DESCRIPTION

COSMETIC COMPOSITION TECHNICAL FIELD

The present invention relates to a composition, in particular for UV screening, comprising a combination of specific selected ingredients, and also relates to a non-therapeutic cosmetic method using the same.

BACKGROUND ART

Aging skin is the result of more than just chronological age. Skin is exposed to various environmental stresses, such as UV rays, which cause free radicals to form in the skin. Free radicals include, for example, singlet oxygen, hydroxyl radicals, the superoxide anion, nitric oxide, and hydrogen radicals. The end result is a loss of elasticity of the skin and the appearance of wrinkles leading to premature aging of the skin. This process is commonly referred to as photo-aging. Generally, UV sunscreen actives are utilized to provide protection from UV light. Numerous cosmetic compositions intended for the photoprotection (UV-A and/or UV-B) of the skin have been proposed to date.

These anti-sun compositions often take the form of oil-in-water or water-in-oil emulsions, of gels, or of non-aqueous products which contain, in various concentrations, one or more insoluble and/or fat-soluble and/or water-soluble, organic and/or inorganic screening agents that are capable of selectively absorbing the harmful UV radiation. These screening agents and their amounts are selected as a function of the desired sun protection factor (SPF). The sun protection factor (SPF) mathematically expresses the ratio of the dose of

UV radiation necessary to achieve the erythematogenic threshold with the UV screening agent to the dose of UV radiation necessary to achieve the erythematogenic threshold without the UV screening agent. Accordingly, an increasing need exists for anti-sun products having a high sun protection factor. High sun protection factors can be obtained by incorporating more screening agents in high concentrations. This cannot always be done since the addition of large quantities of screening agents considerably increases the cost of the anti-sun formulations and the risks of skin irritation.

In addition, it is also required for cosmetic products to be applied onto, for example, the skin, regardless of the purpose of photoprotection, that the irregularities on the skin such as spots, blots, wrinkles, and fine lines be concealed or become less distinct, preferably immediately, and that the cosmetic products have good sensorial texture such as good spreadability, no or little formation of noodles (long, narrow aggregates formed by cosmetic products which may look like eraser dust), and moisturizing feeling.

Thus, there has been a need for a cosmetic product with good UV-shielding ability which can be achieved by without increasing the amount of a UV filter or filters in the product, and good immediate optical effects to conceal the irregularities on the skin or to make them less distinct, as well as good sensorial texture.

DISCLOSURE OF INVENTION One of the objectives of the present invention is to provide a composition which can provide (1) good UV-shielding ability that may be achieved without increasing the amount of a UV filter or filters in the composition, while providing (2) good immediate optical effects and (3) good sensorial texture. The above objective of the present invention can be attained by a composition, comprising, in a physiologically acceptable medium, preferably a cosmetic composition comprising a cosmetically acceptable medium:

(a) at least one UV filter;

(b) at least one particle having a refractive index of 1.5 or more; and

(c) at least one SPF booster.

The (a) UV filter may be selected from inorganic UV filters, organic UV filters, and mixtures thereof. The inorganic UV filter may be selected from the group consisting of silicon carbide, metal oxides, and mixtures thereof.

The organic UV filter may be selected from the group consisting of anthranilic compounds; dibenzoylmethane compounds; cinnamic compounds; salicylic compounds; camphor compounds; benzophenone compounds; β,β-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-diarylbutadiene compounds; and mixtures thereof.

The (b) particle having a refractive index of 1.5 or more may be selected from pigments and lamellar particles other than the pigments. The (b) particle having a refractive index of 1.5 or more may be selected from the group consisting of boron nitride, titanium dioxide, zinc oxide, and mixtures thereof.

The (c) SPF booster may be selected from hollow particles. The (c) SPF booster may be made from at least one material selected from the group consisting of (co)polymers of (meth)acrylic acid, (meth)acrylates, and/or styrene; glass; silica; and mixtures thereof.

The (c) SPF booster may be in the form of a particle with a particle size from 100 to 380 nm.

The amount of the (a) UV filter(s) may be from 0.1 to 50% by weight, preferably from 1 to 40% by weight, and more preferably from 2 to 30% by weight in relation to the total weight of the composition. The amount of the (b) particle(s) having a refractive index of 1.5 or more may be from 0.1% to 10% by weight, preferably from 0.3% to 8% by weight, and more preferably 0.5% to 5% by weight in relation to the total weight of the composition.

The amount of the (c) SPF booster(s) may be from 0.1 % to 10% by weight, preferably from 0.3% to 8%) by weight, and more preferably from 0.5% to 5% by weight in relation to the total weight of the composition.

