprise additional cosmetically acceptable ingredients present in a range from about 2.0 % to about 35.0 % by weight, based on the total weight of the composition. Preferably, the additional cosmetically acceptable ingredients selected from additional sunscreens, perfume/f rag rance, preserving agents, solvents, actives, surfactants, vitamins, fillers, silicones, polymers, pigments, buffering, masking and mixtures thereof and combinations thereof.

In a preferred embodiment, the aqueous gel cosmetic sunscreen composition of the present invention may present a Sun Protection Factor ranging from 10 to 80. In various embodiments, the sunscreen composition of the present invention may present a Sun Protection Factor of 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, and 80.

In an embodiment, the aqueous gel cosmetic sunscreen composition of the present invention may present a Sun Protection Factor of 10.

In an embodiment, the aqueous gel cosmetic sunscreen composition of the present invention may present a Sun Protection Factor of 15.

In an embodiment, the aqueous gel cosmetic sunscreen composition of the present invention may present a Sun Protection Factor of 20.

In an embodiment, the aqueous gel cosmetic sunscreen composition of the present invention may present a Sun Protection Factor of 30.

In an embodiment, the aqueous gel cosmetic sunscreen composition of the present invention may present a Sun Protection Factor of 40.

In an embodiment, the aqueous gel cosmetic sunscreen composition of the present invention may present a Sun Protection Factor of 50.

In an embodiment, the aqueous gel cosmetic sunscreen composition of the present invention may present a Sun Protection Factor of 60.

In an embodiment, the aqueous gel cosmetic sunscreen composition of the present invention may present a Sun Protection Factor of 70.

In an embodiment, the aqueous gel cosmetic sunscreen composition of the present invention may present a Sun Protection Factor of 80.

In a further embodiment, the present invention is directed to a process for manufacturing the aqueous gel cosmetic sunscreen composition of the present invention.

In another preferred embodiment, the present invention is related to the use of the aqueous gel cosmetic sunscreen composition the manufacture of a product to be used as sunscreen daily product.

Terms

The terms “a”, “an”, and “the” are understood to encompass the plural as well as the singular.

As used herein, the expression “at least” means one or more and thus includes individual components as well as mixtures/combinations.

Other than in the operating examples, or where otherwise indicated, all numbers expressing quantities of ingredients and/or reaction conditions are to be understood as being modified in all instances by the term “about,” meaning within +/- 5% of the indicated number.

As used herein, all ranges provided are meant to include every specific range within, and combination of sub ranges between, the given ranges. Thus, a range from 1 -5, includes specifically 1 , 2, 3, 4 and 5, as well as sub ranges such as 2-5, 3-5, 2-3, 2-4, 1 -4, etc. All ranges and values disclosed herein are inclusive and combinable. For examples, any value or point described herein that falls within a range described herein can serve as a minimum or maximum value to derive a sub-range, etc.

As used herein, all ranges provided are meant to include every specific range within, and combination of sub ranges between, the given ranges. For example, “from about 1 %, 2% or 3% to about 5%, 10% or 15%,” includes about 1 % to about 5%, about 1 % to about 10%, about 1 % to about 15%, about 2% to about 5%, about 2% to about 10%, about 2% to about 15%, about 3% to about 5%, about 3% to about 10%, and/or about 3% to about 15%. Other than in the operating examples, or where otherwise indicated, all numbers expressing quantities of ingredients and/or reaction conditions are to be understood as being modified in all instances by the term “about,” meaning within 15% such as within 10%, such as within 5% of the indicated number. All concentrations listed are by weight percent relative to the entire composition unless specifically described otherwise.

Additional UV Filter System

Non-limiting suitable UV filters of the present invention could be as follows:

Water-soluble organic sunscreen ingredient

The “water-soluble organic sunscreen ingredient” means any organic compound for screening out UV radiation, which can be fully dissolved in molecular form or miscible in a liquid aqueous phase or which can be dissolved in colloidal form (for example in micellar form) in a liquid aqueous phase.

Non-limiting examples of water-soluble organic sunscreen ingredients useful in the invention include, for example, terephthalylidene dicamphor sulfonic acid, phenylbenzimidazole sulfonic acid, benzophenone-4, aminobenzoic acid (PABA), 4- Bis(polyethoxy)-para-aminobenzoic acid polyethoxyethyl ester (PEG-25 PABA), camphor benzalkonium methosulfate, methylene bis-benzotriazolyl tetramethylbutylphenol (Bisoctrizole), disodium phenyl dibenzimidazole tetrasulfonate (Bisdisulizole disodium), and tris-biphenyl triazine; their derivatives and corresponding salts; naphthalene bisimide derivatives such as those described in European patent application EP1990372 A2, the entire contents of which is hereby incorporated by reference; and cinnamido amine cationic quaternary salts and derivatives such as those described in United States Patent 5,601 ,81 1 , the entire contents of which is hereby incorporated by reference, and mixtures thereof.

