WO2021016679A1

WO2021016679A1 - Anhydrous sunscreen composition comprising silica aerogel

Info

Publication number: WO2021016679A1
Application number: PCT/BR2019/050296
Authority: WO
Inventors: Beatriz Tavares FERREIRA; Lais Moreira LIMA; Angeles FONOLLA-MORENO
Original assignee: LOreal SA
Current assignee: LOreal SA
Priority date: 2019-07-26
Filing date: 2019-07-26
Publication date: 2021-02-04
Anticipated expiration: 2022-01-26
Also published as: BR112021024034A2

Abstract

An anhydrous sunscreen composition includes at least about 5% by weight of silica aerogel, relative to the total weight of the composition. It further includes a silicone resin, present in a concentration by weight that is at least about 0.5% and less than the concentration by weight of the silica aerogel. Also included are organic UV-filters and an inorganic color pigment. Methods of making an anhydrous sunscreen are also provided. The methods include blending silica aerogel, trimethylsiloxysilicate, an organic UV-filter, a non UV-absorbing fatty compound, an inorganic color pigment, and an uncoated titanium dioxide having a median particle size from about 0.2 microns to about 1 micron to form an anhydrous sunscreen comprising at least about 5% by weight of the silica aerogel by weight in the anhydrous composition.

Description

ANHYDROUS SUNSCREEN COMPOSITION COMPRISING SILICA AEROGEL

FIELD OF THE INVENTION

The present disclosure is directed to anhydrous sunscreen compositions. More specifically, the present disclosure is directed to anhydrous sunscreen compositions having one or more of appealing aesthetics, phase stability, and high SPF, comprising high concentration of silica aerogel.

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, photo-aging, 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 sunscreen compositions used to accomplish photoprotection, namely, inorganic UV- filters and organic UV-filters.

The degree of UV protection afforded by a sunscreen 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, sunscreen 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.

Hydrophobic silica is commonly known in the cosmetic industry for providing anti-oiliness and anti-acne effects, including in sunscreen compositions. However, the maximum concentration of silica in a composition is limited, due to its high hydrophobic properties, thereby rendering the composition instable when high concentrations of silica are applied. In this sense, sunscreen compositions are usually limited to have about 0.5% by weight of silica, relative to the total weight of the composition. The inventors have identified a need for sunscreen compositions having higher concentrations of silica aerogel, in order to enhance the aesthetic appeal. The challenge of incorporating high concentrations of silica aerogel in the sunscreen composition is not only limited due to the hydrophobic nature of the silica, but there is also the challenge of formulating stable compositions while preserving satisfactory properties of the product. Furthermore, the inventors have recognized that to use high concentrations of silica aerogel in a tinted sunscreen, there are additional problems relating to providing good pigment adherence and“coverage” (appearance of uniform distribution of pigment on the skin) of the color to the skin

Considering the current drawbacks of the state of the art and the difficulties to overcome them, the inventors formulated an anhydrous sunscreen composition that enables the high concentration of silica aerogel. The anhydrous sunscreen composition of the present invention having high concentration of silica aerogel surprisingly showed, in certain embodiments, an appealing mousse-like texture, good stability, coverage, as well as SPF.

SUMMARY OF THE INVENTION

The present disclosure relates to an anhydrous sunscreen composition including at least about 5% by weight of silica aerogel, relative to the total weight of the composition. It further includes a silicone resin, present in a concentration by weight that is at least about 0.5% and less than the concentration by weight of the silica aerogel. Also included are organic UV-filters and an inorganic color pigment.

According to another aspect, the present disclosure relates to an anhydrous sunscreen composition including at least 5% by weight of silica aerogel, relative to the total weight of the composition. It further includes a silicone resin, present in a concentration by weight that is at least 0.5% and less than the concentration by weight of the silica aerogel. Also included are from 10% by weight to 40% by weight of organic UV-filters, from 10% to 75% of at least one non UV-absorbing fatty compound, iron oxide, and from 2% by weight to 7% by weight of a titanium dioxide having a median particle size from about 0.2 microns to about 1 micron.