The present invention also relates to a non-therapeutic cosmetic method for caring for and/or making up the skin, comprising applying the composition according to the present invention.

The present invention also relates to a cosmetic skincare process for providing immediate optical effect on the surface of the skin, comprising the step of applying the composition according to the present invention. The present invention also relates to a non-therapeutic cosmetic method for treating aging of the skin, comprising applying the composition according to the present invention.

BEST MODE FOR CARRYING OUT THE INVENTION After diligent research, the inventors have discovered that it is possible to achieve the above objective by a combination of some specific selected ingredients in a composition, preferably for photoprotection from light, in particular UV rays.

Thus, the present invention relates to a composition, comprising, in a physiologically acceptable medium, preferably a cosmetic composition comprising in a cosmetically acceptable medium:

(a) at least one UV filter;

(b) at least one particle having a refractive index of 1.5 or more; and

(c) at least one SPF booster.

The composition according to the present invention can provide (1) high UV-shielding ability without increasing the amount of the (a) UV filter(s) in the composition, (2) good immediate optical effects, and (3) good sensorial texture. Furthermore, the methods according to the present invention can provide cosmetic effects based on the UV-shielding ability and optical effects of the compositions according to the present invention.

Hereinafter, the composition and the method according to the present invention will be explained in a more detailed manner.

[Composition]

The composition according to the present invention includes in a physiologically acceptable medium:

(a) at least one UV filter;

(b) at least one particle having a refractive index of 1.5 or more; and

(c) at least one SPF booster. The "physiologically acceptable medium" here means a medium which is not toxic and can be applied to the skin, lips, hair, scalp, lashes, brows, nails, or any other cutaneous region of the body, and can be rephrased in particular as "cosmetically acceptable medium".

Each of the components (a) to (c) will be explained below.

{UV filter}

The composition according to the present invention includes at least one UV filter. There is no limitation to the type of the UV filter. Two or more types of UV. filters may be used in combination. Thus, a single type of UV filter or a combination of different types of UV filters may be used.

The UV filter can be selected from inorganic UV filters, organic UV filters, and mixtures thereof.

The composition according to the present invention may comprise the UV filter(s) in an amount of from 0.1 to 50% by weight, preferably from 1 to 40% by weight, and more preferably from 2 to 30% by weight in relation to the total weight of the composition.

(Inorganic UV filter)

The composition according to the present invention may comprise at least one inorganic UV filter. If two or more inorganic UV filters are used, they may be the same or different, preferably the same.

The inorganic UV filter used for the present invention may be active in the UV-A and/or UV-B region. The inorganic UV filter may be hydrophilic and/or lipophilic. The inorganic UV filter is preferably insoluble in solvents such as water and ethanol commonly used in cosmetics.

It is preferable that the inorganic UV filter be in the form of a fine particle such that the mean (primary) particle diameter thereof ranges from 1 nm to 50 nm, preferably 5 nm to 40 nm, and more preferably 10 nm to 30 nm. The mean (primary) particle size or mean (primary) particle diameter here is an arithmetic mean diameter.

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. Preferably, the inorganic UV filters are selected from pigments (mean size of the primary particles: generally from 5 nm to 50 nm, preferably from 10 nm to 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. Preferably, the inorganic UV filters are selected from titanium oxide, zinc oxide, and more preferably titanium oxide.

The inorganic UV filter may or may not be coated. The inorganic UV filter may have at least one coating. The coating may comprise at least one compound selected from the group consisting of 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. It is preferable for the coating to include at least one organic UV filter. As the organic UV filter in the coating, a dibenzoylmethane derivative such as butyl methoxydibenzoylmethane (Avobenzone) and 2,2'-Methylenebis[6-(2H-Benzotriazol-2-yl)-4-(l,l,3,3-Tetram ethyl-Butyl) Phenol] (Methylene Bis-Benzotriazolyl Tetramethylbutylphenol) marketed as "TINOSORB M" by BASF may be preferable.

In a known manner, the silicones in the coating(s) may be organosilicon polymers or oligomers comprising a linear or cyclic and branched or cross-linked structure, of variable molecular weight, obtained by polymerization and/or polycondensation of suitable functional silanes and essentially composed of repeated main units in which the silicon atoms are connected to one another via oxygen atoms (siloxane bond), optionally substituted

hydrocarbon radicals being connected directly to said silicon atoms via a carbon atom.

The term "silicones" also encompasses silanes necessary for their preparation, in particular alkylsilanes.