The salts of the compounds that may be used according to the invention are chosen in particular from salts of alkali metals, for example sodium or potassium; salts of alkaline-earth metals, for example calcium, magnesium or strontium; metal salts, for example zinc, aluminum, manganese or copper; salts of ammonium of formula NH4+; quaternary ammonium salts; salts of organic amines, for instance salts of methylamine, dimethylamine, trimethylamine, triethylamine, ethylamine, 2- hydroxyethylamine, bis(2-hydroxyethyl)amine or tris(2-hydroxyethyl)amine; lysine or arginine salts. Salts chosen from sodium, potassium, magnesium, strontium, copper, manganese or zinc salts are preferably used. The sodium salt is preferably used.

Preferably, the water-soluble organic sunscreen ingredient will be chosen from terephthalylidene dicamphor sulfonic acid, methylene bis-benzotriazolyl tetramethylbutylphenol, and mixtures thereof.

The water-soluble organic sunscreen ingredient is preferably present in the composition according to the invention in an amount of from about 0.1 % to about 10% by weight, preferably in an amount of from about 0.5% to about 8% by weight, and most preferably about 1 % to about 7% by weight, based on the total weight of the composition.

The suitable UV filter system of the present invention is preferably selected from the group of phenylbenzimidazole sulfonic acid, butyl methoxydibenzoylmethane, titanium dioxide, ethylhexyl triazone, terephthalylidene dicamphor sulfonic acid, octocrylene, homosalate, bis-ethylhexyloxyphenol methoxyphenyl triazine, silica (and) titanium dioxide, methylene bis-benzotriazolyl tetramethylbutylphenol (and) polyglyceryl-10 laurate, and combinations thereof.

In a preferred embodiment, the aqueous gel cosmetic sunscreen composition of the present invention has an amount of UV filter system from about 0.1 % to about 50% by weight, preferably in an amount of from about 5% to about 40% by weight, more preferably about 5% to about 30% by weight, most preferably about 10% to about 30% by weight, based on the total weight of the composition.