According to another aspect, the present disclosure relates to a method of making an anhydrous sunscreen. The method includes blending silica aerogel, trimethylsiloxysilicate, an organic UV-filter, a non UV-absorbing fatty compound, an inorganic color pigment, and an uncoated titanium dioxide having a median particle size from about 0.2 microns to about 1 micron to form an anhydrous sunscreen comprising at least about 5% by weight of the silica aerogel by weight in the anhydrous composition.

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 anhydrous sunscreen compositions 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.

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

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

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.

The term“essentially free of as used herein means having less than 3% by weight of a particular ingredient or component and“substantially free of as used herein means having less than 2% by weight of a particular ingredient or component.

“Anhydrous” as used herein means that the sunscreen composition of the present invention, and the essential or optional components thereof, are essentially free of water and, in certain embodiments are substantially free of water.

SILICA AEROGEL

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.

The silica aerogel is present in compositions of the invention in a concentration by weight of at least about 5%, such as from about 5% to about 10%, such as from about 5% to about 8%, such as from about 5% to about 7% or about 6% to about 8%, such as from about 6% to about 7%

UV-FILTER SYSTEM

The composition, according to the present invention, comprises a UV- filter system comprising at least one organic (ultraviolet) UV-filter. As one skilled in the art will readily understand, by UV-filter it is meant a material that attenuates ultraviolet radiation appreciably. If two or more organic UV-filters are used, they may be the same or different. The organic UV-filter used for the present invention may be active in the UV- A and/or UV-B region. The organic UV-filter may be hydrophilic and/or lipophilic.

The organic UV-filter may be solid or liquid. The terms "solid" and "liquid" mean solid and liquid, respectively, at 25°C under 1 atm.

The organic UV-filter can be selected from the group consisting of anthranilic compounds; dibenzoylmethane compounds; cinnamic compounds; salicylic compounds; camphor compounds; benzophenone compounds; b,b- diphenylacrylate compounds; triazine compounds; benzotriazole compounds; benzalmalonate compounds; benzimidazole compounds; imidazoline compounds; bis-benzoazolyl compounds; p-aminobenzoic acid (PABA) compounds; methylenebis(hydroxyphenylbenzotriazole) compounds; benzoxazole compounds; screening polymers and screening silicones; dimers derived from a-alkylstyrene; 4,4- diarylbutadienes compounds; guaiazulene and derivatives thereof; rutin and derivatives thereof; flavonoids; bioflavonoids; oryzanol and derivatives thereof; quinic acid and derivatives thereof; phenols; retinol; cysteine; aromatic amino acids; peptides having an aromatic amino acid residue; and mixtures thereof.

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 "Flelisorb 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) b,b- 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 FIEB" by Sigma 3V; 2,4,6-tris(dineopentyl 4'-aminobenzalmalonate)-s-triazine, bis- ethylhexyloxyphenol 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-(2FI-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-893,1 19, 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 consisting 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.

In certain embodiments, the sunscreen compositions of the present invention include an inorganic UV-filter. The inorganic UV-filter used for the present invention may be active in the UV-A and/or UV-B region; and may be hydrophilic and/or lipophilic. The inorganic UV-filter is generally insoluble in solvents, such as water, and ethanol commonly used in cosmetics.

The inorganic UV-filter can be selected from the group consisting of silicon carbide, metal oxides which may or may not be coated, and mixtures thereof. And in some embodiments, the inorganic UV-filters are selected from pigments (mean size of the primary particles: generally from about 5 nm to about 50 nm, and in some embodiments from about 10 nm to about 50 nm) formed of metal oxides, such as, for example, pigments formed of titanium oxide (amorphous or crystalline in the rutile and/or anatase form), iron oxide, zinc oxide, zirconium oxide, or cerium oxide, which are all UV photoprotective agents that are well known per se. And in some embodiments, the inorganic UV-filters are selected from titanium oxide, zinc oxide, and, in some embodiments, titanium oxide. The inorganic UV-filter may or may not be coated. With one or more coatings such as alumina, silica, aluminum hydroxide, silicones, silanes, fatty acids or salts thereof (such as sodium, potassium, zinc, iron, or aluminum salts), fatty alcohols, lecithin, amino acids, polysaccharides, proteins, alkanolamines, waxes, such as beeswax, (meth)acrylic polymers, organic UV-filters, and (per)fluoro compounds.