The silicones used for the coating(s) can preferably be selected from the group consisting of alkylsilanes, polydialkylsiloxanes, and polyalkylhydrosiloxanes. More preferably still, the silicones are selected from the group consisting of octyltrimethylsilane,

polydimethylsiloxanes, and polymethylhydrosiloxanes.

Of course, the inorganic UV filters made of metal oxides may, before their treatment with silicones, have been treated with other surfacing agents, in particular with cerium oxide, alumina, silica, aluminum compounds, silicon compounds, or their mixtures. The coated inorganic UV filter may have been prepared by subjecting the inorganic UV filter to one or more surface treatments of a chemical, electronic, mechanochemical, and/or mechanical nature with any of the compounds as described above, as well as polyethylenes, metal alkoxides (titanium or aluminum alkoxides), metal oxides, sodium hexametaphosphate, and those shown, for example, in Cosmetics & Toiletries, February 1990, Vol. 105, pp. 53-64.

The coated inorganic UV filters may be titanium oxides coated:

with silica, such as the product "Sun veil" from Ikeda, and "Sunsil TIN 50" from Sunjin Chemical;

with silica and with iron oxide, such as the product "Sunveil F" from Ikeda;

with silica and with alumina, such as the products "Microtitanium Dioxide MT 500 SA" from Tayca, "Tioveil" from Tioxide, and "Mirasun TiW 60" from Rhodia;

with alumina, such as the products "Tipaque TTO-55 (B)" and "Tipaque TTO-55 (A)" from Ishihara, and "UVT 14/4" from Kemira;

with alumina and with aluminum stearate, such as the product "Microtitanium Dioxide MT 100 T, MT 100 TX, MT 100 Z or MT-01" from Tayca, the products "Solaveil CT-10 W" and "Solaveil CT 100" from Uniqema, and the product "Eusolex T-AVO" from Merck;

with alumina and with aluminum laurate, such as the product "Microtitanium Dioxide MT 100 S" from Tayca;

with iron oxide and with iron stearate, such as the product "Microtitanium Dioxide MT 100 F" from Tayca; with zinc oxide and with zinc stearate, such as the product "BR351" from Tayca;

with silica and with alumina and treated with a silicone, such as the products "Microtitanium Dioxide MT 600 SAS", "Microtitanium Dioxide MT 500 SAS", and "Microtitanium Dioxide MT 100 SAS" from Tayca;

with silica, with alumina and with aluminum stearate and treated with a silicone, such as the product "STT-30-DS" from Titan Kogyo;

with silica and treated with a silicone, such as the product "UV- Titan X 195" from Kemira; with alumina and treated with a silicone, such as the products "Tipaque TTO-55 (S)" from Ishihara or "UV Titan M 262" from Kemira;

with triethanolamine, such as the product "STT-65-S" from Titan Kogyo;

with stearic acid, such as the product "Tipaque TTO-55 (C)" from Ishihara; or

with sodium hexametaphosphate, such as the product "Microtitanium Dioxide MT 150 W" from Tayca. Other titanium oxide pigments treated with a silicone are preferably Ti0 ₂ treated with octyltrimethylsilane and for which the mean size of the individual particles is from 25 and 40 nm, such as that marketed under the trademark "T 805" by Degussa Silices, Ti0 ₂ treated with a polydimethylsiloxane and for which the mean size of the individual particles is 21 nm, such as that marketed under the trademark "70250 Cardre UF Ti0 ₂ Si ₃ " by Cardre, and

anatase/rutile Ti0 ₂ treated with a polydimethylhydrosiloxane and for which the mean size of the individual particles is 25 nm, such as that marketed under the trademark "Microtitanium Dioxide USP Grade Hydrophobic" by Color Techniques.

Preferably, the following coated Ti0 ₂ can be used as the coated inorganic UV filter:

Stearic acid (and) Aluminum Hydroxide (and) Ti0 ₂ , such as the product "MT-100 TV" from Tayca, with a mean primary particle diameter of 15 nm;

Dimethicone (and) Stearic Acid (and) Aluminum Hydroxide (and) Ti0 ₂ , such as the product "S A-TTO-S4" from Miyoshi Kasei, with a mean primary particle diameter of 15 nm;

Silica (and) Ti0 ₂ , such as the product "MT-100 WP" from Tayca, with a mean primary particle diameter of 15 nm;

Dimethicone (and) Silica (and) Aluminum Hydroxide (and) Ti0 ₂ , such as the product "MT-Y02" and "MT-Y-110 M3S" from Tayca, with a mean primary particle diameter of 10 nm;

Dimethicone (and) Aluminum Hydroxide (and) Ti0 ₂ , such as the product "SA-TTO-S3" from Miyoshi Kasei, with a mean primary particle diameter of 15 nm;

Dimethicone (and) Alumina (and) Ti0 ₂ , such as the product "UV TITAN Ml 70" from Sachtleben, with a mean primary particle diameter of 15 nm;. and

Silica (and) Aluminum Hydroxide (and) Alginic Acid (and) Ti0 ₂ , such as the product "MT- 100 AQ" from Tayca, with a mean primary particle diameter of 15 nm.