Other UV filters Mention may be made, as examples of the organic UV-filter(s), of those denoted below under their INCI names, and mixtures thereof. Anthranilic compounds: menthyl anthranilates, such as marketed under the trademark "Neo Heliopan MA" by Haarmann and Reimer. The dibenzoylmethane compounds: Butyl methoxydibenzoylmethane, such as marketed in particular under the trademark "Parsol 1789" by Hoffmann-La Roche; and isopropyl dibenzoylmethane. Cinnamic compounds: Ethylhexyl methoxycinnamate, such as marketed in particular under the trademark "Parsol MCX" by Hoffmann-La Roche; isopropyl methoxycinnamate; isopropoxy methoxycinnamate; isoamyl methoxycinnamate, such as marketed under the trademark "Neo Heliopan E 1000" by Haarmann and Reimer; cinoxate (2- ethoxyethyl-4-methoxy cinnamate); DEA methoxycinnamate; diisopropyl methylcinnamate; and glyceryl ethylhexanoate dimethoxycinnamate. Salicylic compounds: Homosalate (homomentyl salicylate), such as marketed under the trademark "Eusolex HMS" by Rona/EM Industries; ethylhexyl salicylate, such as marketed under the trademark "Neo Heliopan OS" by Haarmann and Reimer; glycol salicylate; butyloctyl salicylate; phenyl salicylate; dipropyleneglycol salicylate, such as marketed under the trademark "Dipsal" by Scher; and TEA salicylate, such as marketed under the trademark "Neo Heliopan TS" by Haarmann and Reimer. Camphor compounds, in particular, benzylidenecamphor derivatives: 3-benzylidene camphor, such as manufactured under the trademark "Mexoryl SD" by Chimex; 4- methylbenzylidene camphor, such as marketed under the trademark "Eusolex 6300" by Merck; benzylidene camphor sulfonic acid, such as manufactured under the trademark "Mexoryl SL" by Chimex; camphor benzalkonium methosulfate, such as manufactured under the trademark "Mexoryl SO" by Chimex; terephthalylidene dicamphor sulfonic acid, such as manufactured under the trademark "Mexoryl SX" by Chimex; and polyacrylamidomethyl benzylidene camphor, such as manufactured under the trademark "Mexoryl SW" by Chimex. Benzophenone compounds: Benzophenone-1 (2,4-dihydroxybenzophenone), such as marketed under the trademark "Uvinul 400" by BASF; benzophenone-2 (Tetrahydroxybenzophenone), such as marketed under the trademark "Uvinul D50" by BASF; Benzophenone-3 (2- hydroxy-4-methoxybenzophenone) or oxybenzone, such as marketed under the trademark "Uvinul M40" by BASF; benzophenone-4 (hydroxymethoxy benzophonene sulfonic acid), such as marketed under the trademark "Uvinul MS40" by BASF; benzophenone-5 (Sodium hydroxymethoxy benzophenone Sulfonate); benzophenone-6 (dihydroxy dimethoxy benzophenone); such as marketed under the trademark "Helisorb 11" by Norquay; benzophenone-8, such as marketed under the trademark "Spectra-Sorb UV-24" by American Cyanamid; benzophenone-9 (Disodium dihydroxy dimethoxy benzophenonedisulfonate), such as marketed under the trademark "Uvinul DS-49" by BASF; and benzophenone-12, and n-hexyl 2-(4- diethylamino-2-hydroxybenzoyl)benzoate (such as UVINUL A+ by BASF). |3,|3- Diphenylacrylate compounds: Octocrylene, such as marketed in particular under the trademark "Uvinul N539" by BASF; and Etocrylene, such as marketed in particular under the trademark "Uvinul N35" by BASF. Triazine compounds: Diethylhexyl butamido triazone, such as marketed under the trademark "Uvasorb HEB" by Sigma 3V; 2,4,6-tris(dineopentyl 4'-aminobenzalmalonate)-s-triazine, bisethylhexyloxyphenol methoxyphenyl triazine, such as marketed under the trademark «TINOSORB S >> by CIBA GEIGY, and ethylhexyl triazone, such as marketed under the trademark «UVTNUL T150 >> by BASF. Benzotriazole compounds, in particular, phenylbenzotriazole derivatives: 2-(2H-benzotriazole-2-yl)-6-dodecyl-4- methylpheno, branched and linear; and those described in USP 5240975. Benzalmalonate compounds: Dineopentyl 4'-methoxybenzalmalonate, and polyorganosiloxane comprising benzalmalonate functional groups, such as polysilicone-15, such as marketed under the trademark "Parsol SLX" by Hoffmann- LaRoche. Benzimidazole compounds, in particular, phenylbenzimidazole derivatives: Phenylbenzimidazole sulfonic acid, such as marketed in particular under the trademark "Eusolex 232" by Merck, and disodium phenyl dibenzimidazole tetrasulfonate, such as marketed under the trademark "Neo Heliopan AP" by Haarmann and Reimer. Imidazoline compounds: Ethylhexyl dimethoxybenzylidene dioxoimidazoline propionate. Bis-benzoazolyl compounds: The derivatives as described in EP-669,323 and U.S. Pat. No. 2,463,264. Para-aminobenzoic acid compounds: PABA (p-aminobenzoic acid), ethyl PABA, Ethyl dihydroxypropyl PABA, pentyl dimethyl PABA, ethylhexyl dimethyl PABA, such as marketed in particular under the trademark "Escalol 507" by ISP, glyceryl PABA, and PEG-25 PABA, such as marketed under the trademark "Uvinul P25" by BASF. Methylene bis- (hydroxyphenylbenzotriazol) compounds, such as 2,2'-methylenebis[6-(2H- benzotriazol-2-yl)-4-methyl-phenol], such as marketed in the solid form under the trademark "Mixxim BB/200" by Fairmount Chemical, 2,2'-methylenebis[6-(2H- benzotriazol-2-yl)-4-(l,l,3,3-tetramethylbutyl)phenol], such as marketed in the micronized form in aqueous dispersion under the trademark "Tinosorb M" by BASF, or under the trademark "Mixxim BB/100" by Fairmount Chemical, and the derivatives as described in U.S. Pat. Nos. 5,237,071 and 5,166,355, GB-2,303,549, DE- 197,26,184, and EP-893,119, and Drometrizole trisiloxane, such as marketed under the trademark "Silatrizole" by Rhodia Chimie or- "Mexoryl XL" by L’Oreal. Benzoxazole compounds: 2,4-bis[5-l(dimethylpropyl)benzoxazol-2-yl-(4- phenyl)imino]- 6-(2-ethylhexyl)imino-l,3,5-triazine, such as marketed under the trademark of Uvasorb K2A by Sigma 3V. Screening polymers and screening silicones: The silicones described in WO 93/04665. Dimers derived from a- alkylstyrene: The dimers described in DE-19855649. 4,4-Diarylbutadiene compounds: l,l-dicarboxy(2,2'-dimethylpropyl)-4,4-diphenylbutadiene.