The composition, according to the present invention, may include the UV-filter system in an amount of from about 0.1 % by weight to about 50% by weight, and in some embodiments from about 1 % by weight to about 40% by weight, and in some embodiments from about 10% by weight to about 40% by weight, such as about 15% to about 30% in relation to the total weight of the composition. In certain embodiments, the concentration of organic UV-filters is present in one or more of the concentration ranges noted in this paragraph.

INORGANIC COLOR PIGMENT

In order to provide tinting to the user’s skin, compositions of the present invention include an inorganic color pigment (i.e., inorganic pigments having at least some inorganic substrate, coating or constituent). Suitable inorganic color pigments include any of various inorganic pigments that impart tinting or color in a cosmetic composition, such as iron oxides, ultramarine blue pigments, manganese violet, ferric ferrocyanide and chromium green pigments, pearlescent pigments, effect pigments, and the like. The color pigments may be coated or uncoated, however, in certain notable embodiments uncoated color pigments are used to make the compositions. In certain embodiments, the inorganic color pigments include or consist of iron oxide.

Any of various cosmetic grades of color pigments are suitable for use in compositions of the present invention. In certain embodiments the color pigments have an average particle size in a range from about 1 micron to about 100 microns, such as from about 1 micron to about 10 microns.

The concentration by weight of the inorganic color pigments in the composition may range from about 0.01%, 0.05%, or 0.25% to about 1 %, 2%, 5%, or 10% by weight, including all ranges and subranges therebetween.

The uncoated iron oxide pigments are, for example, marketed by

Arnaud under the trademarks "Nanogard WCD 2002 (FE 45B)", "Nanogard Iron FE 45 BL AQ", "Nanogard FE 45R AQ", and "Nanogard WCD 2006 (FE 45R)", or by Mitsubishi under the trademark "TY-220".

The coated iron oxide pigments are, for example, marketed by Arnaud under the trademarks "Nanogard WCD 2008 (FE 45B FN)", "Nanogard WCD 2009 (FE 45B 556)", "Nanogard FE 45 BL 345", and "Nanogard FE 45 BL", or by BASF under the trademark "Oxyde de fer transparent".

INORGANIC FILLER

According to certain embodiments of the invention, the sunscreen compositions may include inorganic fillers. The inventors have found that incorporating inorganic fillers having a median particle size from about 0.2 microns to about 1 micron are able to provide a pleasant “mousse-like” texture. In certain embodiments, the inorganic filler has at least 90% of its particles less than about 1 micron and more than 90% of its particles greater than about 0.33 microns. In certain notable embodiments, the inorganic filler is uncoated; i.e., free of any surface coatings, for example, those coatings that include organic or siloxane moieties. In certain notable embodiments, the inorganic filler includes particles that include titanium dioxide. In certain embodiments, the inorganic filler is a titanium dioxide particle, i.e., is composed of at least 90%, such as greater than about 95% by weight of titanium dioxide.

Suitable (uncoated) titanium oxide pigments are, for example, marketed by Sachtleben Chemie of Duisburg, Germany, under the name "Hombitan FF."

Other suitable inorganic fillers having a median particle size from about 0.2 microns to about 1 micron include mica, talc, and the like.

The concentration by weight of the inorganic fillers having a median particle size from about 0.2 microns to about 1 micron in the composition may range from about 1 %, 1.5%, or 2.0% to about 3.5%, 5%, 7%, or 10% by weight, including all combinations of such ranges.