In terms of UV filtering ability, Ti0 ₂ coated with at least one organic UV filter is more preferable. For example, Avobenzone (and) Stearic Acid (and) Aluminum Hydroxide (and) Ti0 ₂ , such as the product "HXMT-100ZA" from Tayca, with a mean primary particle diameter of 15 nm, can be used.

The uncoated titanium oxide pigments are, for example, marketed by Tayca under the trademarks "Microtitanium Dioxide MT500B" or "Microtitanium Dioxide MT600B", by Degussa under the trademark "P 25", by Wacker under the trademark "Oxyde de titane transparent PW", by Miyoshi Kasei under the trademark "UFTR", by Tomen under the trademark "ITS" and by Tioxide under the trademark "Tioveil AQ". The uncoated zinc oxide pigments are, for example:

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

those marketed under the trademark "Nanox" by Elementis; and

those marketed under the trademark "Nanogard WCD 2025" by Nanophase Technologies.

The coated zinc oxide pigments are, for example:

those marketed under the trademark "Oxide Zinc CS-5" by Toshiba (ZnO coated with polymethylhydrosiloxane);

those marketed under the trademark "Nanogard Zinc Oxide FN" by Nanophase Technologies (as a 40% dispersion in Finsolv TN, C ₁₂ -C ₁₅ alkyl benzoate);

those marketed under the trademark "Daitopersion Zn-30" and "Daitopersion Zn-50" by Daito (dispersions in oxyethylenated polydimethylsiloxane/cyclopolymethylsiloxane comprising 30% or 50% of zinc nano-oxides coated with silica and

polymethylhydrosiloxane) ;

those marketed under the trademark "NFD Ultrafme ZnO" by Daikin (ZnO coated with phosphate of perfiuoroalkyl and a copolymer based on perfluoroalkylethyl as a dispersion in cyclopentasiloxane);

those marketed under the trademark "SPD-Z1" by Shin-Etsu (ZnO coated with a

silicone-grafted acrylic polymer dispersed in cyclodimethylsiloxane);

those marketed under the trademark "Escalol Z100" by ISP (alumina- treated ZnO dispersed in an ethylhexyl methoxycinnamate/PVP-hexadecene copolymer/methicone mixture);

those marketed under the trademark "Fuji ZnO-SMS-10" by Fuji Pigment (ZnO coated with silica and polymethylsilsesquioxane); and those marketed under the trademark "Nanox Gel TN" by Elementis (ZnO dispersed at 55% in C ₁₂ -C ₁₅ alkyl benzoate with hydroxystearic acid polycondensate).

The uncoated cerium oxide pigments are marketed, for example, under the trademark

"Colloidal Cerium Oxide" by Rhone-Poulenc.

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".

Mention may also be made of mixtures of metal oxides, in particular of titanium dioxide and of cerium dioxide, including a mixture of equal weights of titanium dioxide coated with silica and of cerium dioxide coated with silica marketed by Ikeda under the trademark "Sunveil A", and also a mixture of titanium dioxide and of zinc dioxide coated with alumina, with silica and with silicone, such as the product "M 261" marketed by Kemira, or coated with alumina, with silica and with glycerol, such as the product "M 211" marketed by Kemira.

Coated inorganic UV filters are preferable, because the UV filtering effects of the inorganic UV filters can be enhanced. In addition, the coating(s) may help uniformly or

homogeneously disperse the UV filters in the composition according to the present invention. (Organic UV filter)

The composition according to the present invention may comprise at least one organic UV filter. If two or more organic UV filters are used, they may be the same or different, preferably the same.

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; β,β-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 anthranilate, marketed under the trademark "Neo Heliopan MA" by Haarmann and Reimer.

- Dibenzoylmethane compounds: Butyl methoxydibenzoylmethane, marketed in particular under the trademark "Parsol 1789" by Hoffmann-La Roche; and isopropyl dibenzoylmethane.