It is in some embodiments desirable that the organic UV-filter(s) be selected from the group of: butyl methoxydibenzoylmethane, ethylhexyl methoxycinnamate, homosalate, ethylhexyl salicylate, octocrylene, phenylbenzimidazole sulfonic acid, benzophenone-3, benzophenone-4, benzophenone-5, n-hexyl 2-(4-diethylamino-2-hydroxybenzoyl)benzoate, l,r-(l,4- piperazinediyl)bis[l-[2-[4-(diethylamino)-2-hydroxybenzoyl]phenyl]-methanone 4- methylbenzylidene camphor, terephthalylidene dicamphor sulfonic acid, disodium phenyl dibenzimidazole tetrasulfonate, ethylhexyl triazone, bis-ethylhexyloxyphenol methoxyphenyl triazine, 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' -aminobenzalmalonate)-6- [(3 - { 1 ,3 ,3 ,3 -tetramethyl- 1 - [(trimethylsilyloxy] - disiloxanyl}propyl)amino]-s-triazine, 2,4,6-tris-(di-phenyl)-triazine, 2,4,6-tris-(ter-phenyl)-triazine, methylene bis-benzotriazolyl tetramethylbutylphenol, drometrizole trisiloxane, polysilicone-15, dineopentyl 4'-methoxybenzalmalonate, l,l- dicarboxy(2,2'-dimethylpropyl)-4,4-diphenylbutadiene, 2,4-bis[5-l (dimethylpropyl) benzoxazol-2-yl-(4-phenyl)imino]-6-(2-ethylhexyl)imino-l,3,5-triazine, camphor benzylkonium methosulfate, and mixtures thereof.

Additional Polymers

Further to the stabilizing polymer, the aqueous gel cosmetic sunscreen composition of the present invention may further comprise additional polymers.

The suitable additional polymers of the present invention are selected from rheology modifier polymers and anionic polymers which may be water-soluble or water-dispersible at a pH from 4.0 of 7.5 and at room temperature (25°C). According to the present invention, the suitable polymers of the present invention could be as follows.

The rheology modifier polymers are pre-neutralized and preferably selected from taurate polymers. Such polymers comprise an ionic monomer portion, 2-acrylamido-2-methylpropane sulfonic acid (AMPS), as well as a further, less polar monomer portion (vinylpyrrolidone or beheneth-25 methacrylate). These polymers are used as thickener and as stabilizer for oil-in-water emulsions and form extremely stable emulsions already at low concentrations. In particular, these polymers can be used in conjunction with almost any oil phase, comprising silicone oils, hydrocarbons/waxes and ester oils.

Examples of taurate polymers are acrylates/vinyl isodecanoate crosspolymer (such as Stabylen 30), acrylates/Cio-30 alkyl acrylate crosspolymer (such as Pemulen TR1 and TR2), carbomers (Aqua SF-1 ), ammonium acryloyldimethyltaurate/VP copolymer (such as Aristoflex AVC), ammonium acryloyldimethyltaurate/beheneth-25 methacrylate crosspolymer (such as Aristoflex HMB), acrylates/ceteth-20 itaconate copolymer (such as Structure 3001 ), polyacrylamide (such as Sepigel 305), non-ionic thickener (such as Aculyn 46), or mixtures thereof.

Acrylic polymer powders useful in the invention include, for example, acrylic polymer powders such as methyl methacrylate crosspolymer.

Anionic polymers may be polymers with anionic groups distributed along the polymer backbone. Anionic groups, which may include carboxylate, sulfonate, sulphate, phosphate, nitrate, or other negatively charged or ionizable groupings, may be disposed upon groups pendant from the backbone or may be incorporated in the backbone itself.

The anionic polymers may comprise at least one hydrophilic unit of olefinic unsaturated carboxylic acid type, and at least one hydrophobic unit exclusively of (Cio-C3o)alkyl ester of unsaturated carboxylic acid type.

In certain exemplary and non-limiting embodiments, the copolymers are chosen from the copolymers resulting from the polymerization of:

(1 ) at least one monomer of formula (I):

CHa^CHCR COOH (i) wherein Ri is chosen from H or CH3 or C2H5, providing acrylic acid, methacrylic acid, or ethacrylic acid monomers, and (2) at least one monomer of (Cio-C3o)alkyl ester of unsaturated carboxylic acid type corresponding to the monomer of formula (II):

CH₂=CH(R₂)COOR₃ (II)

Non-limiting examples of (Cio-C3o)alkyl esters of unsaturated carboxylic acids are for example chosen from lauryl acrylate, stearyl acrylate, decyl acrylate, isodecyl acrylate, dodecyl acrylate and the corresponding methacrylates, such as lauryl methacrylate, stearyl methacrylate, decyl methacrylate, isodecyl methacrylate and dodecyl methacrylate, and mixtures thereof.

Additionally, crosslinked polymers may be chosen according to further exemplary embodiments. For example, such polymers may be chosen from polymers resulting from the polymerization of a mixture of monomers comprising:

(1 ) acrylic acid,

(2) an ester of formula (II) described above, in which R2 is chosen from H or CH3, R3 denoting an alkyl radical having from 12 to 22 carbon atoms, and

(3) a crosslinking agent, which is a well-known copolymerizable polyethylenic unsaturated monomer, such as diallyl phthalate, allyl (meth)acrylate, divinylbenzene, (poly)ethylene glycol dimethacrylate and methylenebisacrylamide.