SILICONE RESIN

The inventors have found that anhydrous sunscreen compositions having high levels of silica aerogel, coverage can be surprisingly improved by incorporating a silicone resin. As used herein, the term "resin" means a crosslinked or non- crosslinked three-dimensional structure. Silicone resin nomenclature is known in the art as "MDTQ" nomenclature, whereby a silicone resin is described according to the various monomeric siloxane units which make up the polymer.

Each letter of "MDTQ" denotes a different type of unit. The letter M denotes the monofunctional unit (CH3)3Si01 12. This unit is considered to be monofunctional because the silicone atom only shares on oxygen when the unit is part of a polymer. The "M" unit can be represented by the following structure:

At least one of the methyl groups of the M unit may be replaced by another group, e.g., to give a unit with formula [R(CFI3)2]Si01 12, as represented in the following structure: wherein R is chosen from groups other than methyl groups. Non-limiting examples of such groups other than methyl groups include alkyl groups other than methyl groups, alkene groups, alkyne groups, hydroxyl groups, thiol groups, ester groups, acid groups, ether groups, wherein the groups other than methyl groups may be further substituted.

The symbol D denotes the difunctional unit (CH3)2Si02/2 wherein two oxygen atoms bonded to the silicone atom are used for binding to the rest of the polymer. The "D" unit, which is the major building block of dimethicone oils, can be represented as:

At least one of the methyl groups of the D unit may be replaced by another group, e.g., to give a unit with formula [R(CH3)2]Si01 /2. [0088] The symbol T denotes the trifunctional unit, (CH3)Si03/2 and can be represented as:

At least one of the methyl groups of the T unit may be replaced by another group, e.g., to give a unit with formula [R(CH3)2]Si01 /2.

Finally, the letter Q means a tetrafunctional unit Si04/2 in which the silicon atom is bonded to four hydrogen atoms, which are themselves bonded to the rest of the polymer.

Thus, a vast number of different silicone polymers can be manufactured. Further, it would be clear to one skilled in the art that the properties of each of the potential silicone polymers will vary depending on the type(s) of monomer(s), the type(s) of substitution(s), the size of the polymeric chain, the degree of cross linking, and size of any side chain(s).

Non-limiting examples of silicone polymers include siloxysilicates and silsesquioxanes.

A non-limiting example of a siloxysilicate is trimethylsiloxysilicate, which may be represented by the following formula:

[(CH3)3XSiXO]xX(Si04/2)y (i.e., MQ units) wherein x and y may, for example, range from 50 to 80.

Silsesquioxanes, on the other hand, may be represented by the following formula:

(CH3Si03/2).x (i.e., T Units) wherein x may, for example, have a value of up to several thousand.

Resin MQ, which is available from Wacker, General Electric and Dow Corning, is an example of an acceptable commercially-available siloxysilicate. For example, trimethylsiloxysilicate (TMS) is commercially available from Momentive Performance Materials under the tradename SR1000.

In certain notable embodiments, the silicone resin (e.g., MQ resin) is free of substitutions other than alkyl groups. In certain the silicone resin (e.g., trimethylsiloxysilicate) is free of substitutions other than methyl groups.

The concentration by weight of the silicone resin in the composition may be at least about 0.5% and range from about 0.5%, 1.0%, or 2.0% to about 3.5%, 4%, 5%, or 10% by weight, including all combinations of such ranges. The concentration by weight of the silicone resin in the composition may be less than the concentration by weight of the silica aerogel.

NON UV-ABSORBING FATTY COMPOUNDS

In addition to the constituents of the anhydrous sunscreen composition described above, the composition of the present invention may also include additional fatty compounds selected from oils, waxes, fatty acids, fatty alcohols, and mixtures thereof. The non UV-absorbing fatty compounds do not appreciably absorb or scatter ultraviolet radiation. Accordingly, as used herein, the term“additional fatty compounds” does not include UV-filters described above described above.