- Cinnamic compounds: Ethylhexyl methoxycinnamate, marketed in particular under the trademark "Parsol MCX" by Hoffmann-La Roche; isopropyl methoxycinnamate; isopropoxy methoxycinnamate; isoamyl methoxycinnamate, 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), marketed under the trademark "Eusolex HMS" by Rona/EM Industries; ethylhexyl salicylate, marketed under the trademark

"Neo Heliopan OS" by Haarmann and Reimer; glycol salicylate; butyloctyl salicylate; phenyl salicylate; dipropyleneglycol salicylate, marketed under the trademark "Dipsal" by Scher; and TEA salicylate, marketed under the trademark "Neo Heliopan TS" by Haarmann and Reimer.

- Camphor compounds, in particular, benzylidenecamphor derivatives: 3-benzylidene camphor, manufactured under the trademark "Mexoryl SD" by Chimex; 4-methylbenzylidene camphor, marketed under the trademark "Eusolex 6300" by Merck; benzylidene camphor sulfonic acid, manufactured under the trademark "Mexoryl SL" by Chimex; camphor benzalkonium methosulfate, manufactured under the trademark "Mexoryl SO" by Chimex; terephthalylidene dicamphor sulfonic acid, manufactured under the trademark "Mexoryl SX" by Chimex; and polyacrylamidomethyl benzylidene camphor, manufactured under the trademark "Mexoryl SW" by Chimex.

- Benzophenone compounds: Benzophenone-1 (2,4-dihydroxybenzophenone), marketed under the trademark "Uvinul 400" by BASF; benzophenone-2 (Tetrahydroxybenzophenone), marketed under the trademark "Uvinul D50" by BASF; Benzophenone-3

(2-hydroxy-4-methoxybenzophenone) or oxybenzone, marketed under the trademark "Uvinul M40" by BASF; benzophenone-4 (hydroxymethoxy benzophonene sulfonic acid), marketed under the trademark "Uvinul MS40" by BASF; benzophenone-5 (Sodium hydroxymethoxy benzophenone Sulfonate); benzophenone-6 (dihydroxy dimethoxy benzophenone); marketed under the trademark "Helisorb 11" by Norquay; benzophenone-8, marketed under the trademark "Spectra-Sorb UV-24" by American Cyanamid; benzophenone-9 (Disodium dihydroxy dimethoxy benzophenonedisulfonate), marketed under the trademark "Uvinul DS-49" by BASF; and benzophenone- 12, and n-hexyl

2-(4-diethylamino-2-hydroxybenzoyl)benzoate (UVINUL A+ by BASF).

- β,β-Diphenylacrylate compounds: Octocrylene, marketed in particular under the trademark "Uvinul N539" by BASF; and Etocrylene, marketed in particular under the trademark

"Uvinul N35" by BASF.

- Triazine compounds: Diethylhexyl butamido triazone, marketed under the trademark "Uvasorb HEB" by Sigma 3V; 2,4,6-tris(dineopentyl 4'-aminobenzalmalonate)-s-triazine, bis-ethylhexyloxyphenol methoxyphenyl triazine marketed under the trademark «TINOSORB S » by CIBA GEIGY, and ethylhexyl triazone 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, marketed under the trademark "Parsol SLX" by Hoffmann-LaRoche.

- Benzimidazole compounds, in particular, phenylbenzimidazole derivatives:

Phenylbenzimidazole sulfonic acid, marketed in particular under the trademark "Eusolex 232" by Merck, and disodium phenyl dibenzimidazole tetrasulfonate, 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, marketed in particular under the trademark "Escalol 507" by ISP, glyceryl PABA, and PEG-25 PABA, marketed under the trademark "Uvinul P25" by BASF.

- Methylene bis-(hydroxyphenylbenzotriazol) compounds, such as

2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-methyl-pheno l] 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-tetram ethylbutyl)phenol] 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, marketed under the trademark "Silatrizole" by Rhodia Chimie or- "Mexoryl XL" by L'Oreal, as represented below.

- Benzoxazole compounds: 2,4-bis[5-l(dimethylpropyl)benzoxazol-2-yl-(4-phenyl)imino]- 6-(2-ethylhexyl)imino-l,3,5-triazine, 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 preferable 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-hydr oxybenzoyl]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-eth ylhexyl)imino-l,3,5-triazine, camphor benzylkonium methosulfate, and mixtures thereof.

{Particle Having Refractive Index of 1.5 or More}

The composition according to the present invention comprises at least one particle having a refractive index of 1.5 or more, which may be referred to as "highly refractive particle". If two or more highly refractive particles are used, they may be the same or different, preferably the same.