For example, acrylate/C -Cso alkyl acrylate copolymers (INCI name: Acrylates/Cio-30 Alkyl Acrylate Crosspolymer), such as the products PEMULEN TR1 , PEMULEN TR2, CARBOPOL 1382 and CARBOPOL EDT 2020 may be chosen.

Anionic polymers useful herein include, for example: polyacrylic acid; polymethacrylic acid; parboxyvinylpolymer; acrylate copolymers such as pcrylate/Cw- 30 alkyl acrylate crosspolymer, acrylic acid/vinyl ester copolymer/acrylatesninyl isodecanoate crosspolymer, acrylates/palmeth-25 acrylate copolymer, acrylate/steareth-20 itaconate copolymer, and acrylate/celeth-20 itaconate copolymer; sulfonate polymers such as polysulfonic acid, sodium polystyrene sulfonate, copolymers of methacrylic acid and acrylamidomethylpropane sulfonic acid, and copolymers of acrylic acid and acrylamidomethylpropane sulfonic acid; carboxymethycellulose; carboxy guar gum; copolymers of ethylene and maleic acid; and acrylate silicone polymer. In some instances, the anionic polymers include, for example, Carbomer and CARBOPOL 980; acrylates/Cio-30 alkyl acrylate crosspolymer such as Pemulen TR-1 , PEMULEN TR-2, CARBOPOL 1342, CARBOPOL 1382, and CARBOPOL ETD 2020; sodium carboxymethylcellulose such as CMC series; and acrylate copolymer such Capigel; acrylates copolymer such as CARBOPOL Aqua SF- 1 as an aqueous dispersion, and acrylates crosspolymer-4 such as CARBOPOL Aqua SF-2 as an aqueous dispersion.

In an embodiment, the anionic polymer of the invention is carbomer such as CARBOPOL 980. Exemplary of non-ionic polymers could be as follows:

(i) hydroxyethylcellulose, for instance the product NATROSOL 250 HHR PC or NATROSOL 250 HHR CS;

(ii) celluloses modified with groups comprising at least one fatty chain; examples that may be mentioned include:

- hydroxyethylcelluloses modified with groups comprising at least one fatty chain, such as alkyl, arylalkyl or alkylaryl groups, or mixtures thereof, and in which the alkyl groups are preferably C8-C22, for instance the product NATROSOL Plus Grade 330 CS (C16 alkyls), or the product BERMOCOLL EHM 100; methyl hydroxyethylcellulose; methyl ethyl hydroxyethylcellulose, known as the product STRUCTURE CEL 8000 M; or hydroxypropyl cellulose, known as the product KLUCEL MF PHARM HYDROXYPROPYLCELLULOSE;

- hydroxyethylcelluloses modified with alkylphenyl polyalkylene glycol ether groups, such as the product Amercell Polymer HM-1500 (nonylphenyl polyethylene glycol (15) ether); or

(iii) hydroxypropyl guars such as hydroxypropyl guar and hydroxypropyl guars modified with groups comprising at least one fatty chain, such as the product Esaflor HM 22 (C22 alkyl chain), and the products RE210-18 (C14 alkyl chain) and RE205-1 (C20 alkyl chain).

SILICA AEROGEL

If present, the “silica aerogel” according to the present invention is a porous material obtained by replacing (by drying) the liquid component of a silica gel with air. Silica aerogels are generally synthesized via a sol-gel process in a liquid medium and then dried, usually by extraction with a supercritical fluid, such as, but not limited to, supercritical carbon dioxide (CO2). This type of drying makes it possible to avoid shrinkage of the pores and of the material. The sol-gel process and the various drying processes are described in detail in Brinker, C.J., and Scherer, G.W., Sol-Gel Science: New York: Academic Press, 1990.

In a preferred embodiment, the amount of silica aerogel in the anhydrous sunscreen composition of the present invention is at least about 5% by weight, relative to the total weight of the composition, preferably from about 5% by weight to about 10% by weight, more preferably from about 5% by weight to about 8% by weight such as from about 5% to about 7% by weight, relative to the total weight of the composition.

The silica aerogel (e.g., hydrophobic silica aerogel particles) used in the present invention have a specific surface area per unit of mass (SM) ranging from about 500 to about 1500 m²/g, or alternatively from about 600 to about 1200 m²/g, or alternatively from about 600 to about 800 m²/g, and a size expressed as the mean volume diameter (D[0.5]), ranging from about 1 to about 30 pm, or alternatively from about 5 to about 25 pm, or alternatively from about 5 to about 20 pm, or alternatively from about 5 to about 15 pm. The specific surface area per unit of mass may be determined via the BET (Brunauer-Emmett-Teller) nitrogen absorption method described in the Journal of the American Chemical Society, vol. 60, page 309, February 1938, corresponding to the international standard ISO 5794/1. The BET specific surface area corresponds to the total specific surface area of the particles under consideration.