Suitable non UV-absorbing fatty compounds include those suitable for providing emolliency to the skin. Examples of such compounds compounds generally insoluble in water and includes a hydrophobic moiety, such as one meeting one or more of the following three criteria: (a) has a carbon chain of at least six carbons in which none of the six carbons is a carbonyl carbon or has a hydrophilic moiety (defined below) bonded directly to it; (b) has two or more alkyl siloxy groups; or (c) has two or more oxypropylene groups in sequence. The hydrophobic moiety may include linear, cyclic, aromatic, saturated or unsaturated groups. The hydrophobic compound is in certain embodiments not amphiphilic and, as such, in this embodiment does not include hydrophilic moieties, such as anionic, cationic, zwitterionic, or nonionic groups, that are polar, including sulfate, sulfonate, carboxylate, phosphate, phosphonate, ammonium, including mono-, di-, and trialkylammonium species, pyridinium, imidazolinium, amidinium, poly(ethyleneiminium), ammonioalkylsulfonate, ammonioalkylcarboxylate, amphoacetate, and poly(ethyleneoxy)sulfonyl moieties. In certain embodiments, the oil does not include hydroxyl moieties.

Suitable examples of compounds of oils include vegetable oils (glyceryl esters of fatty acids, monoglycerides, diglycerides, triglycerides) and fatty esters. Specific non-limiting examples include, without limitation, esters such as isopropyl palmitate, isopropyl myristate, isononyl isonanoate C12-C15 alkyl benzoates, caprylic/capric triglycerides, ethylhexyl hydroxystearate, silicone oils (such as dimethicone and cyclopentasiloxane), pentaerythritol tetraoctanoate and mineral oil. Other examples of oils include liquid organic ultraviolet filter commonly used for example as UV-absorbing sunscreens such as octocrylene, octyl salicylate, octyl methoxyxcinnamate, among others.

Suitable oils include volatile and/or non-volatile oils. Such oils can be any acceptable oil including but not limited to silicone oils and/or hydrocarbon oils.

According to certain embodiments, the compositions of the present invention may include one or more volatile silicone oils. Examples of such volatile silicone oils include linear or cyclic silicone oils having a viscosity at room temperature less than or equal to 6cSt and having from 2 to 7 silicon atoms, these silicones being optionally substituted with alkyl or alkoxy groups of 1 to 10 carbon atoms. Specific oils that may be used in the invention include octamethyltetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethyloctyltrisiloxane, hexamethyldisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane and their mixtures. Other volatile oils which may be used include KF 96A of 6 cSt viscosity, a commercial product from Shin Etsu having a flash point of 94°C.

In certain notable embodiments, the non UV-absorbing compound has a melting point of less than about 30°C. In certain other embodiments, the compositions are substantially free of waxes, e,g, non UV-absorbing fatty compounds that are solid at room temperature (about 25° C.) and atmospheric pressure (760 mm Hg, i.e., 105 Pa), which undergo a reversible solid/liquid change of state and which have a melting point of greater than 30°C., and in some embodiments, greater than about 55° C. up to about 120° C. or even as high as about 200° C.

The concentration by weight of non UV-absorbing fatty compounds in the anhydrous sunscreen composition according to the invention is generally from about 10%, 15%, 20%, 30%, or 40% by weight to about 60%, 70%, 75%, or 80% by weight, relative to the total weight of composition, preferably from about 20% by weight to about 80% by weight, more preferably from about 20% by weight to about 70% by weight, relative to 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 perfume/fragrance, preserving agents, antioxidants, solvents, actives, vitamins, fillers, silicones, polymers, 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.

Suitable polymers include, but are not limited to, aluminum starch octenylsuccinate, xanthan gum, poly C10-30 alkyl acrylate, acrylates/Cio-30 alkyl acrylate crosspolymer, styrene/acrylates copolymer, and mixtures thereof.

Non-limiting example of preserving agent which can be used in accordance with the invention include phenoxyethanol. An example of antioxidant is pentaerythrityl tetra-di-t-butyl hydroxyhydrocinnamate.

Suitable solvents include, but are not limited alcohols, glycols and polyols such as glycerin, caprylyl glycol, pentylene glycol, propylene glycol, butylene glycol, and mixtures thereof.