The refractive index of the highly refractive particles can be measured according to known methods for measuring this index. The refractive index can be measured in accordance with known methods in the art. In the case of organic particles, for example, the refractive index can be measured according to the method described in the article "The refractive index of organic pigments. Its determination and significance", by A.C. Cooper, B.SC, A.R.I. C, in Journal of the oil & colour chemists ' association, September 1948, No. 339, Vol. XXXI. It is preferable that the highly refractive particle have a refractive index of 1.6 or more, more preferably 1.7 or more, and even more preferably 1.8 or more.

The particle having a refractive index of 1.5 or more may be selected from pigments and lamellar particles other than the pigments. (Pigment)

The composition according to the invention may comprise at least one pigment.

The expression "pigments" should be understood to mean particles of any shape, which are white or coloured, inorganic or organic, insoluble in the physiological medium or cosmetically acceptable medium, and intended to colour the composition. Thus, the highly refractive particle may be white and/or coloured, inorganic and/or organic.

According to a particular embodiment, the composition according to the invention may comprise at least one pigment chosen from inorganic pigments. The term "inorganic pigment" is intended to mean any pigment that corresponds to the definition in Ullmann's encyclopaedia in the inorganic pigment chapter. These inorganic pigments may in particular be chosen from pigments of metal oxides.

There may be mentioned, among the inorganic pigments, titanium dioxide, which is optionally surface-treated, zirconium or cerium oxides, zinc, iron (black, yellow, or red), or chromium oxides, manganese violet, ultramarine blue, chromium hydrate, and ferric blue, and metallic powders such as aluminium powder and copper powder.

According to a preferred embodiment, the inorganic pigments, in particular of metal oxides, present in the composition according to the invention are chosen from titanium dioxide, zinc oxide, and/or iron oxide. It is preferable that the titanium oxide as pigments have a particle size of 0.1 μηι or more, more preferably 0.2 μπι or more, and even more preferably 0.3 μηι or more. Typically, titanium oxide as pigments may have a particle size of 0.2 to 0.4 μηι.

According to a particular embodiment, the composition according to the invention may comprise at least two different pigments.

According to a further preferred embodiment, the composition according to the invention may comprise at least a first pigment chosen from iron oxides and at least a second pigment chosen from zinc oxides and/or titanium dioxide.

The iron oxides may be present in the composition according to the invention in an amount ranging from 0.001 to 10% by weight, relative to the total weight of the composition, preferably from 0.005 to 5%, and more preferably from 0.01 to 1% by weight. The zinc oxides may be present in the composition according to the invention in an amount ranging from 1 to 20% by weight, relative to the total weight of the composition, preferably from 2 to 15% by weight, and more preferably from 3 to 10% by weight.

The titanium dioxide may be present in the composition according to the invention in an amount ranging from 1 to 20% by weight, relative to the total weight of the composition, preferably from 2 to 15% by weight, and more preferably from 3 to 10% by weight.

According to a preferred embodiment, the titanium dioxide and/or zinc oxide pigments and the iron oxide pigments may be present in the composition according to the invention in an amount such that the titanium oxide to iron oxide weight ratio ranges from 1 to 100, preferably from 5 to 50, and more preferably still from 10 to 30.

In addition to or instead of the inorganic pigments, the composition according to the invention may comprise organic pigments.

The term "organic pigment" is intended to mean any pigment that corresponds to the definition in Ullmann's encyclopaedia in the organic pigment chapter. The organic pigment may in particular be chosen from nitroso, nitro, azo, xanthene, quinoline, anthraquinone, and phthalocyanin compounds, compounds of metal complex type, and isoindolinone, isoindoline, quinacridone, perinone, perylene, diketopyrrolopyrrole, thioindigo, dioxazine,

triphenylmethane, and quinophthalone compounds.

The organic pigment(s) may be chosen, for example, from carmine, carbon black, aniline black, azo yellow, quinacridone, phthalocyanin blue, sorghum red, the blue pigments codified in the Color Index under the references CI 42090, 69800, 69825, 73000, 74100, and 74160, the yellow pigments codified in the Color Index under the references CI 11680, 11710, 15985, 19140, 20040, 21100, 21108, 47000, and 47005, the green pigments codified in the Color Index under the references CI 61565, 61570, and 74260, the orange pigments codified in the Color Index under the references CI 11725, 15510, 45370, and 71105, the red pigments codified in the Color Index under the references CI 12085, CI 12120, 12370, 12420, 12490, 14700, 15525, 15580, 15620, 15630, 15800, 15850, 15865, 15880, 17200, 26100, 45380, 45410, 58000, 73360, 73915, and 75470, and the pigments obtained by oxidative

polymerization of indole or phenolic derivatives as described in patent FR 2 679 771. These pigments may also be in the form of composite pigments as described in patent