The size of the particles may be measured by static light scattering using a commercial granulometer such as the MasterSizer 2000 machine from Malvern. The data are processed on the basis of the Mie scattering theory. This theory, which is exact for isotropic particles, makes it possible to determine, in the case of non-spherical particles, an "effective" particle diameter. This theory is especially described in the publication by Van de Hulst, H.C., "Light Scattering by Small Particles," Chapters 9 and 10, Wiley, New York, 1957.

The particles used in the present invention may advantageously have a tamped (or tapped) density ranging from about 0.04 g/cm³ to about 0.10 g/cm³’ or alternatively from about 0.05 g/cm³ to about 0.08 g/cm³. In the context of the present invention, this density, known as the tamped density, may be assessed according to the following protocol: 40 g of powder are poured into a measuring cylinder; the measuring cylinder is then placed on a Stav 2003 machine from Stampf Volumeter; the measuring cylinder is then subjected to a series of 2500 packing motions (this operation is repeated until the difference in volume between two consecutive tests is less than 2%); the final volume Vf of packed powder is then measured directly on the measuring cylinder. The tamped density is determined by the ratio m/Vf, in this instance 40/Vf (Vf being expressed in cm³ and m in g).

According to one embodiment, the hydrophobic silica aerogel particles used in the present invention have a specific surface area per unit of volume Sv ranging from about 5 to about 60 m²/cm³, or alternatively from about 10 to about 50 m²/cm³, or alternatively from about 15 to about 40 m²/cm³. The specific surface area per unit of volume is given by the relationship: Sv = SM.r where r is the tamped density expressed in g/cm³ and SM is the specific surface area per unit of mass expressed in m²/g, as defined above.

In some embodiments, the silica aerogel particles, according to the invention, have an oil-absorbing capacity, measured at the wet point, ranging from about 5 to about 18 ml/g, or alternatively from about 6 to about 15 ml/g, or alternatively from about 8 to about 12 ml/g. The oil-absorbing capacity measured at the wet point, noted Wp, corresponds to the amount of water that needs to be added to 100 g of particle in order to obtain a homogeneous paste. Wp is measured according to the wet point method or the method for determining the oil uptake of a powder described in standard NF T 30-022. Wp corresponds to the amount of oil adsorbed onto the available surface of the powder and/or absorbed by the powder by measuring the wet point, described below: An amount = 2 g of powder is placed on a glass plate, and the oil (isononyl isonanoate) is then added dropwise. After addition of 4 to 5 drops of oil to the powder, mixing is performed using a spatula, and addition of oil is continued until a conglomerate of oil and powder has formed. At this point, the oil is added one drop at a time and the mixture is then triturated with the spatula. The addition of oil is stopped when a firm, smooth paste is obtained. This paste must be able to be spread on the glass plate without cracking or forming lumps. The volume Vs (expressed in ml) of oil used is then noted. The oil uptake corresponds to the ratio Vs/m.

The aerogels used, according to the present invention, are hydrophobic silica aerogels, preferably of silylated silica (INCI name: silica silylate). The term "hydrophobic silica" means any silica whose surface is treated with silylating agents refers to any silica whose surface is treated with silylating agents, for example, halogenated silanes, such as alkylchlorosilanes, siloxanes, in particular dimethylsiloxanes, such as hexamethyldisiloxane, or silazanes, so as to functionalize the OH groups with silyl groups Si-Rn, for example, trimethylsilyl groups. Preparation of hydrophobic silica aerogel particles that have been surface-modified by silylation, is found in U.S. Patent No. 7,470,725, incorporated herein by reference. In one embodiment, hydrophobic silica aerogel particles surface-modified with trimethylsilyl groups are desirable. Suitable examples of hydrophobic silica aerogels, may include, but are not limited to, the aerogels sold under the tradenames of VM-2260 (INCI name: Silica silylate) and VM-2270 (INCI name: Silica silylate), both available from Dow Corning Corporation (Midland, Michigan). The particles of VM-2260 have a mean size of about 1000 microns and a specific surface area per unit of mass ranging from 600 to 800 m²/g. The particles of VM-2270 have a mean size ranging from 5 to 15 microns and a specific surface area per unit of mass ranging from 600 to 800 m²/g. Another suitable example of a hydrophobic silica aerogel may include, but is not limited to, the aerogels commercially available from Cabot Corporation (Billerica, Massachusetts) under the tradename of Aerogel TLD 201 , Aerogel OGD 201 and Aerogel TLD 203, Enova Aerogel MT 1 100 and Enova Aerogel MT 1200.