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

The additional ingredients may represent from 0.1 % to 20%, such as from 0.1 % to 10% or such as from 0.1 to 8% by weight of the total weight of the composition of the invention.

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

Anhydrous sunscreen compositions were prepared with 20% by weight of organic UV-filters (octocrylene, butyl methoxydibenzoylmethane, bis- ethylhexyloxyphenol methoxyphenyltriazzine, drometrizole trisiloxane, ethylhexylsalicylate, and ethylhexyl triazone), and amount of silica silylate ranging from 2% to 7%, and the remainder consisted of non UV-absorbing fatty compounds (diisopropyl sebacate, C12-C15 alkyl benzoate, and dicaprylyl ether) and an amount of silica silylate. Specifically, seven samples were made with concentrations of silica silylate ranging from 2% to 8% in one percent increments. The concentration of C12- C15 alkyl benzoate was reduced to accommodate the increasing levels of silica silylate. The samples were evaluated visually and select samples were evaluated on the skin.

The samples with 2% and 3% of silica silylate were not viscous. The samples with 4% and 5% silica silylate had no remaining sediment and were viscous. These latter two samples were evaluated for phase stability after being placed for one week at 55°C and also at 4°C and was found to be stable. The sample was evaluated tactilly on the skin and the sample with 4% silica silylate showed a very oily texture to the skin and the sample with 5% silica silylate showed a somewhat oily texture to the skin.

The sample with 6% silica silylate had no remaining sediment and was viscous. The sample was evaluated for phase stability after being placed for one week at 55°C and also at 4°C and was found to be stable. The sample was evaluated tactilly on the skin and showed a dry texture to the skin, but did not seem to hide imperfections instantly.

The sample with 7% silica silylate had no remaining sediment and was viscous. The samples were evaluated for phase stability after being placed for one week at 55°C and also at 4°C and was found to be stable. The sample was evaluated tactilly on the skin and showed a dry texture to the skin, and did seem to hide imperfections instantly.

The sample with 8% silica silylate had no remaining sediment and was very viscous. The samples were evaluated for phase stability after being placed for one week at 55°C and also at 4°C and was found to be stable. The sample was not evaluated tactilly on the skin. Three similar anhydrous sunscreens were made with 2%, 3% and 4% EVONIK Tego SP (C12-C22 alkyl acrylate) replacing the silica silylate. The first two were not viscous and the 4% lost its viscosity and became unstable at room temperature.

Three similar anhydrous sunscreens were made with 2%, 3% and 4%

EVONIK TEGOFEEL C10 (cellulose) replacing the silica silylate. Each of these were not homogenous and sedimentation formed that did not disappear after mixing.

Anhydrous sunscreen compositions were prepared with 20% by weight of organic UV-filters (octocrylene, butyl methoxydibenzoylmethane, bis-ethylhexyloxyphenol methoxyphenyltriazzine, drometrizole trisiloxane, ethylhexylsalicylate, and ethylhexyl triazone), 7%, silica silylate, 5% of a filler material (each sample with a different filler material), and the remainder consisted of non UV-absorbing fatty compounds (diisopropyl sebacate, C12-C15 alkyl benzoate, and dicaprylyl ether) and an amount of silica silylate. Specifically, six samples were made.

The first sample was made with an inorganic filler, specifically uncoated titanium dioxide, having a median particle size from about 0.2 microns to about 1 micron and having at least 90% of its particles less than about 1 micron and more than 90% of its particles greater than about 0.33 microns (Hombitan FF from Sachtlaben). The sample had pleasant mousse-like texture and was very white.

The second sample was made with an inorganic filler, specifically titanium dioxide coated with stearic acid and aluminum hydroxide, having a particle size of about 15nm. The sample was paste-like and hard to spread and showed residue on the skin.

The third sample was made with a spherical amorphous silica

(Sunsphere® H51 from Asahi Glass). The sample had a pleasant thick, honey-like texture.