EP 1 184 426. This composite pigment may be composed in particular of particles containing an inorganic core, at least one binder providing attachment of the organic pigments to the core, and at least one organic pigment that at least partially covers the core. By way of example, mention may be made of pigmentary pastes of organic pigment such as the products sold by the company Hoechst under the names:

- JAUNE COSMENYL IOG: Pigment YELLOW 3 (CI 11710)

- JAUNE COSMENYL G: Pigment YELLOW 1 (CI 1 1680)

- ORANGE COSMENYL GR: Pigment ORANGE 43 (CI 71 105)

- ROUGE COSMENYL R: Pigment RED 4 (CI 12085)

- CARMIN COSMENYL FB: Pigment RED 5 (CI 12490)

- VIOLET COSMENYL RL: Pigment VIOLET 23 (CI 51319)

- BLEU COSMENYL A2R: Pigment BLUE 15.1 (CI 74160)

- VERT COSMENYL GG: Pigment GREEN 7 (CI 74260)

- NOIR COSMENYL R Pigment BLACK 7 (CI 77266)

The coloured pigment may also be a lake. The term "lake" is intended to mean dyes adsorbed onto insoluble particles, the assembly thus obtained remaining insoluble during use. The inorganic substrates onto which the dyes are adsorbed are, for example, alumina, silica, calcium sodium borosilicate or calcium aluminium borosilicate, and aluminium. Among the organic dyes, mention may be made of cochineal carmine.

By way of examples of lakes, mention may be made of the products known under the following names: D & C Red 21 (CI 45 380), D & C Orange 5 (CI 45 370), D & C Red 27 (CI 45 410), D & C Orange 10 (CI 45 425), D & C Red 3 (CI 45 430), D & C Red 7 (CI 15 850:1), D & C Red 4 (CI 15 510), D & C Red 33 (CI 17 200), D & C Yellow 5 (CI 19 140), D & C Yellow 6 (CI 15 985), D & C Green (CI 61 570), D & C Yellow 1 O (CI 77 002), D & C Green 3 (CI 42 053), and D & C Blue 1 (CI 42 090). Among the organic pigments, there may be mentioned carbon black, D & C type pigments, and lacquers based on carmine, barium, strontium, calcium, and aluminium.

The composition according to the invention may also comprise goniochromatic pigments; these pigments exhibit a relatively high change of colour with the angle of observation.

The goniochromatic pigment may be chosen, for example, from pigments with an

interferential multilayer structure and from liquid crystal pigments.

In the case of a multilayer structure, the latter may comprise, for example, at least two layers, each layer, independently of the other layer(s) or not, being produced for example from at least one material chosen from the group consisting of the following materials: MgF ₂ , CeF ₃ , ZnS, ZnSe, Si, Si0 ₂ , Ge, Te, Fe ₂ 0 ₃ , Pt, Va, A1 ₂ 0 ₃ , MgO, Y ₂ 0 ₃ , S ₂ 0 ₃ , SiO, Hf0 ₂ , Zr0 ₂ , Ce0 ₂ , Nb ₂ 0 ₅ , Ta ₂ 0 ₅ , Ti0 ₂ , Ag, Al, Au, Cu, Rb, Ti, Ta, W, Zn, MoS ₂ , cryolite, alloys, polymers, and combinations thereof. The goniochromatic agents with multilayer structures are in particular those described in the following documents: US-A-3 438 796, EP-A-227423,

US-A-5 135 812, EP-A-170439, EP-A-341002, US-A-4 930 866, US-A-5 641 719,

EP-A-472371, EP-A-395410, EP-A-753545, EP-A-768343, EP-A-571836, EP-A-708154, EP-A-579091, US-A-5 411 586, US-A-5 364 467, WO-A-97/39066, DE-A-4 225 031, WO 9517479 (BASF), and DE-A-196 14 637. They exist in the form of glitter with a metallic colour.