The silica aerogel is preferably hydrophobic silica aerogel, more preferably silica silylate.

If present, the amount of silica aerogel is ranging from about 0.2 to about 2.0 % by weight, preferably from about 0.4 to about 1 .8 % by weight, from about 0.6 to 1 .0, more preferably from about 0.5 to about 1 .2 % by weight of silica silylate, based on the total weight of the composition.

Additional Ingredients

In addition to the essential components described hereinbefore, the composition of the invention may further comprise any usual cosmetically acceptable ingredient, which may be chosen especially from such as additional sunscreens, perfume/f rag rance, preserving agents, solvents, actives, surfactants, fatty compounds, vitamins, fillers, silicones, pigments, buffering, masking and mixtures thereof.

A person skilled in the art will take care to select the optional additional ingredients and/or the amount thereof such that the advantageous properties of the composition according to the invention are not, or are not substantially, adversely affected by the envisaged addition.

Non-limiting example of preserving agent which can be used in accordance with the invention include phenoxyethanol.

Suitable fillers of the invention could be as examples of oil-absorbing fillers: mica, silica, kaolin, zea may (corn) starch, magnesium oxide, nylon-12, nylon- 66, cellulose, polyethylene, talc, talc (and) methicone, talc (and) dimethicone, perlite, sodium silicate, pumice, PTFE, polymethyl methacrylate, oryza sativa (rice) starch, aluminum starch octenylsuccinate, potato starch modified, alumina, silica silylate, calcium sodium borosilicate, magnesium carbonate, hydrated silica, dimethicone/vinyl dimethicone crosspolymer, sodium carboxylmethyl starch.

Additionally, the composition of the present invention may comprise polymeric fillers such as polylactic acid.

Suitable solvents include, but are not limited to water, alcohols, glycols and polyols such as glycerin, water, caprylyl glycol, pentylene glycol, propylene glycol, butylene glycol, C12-15 alkyl benzoate and mixtures thereof.

In various embodiments, the solvent is present in a concentration from about 15 to 100% by weight, or from about 20 to about 80% by weight, or from about 30 to about 70% by weight, or from about 35 to about 75% by weight, or preferably from about 40 to about 70% by weight, and more preferably from about 45 to about 65% by weight, including ranges and sub-ranges there between, based on the total weight of the combinations and/or compositions of the present disclosure.

Suitable additional actives include, but are not limited to, disodium EDTA, triethanolamine, and mixtures thereof.

Non-limiting examples of additional surfactants suitable for use are fatty acids, glyceryl esters in addition to glyceryl stearate, alkoxylated fatty alcohols, such as stearic acid, laureth-12, laureth-21 , glyceryl isostearate, disodium stearoyl glutamate, potassium cetyl phosphate, poloxamer 338, sodium methyl stearoyl taurate and mixtures thereof.

Non-limiting example of vitamins suitable for the composition of the present invention includes tocopherol.

The additional ingredients may represent from 60% to 85%, such as from 60% to 82% or such as from 65 to 80% by weight of the total weight of the composition of the invention.

PROCESS FOR MANUFACTURING AN AQUEOUS GEL COSMETIC SUNSCREEN COMPOSITION

A non-limitative process for manufacturing the aqueous gel cosmetic sunscreen composition of to the present invention comprises the following steps:

- Phase 1

(1 ) adding the UV filter system;

(2) correcting the pH;

(3) mixing until homogenization;

(4) adding additional ingredients; (5) correcting the pH;

- Phase 2

(6) adding water and the gelling agent under agitation;

- Mixing step

(7) adding Phase 1 to Phase 2 under agitation;

(8) adding glycerin.

In a preferred embodiment, the before step (8), the process further comprises the steps of (i) mixing silica silylate with polyol to pre disperse it, and (ii) adding the mixture obtained in (i) to the main vessel.

EMBODIMENTS

According to the invention, an aqueous gel cosmetic sunscreen composition may comprise:

(a) from 7.0 to 17.0 % by weight, based on the total weight of the composition, of a hydrophilic UV filter system,

(b) from 1.0 to 8.0 % by weight, based on the total weight of the composition, of a solubilizing agent selected from PPG-26-BUTETH-26 (and) PEG-40 hydrogenated castor oil , and

(c) from 0.5 to 1.0 % by weight, based on the total weight of the composition, of a polymer, selected from carbomer and acrylates/C10-30 alkyl acrylate crosspolymer, and mixtures thereof.

In another embodiment, the aqueous gel cosmetic sunscreen composition may comprise:

(b) from 1.0 to 4.0 % by weight, based on the total weight of the composition, of a solubilizing agent selected from PPG-26-BUTETH-26 (and) PEG-40 hydrogenated castor oil , and

EXAMPLES

By way of non-limiting illustration, the invention will now be described with reference to the following examples.