The fourth sample was made mica having a particle size from about 5- 10 microns. The sample showed a thick, pinkish texture that was opaque and not aesthetically pleasing.

The fifth sample was made with expanded perlite having a particle size of about 25 microns. The sample showed a thick, pinkish texture that was not aesthetically pleasing. The sixth sample was made with titanium dioxide encapsulated in silica and having an average particle size more than 2 microns. The sample appeared yellow, opaque and showed some evidence of instability.

EXAMPLE III

Anhydrous sunscreen compositions were prepared with 20% by weight of organic UV-filters (octocrylene, butyl methoxydibenzoylmethane, bis- ethylhexyloxyphenol methoxyphenyltriazzine, drometrizole trisiloxane, ethylhexylsalicylate, and ethylhexyl triazone), 7%, silica silylate, 5% of inorganic filler material (uncoated titanium dioxide, having a median particle size from about 0.2 microns to about 1 micron and having at least 90% of its particles less than about 1 micron and more than 90% of its particles greater than about 0.33 microns), about about 64% of non UV-absorbing fatty compounds (diisopropyl sebacate, C12-C15 alkyl benzoate, and isononyl isonanoate, diisopropyl adipate), about 1 % of inorganic color pigments and 3% of a film forming polymer (all on actives basis). Specifically, eight samples were made.

The samples were evaluated by seven individual panelists very familiar with cosmetic formulations, for coverage, transference, and dry-touch sensorial. The panelists tested the samples on the forearm or face and gave their impressions during application and after the samples dried of oiliness/ tacky/shininess and also for coverage of skin tone/imperfections. The panelists also tested the samples using a paper tissue for transference to evaluate if the color/product were fixing to the skin or not. The panelists were asked to vote for the best overall sample or samples.

The first sample was made with a film forming polymer that was a silicone acrylate, specifically an acrylates/polytrimethylsiloxy-methacrylate copolymer (DOWSIL FA 4003 DM Silicone Acrylate). This composition received zero votes from the panelists. Comments included that the composition did not resist transfer well and the sensorial was inferior to the other samples.

The second sample was made with a film forming polymer that was a Hydrogenated Polycyclopentadiene (KOBOGUARD 5400). This composition received two votes from the panelists. Comments included that the transfer resistance was better than the first sample, but the majority of the panelists felt that this needed sensorial improvement.

The third sample was made with a film forming polymer that was a Hydrogenated Dimer Dilinoleyl Dimethylcarbonate Copolymer (COSMEDIA DC from BASF). This composition received zero votes. Comments included that the composition did not resist transfer well.

The fourth sample was made with a film forming polymer that was a silicone (MQ) resin, specifically trimethylsiloxysilicate (SILSOFT 74 from Momentive). This composition received six votes. Comments included that the composition resisted transfer very well.

The fifth sample was made with a film forming polymer that was a vinylpyrrolidone polymer, (GANEX ANTARON V216 from Ashland). This composition received zero votes. Comments included that the composition did not resist transfer well.

The sixth sample was made with a film forming polymer that was an ethylene oxide/propylene oxide block copolymer. (SYNPERONIC from Croda). This composition received zero votes. Comments included that the composition resisted transfer, but sensorial was poor as it gave an unpleasant oily feeling.

The seventh sample was made with a film forming polymer that was an amine functional silicone. This composition received three votes. Comments included that the composition resisted transfer, but sensorial was poor as it gave an unpleasant, very oily feeling.

Those skilled in the art will recognize or be able to ascertain using no more than routine experimentation many equivalents to the specific embodiments of the invention described herein. Such equivalents are intended to be encompassed by the following claims.

Claims

SET OF CLAIMS

1. An anhydrous sunscreen composition, comprising:

(a) at least about 5% by weight of silica aerogel, relative to the total weight of the composition;

(b) a silicone resin, present in a concentration by weight that is at least about 0.5% and less than the concentration by weight of the silica aerogel; and

(c) organic UV-filters; and

(d) an inorganic color pigment.