Examples 1 to 4 A suitable composition according to the state of the art is as Example 1 and a suitable composition according to the present invention is as Examples 2 to 4, as follows:

Table 1 - Compositions of the state of the art and of the present invention

Product Performance Evaluation

In order to evaluate the Sun Protection Factor of the aqueous gel cosmetic sunscreen composition of to the present invention, a composition according to Ex. 2 was studied according the ISO 24444-2010 method (SPF), and compared to the results of a composition according to the state of the art, to validate the results.

The aqueous gel cosmetic sunscreen composition according to Ex. 2 obtained an average static SPF of 38.9 (3.9).

Example 6 Stability Test A stability test was conducted in different temperature and timings in order to evaluate the stability of the aqueous gel cosmetic sunscreen composition of the present invention, according to Ex. 2, considering 1 week, 1 month and 2 months to comprehend the possible evolution of the cosmetic formula, especially in terms of pH, viscosity, aspect (transparency and visual separation) and microscopy (considering UV filters crystallization).

Aqueous UV filters have a pH range in which they are active, stable as molecules. Also, as they form a high containing electrolytes environment the gel could break and lose viscosity. None of those signs were noticed as the formula ended completely clear, and within the desired results for all tests.

Claims

SET OF CLAIMS

1 . An aqueous gel cosmetic sunscreen composition comprising:

(a) from 5.0 to 25.0 % by weight, based on the total weight of the composition, of a hydrophilic UV filter system,

(b) from 0.5 to 10.0 % by weight, based on the total weight of the composition, of a solubilizing agent selected from PPG-26-BUTETH-26 (and) PEG-40 hydrogenated castor oilacrylates/C10-30 alkyl acrylate crosspolymer, and mixtures thereof.

2. The aqueous gel cosmetic sunscreen composition, according to claim 1 , comprising from 15.0 to 20.0 % by weight of the hydrophilic UV filter system, based on the total weight of the composition.

3. The aqueous gel cosmetic sunscreen composition, according to claim 1 , wherein the hydrophilic UV system comprises one or more filters selected from the group of phenylbenzimidazole sulfonic acid, terephthalylidene dicamphor sulfonic acid, and mixtures thereof.

4. The aqueous gel cosmetic sunscreen composition, according to claim 1 , comprising from 1 .0 to 5.0 % by weight of the solubilizing agent, based on the total weight of the composition.

5. The aqueous gel cosmetic sunscreen composition, according to claim 1 , comprising from 0.5 to 1 .2 % by weight of the polymer, based on the total weight of the composition.

6. The aqueous gel cosmetic sunscreen composition, according to claim 1 , further comprising from 8.0 to 12.0 % by weight of the one or more polyol, selected from glycols.

7. The aqueous gel cosmetic sunscreen composition, according to claim 1 , further comprising from 0.2 to 2.0 % by weight, based on the total weight of the composition, of silica aerogel.

8. The aqueous gel cosmetic sunscreen composition, according to claim 1 , further comprising additional cosmetically acceptable ingredients are present in a range from 2.0 to 35.0 % by weight, based on the total weight of the composition.

9. The aqueous gel cosmetic sunscreen composition, according to claim 1 , wherein it further comprises cosmetically acceptable ingredients selected from additional UV filters, perfume/fragrance, preserving agents, solvents, actives, surfactants, fatty compounds, vitamins, fillers, silicones, polymers, pigments, buffering, masking and mixtures thereof.

10. A process for manufacturing the aqueous gel cosmetic sunscreen composition, comprising:

(b) from 0.5 to 10.0 % by weight, based on the total weight of the composition, of a solubilizing agent, and

(c) from 0.2 to 2.0 % by weight, based on the total weight of the composition, of a polymer, selected from carbomer, wherein the process comprises the steps of:

- Phase 1

(7) adding the UV filter system;

(8) correcting the pH;

(9) mixing until homogenization;

(10) adding additional ingredients;

(1 1 ) correcting the pH;

- Phase 2

(12) adding water and the gelling agent under agitation;

- Mixing step

(7) adding Phase 1 to Phase 2 under agitation;

(8) adding glycerin.

1 1. Process, according to claim 10, wherein before step (8), the process further comprises the steps of (i) mixing silica silylate with polyol to pre disperse it, and (ii) adding the mixture obtained in (i) to the main vessel.

12. Use of the aqueous gel cosmetic sunscreen composition, comprising:

(b) from 0.5 to 10.0 % by weight, based on the total weight of the composition, of a solubilizing agent selected from PPG-26-BUTETH-26 (and) PEG-40 hydrogenated castor oil, and (c) from 0.2 to 2.0 % by weight, based on the total weight of the composition, of a polymer, selected from carbomer and acrylates/C10-30 alkyl acrylate crosspolymer, and mixtures thereof, wherein said use is for the manufacture of a product to be used as a sunscreen daily product.