2. The anhydrous sunscreen composition, according to claim 1 , wherein the amount of silica aerogel in the sunscreen composition is from about 5% by weight to about 8% by weight, relative to the total weight of the composition.

3. The anhydrous sunscreen composition, according to claim 1 , wherein the silicone resin is trimethylsiloxysilicate.

4. The anhydrous sunscreen composition, according to claim 1 , further comprising at least one non UV-absorbing fatty compound, wherein the concentration of the at least one non UV-absorbing fatty compounds in the sunscreen composition is from about 10% by weight to about 75% by weight, relative to the total weight of the composition.

5. The anhydrous sunscreen composition, according to claim 1 , wherein the amount of organic UV-filters are present in the sunscreen composition in a concentration by weight from about 10% by weight to about 40% by weight, relative to the total weight of the composition.

6. The anhydrous sunscreen composition, according to claim 1 , wherein the amount of inorganic color pigment is present in the sunscreen composition in a concentration by weight from about 0.25% by weight to about 5% by weight, relative to the total weight of the composition.

7. The anhydrous sunscreen composition, according to claim 1 , wherein the organic UV-filters comprises at least one organic UV-filter selected from the group consisting of anthranilic compounds; dibenzoylmethane compounds; cinnamic compounds; salicylic compounds; camphor compounds; benzophenone compounds; b,b-diphenylacrylate compounds; triazine compounds; benzotriazole compounds; benzalmalonate compounds; benzimidazole compounds; imidazoline compounds; bis-benzoazolyl compounds; p-aminobenzoic acid (PABA) compounds; methylenebis(hydroxyphenylbenzotriazole) compounds; benzoxazole compounds; screening polymers and screening silicones; dimers derived from a-alkylstyrene; 4,4- diarylbutadienes compounds; guaiazulene and derivatives thereof; rutin and derivatives thereof; flavonoids; bioflavonoids; oryzanol and derivatives thereof; quinic acid and derivatives thereof; phenols; retinol; cysteine; aromatic amino acids; peptides having an aromatic amino acid residue; and mixtures thereof.

8. The anhydrous sunscreen composition, according to claim 1 wherein the inorganic color pigment is uncoated.

9. The anhydrous sunscreen composition, according to claim 1 wherein the inorganic pigment is iron oxide.

10. The anhydrous sunscreen composition of claim 1 , further comprising an inorganic filler having a median particle size from about 0.2 microns to about 1 micron.

1 1. The anhydrous sunscreen composition of claim 9, wherein the inorganic filler is a titanium dioxide particle.

12. The anhydrous sunscreen composition, according to claim 1 , wherein the amount of organic UV-filters are present in the sunscreen composition in a concentration by weight from about 15% by weight to about 30% by weight, relative to the total weight of the composition.

13. The anhydrous sunscreen composition, according to claim 1 , wherein the composition is substantially free of waxes.

14. The anhydrous sunscreen composition, according to claim 1 , wherein the silicone resin is present in a concentration by weight from about 1 % to about 4%.

15. An anhydrous sunscreen composition, comprising:

(a) at least 5% by weight of silylated silica, relative to the total weight of the composition;

(b) trimethylsiloxysilicate, present in a concentration by weight that is at least 0.5% and less than the concentration by weight of the silica aerogel;

(c) from 10% by weight to 40% by weight of organic UV-filters;

(d) from 10% to 75% of at least one non UV-absorbing fatty compound;

(e) iron oxide; and

(f) from 2% by weight to 7% by weight of a titanium dioxide having a median particle size from 0.2 microns to 1 micron.

16. A method of making an anhydrous sunscreen, comprising the step of blending silica aerogel, trimethylsiloxysilicate, an organic UV-filter, a non UV- absorbing fatty compound, an inorganic color pigment, and an uncoated titanium dioxide having a median particle size from about 0.2 microns to about 1 micron to form an anhydrous sunscreen comprising at least about 5% by weight of the silica aerogel by weight in the anhydrous composition.