The multilayer structures which can be used in the invention are, for example, the following structures: Al/Si0 ₂ /Al/Si0 ₂ /Al; Cr/MgF ₂ /Al/MgF ₂ /Al; MoS ₂ /Si0 ₂ /Al/Si0 ₂ /MoS ₂ ;

Fe ₂ 0 ₃ /Si0 ₂ /Al/Si0 ₂ /Fe ₂ 0 ₃ ; Fe ₂ 0 ₃ /Si0 ₂ /Fe ₂ 0 ₃ /Si0 ₂ /Fe ₂ 0 ₃ ;

MoS ₂ /Si0 ₂ /mica-oxide/Si0 ₂ /MoS ₂ ; and Fe ₂ 0 ₃ /Si0 ₂ /mica-oxide/Si0 ₂ /Fe ₂ 0 ₃ . Various colours are obtained according to the thickness of the various layers. Thus, with the

Fe ₂ 03/Si0 ₂ /Al/Si0 ₂ /Fe ₂ 0 ₃ structure, the colour goes from golden-green to grey-red for Si0 ₂ layers from 320 to 350 nm; from red to golden for Si0 ₂ layers from 380 to 400 nm; from violet to green for Si0 ₂ layers from 410 to 420 nm; from copper to red for Si0 ₂ layers from 430 to 440 nm.

Consequently, the multilayer structure may be mainly inorganic or organic. Various colours are obtained depending on the thickness of each of the various layers. The goniochromatic pigments with an interferential multilayer structure according to the invention are in particular those described in the following documents: US-A-3 438 796, EP-A-227423, US-A-5 135 812, EP-A-170439, EP-A-341002, US-A-4 930 866,

US-A-5 641 719, EP-A-472371, EP-A-395410, EP-A-753545, EP-A-768343, EP-A-571836, EP-A-708154, EP-A-579091, US-A-5 411 586, US-A-5 364 467, WO-A-97/39066,

DE-A-4 225 031, WO 9517479 (BASF), DE-A-196 14 637, and combinations thereof. They exist in the form of glitter with a metallic colour.

The goniochromatic pigment with an interferential multilayer structure may be chosen from the group consisting of the following commercial goniochromatic pigments: Infinite Colors from the company Shiseido, Sicopearl Fantastico from BASF, Colorstream, Xirallic, Xirona from Merck, Colorglitter from FLEX, and mixtures thereof.

Liquid crystal pigments are in particular described in application EP-A- 1046692. As liquid crystal particles, it is possible to use in particular those known under the CTFA name polyacrylate-4 and sold under the names "HELICONE® HC Sapphire", "HELICONE® HC Scarabeus", "HELICONE® HC Jade", "HELICONE® HC Maple", "HELICONE® HC XL Sapphire", "HELICONE® HC XL Scarabeus", "HELICONE® HC XL Jade", and "HELICONE® HC XL Maple" by the company WACKER.

The pigments may be present in the composition according to the invention in an amount ranging from 0.01 to 10% by weight, relative to the total weight of the composition, preferably from 0.05 to 7% by weight, more preferably from 0.1 to 5% by weight, and more preferably still from 0.4 to 3% by weight.

(Lamellar Particles)

The composition according to the invention may comprise at least one lamellar particle other than the pigments described above.

The expression "lamellar particle" for the purposes of the present invention is understood to mean particles existing in the form of optionally stratified sheets.

These sheets are characterized by a thickness which is smaller than the largest dimension. Preferably, the ratio between the largest dimension and the thickness is between 2 and 100.

The lamellar particles present in the composition according to the invention may be chosen from lamellar pearlescent agents, lamellar fillers, and/or lamellar reflecting particles. The expression pearlescent agents should be understood to mean iridescent particles, in particular produced by certain molluscs in their shell or alternatively synthesized.

The lamellar pearlescent agents may be chosen from white pearlescent agents such as mica coated with titanium or with bismuth oxychloride, coloured pearlescent agents such as mica-titanium coated with iron oxides, mica-titanium coated with in particular ferric blue or chromium oxide, mica-titanium coated with an organic pigment of the abovementioned type, and pearlescent agents made of bismuth oxychloride or based on bismuth oxychloride.

According to a preferred embodiment, the lamellar pearlescent agent is a pearlescent agent made of bismuth oxychloride, in particular sold under the name BIRON LF 2000 by the company MERCK.

The lamellar pearlescent agents may be present in the composition according to the invention in an amount ranging from 0.01 to 8% by weight, preferably from 0.1 to 5% by weight, relative to the total weight of the composition.

The lamellar fillers may be chosen from:

- talc which is a magnesium silicate hydrate, and in particular those marketed under the names "Talc Luzenac 00" by the company LUZENAC and "Talc P3" by the company NIPPON TALC; - kaolin which is an aluminium silicate hydrate which exists in the form of particles with an anistropic shape having sizes generally less than 30 μπι; as kaolin, it is possible to use the one sold under the name "Kaolin Supreme 1" from ENGLISH CHINA LAYS;

- boron nitride, and in particular those marketed under the names "Ceram Blanche 1 " and "Ceram Blanche" sold by the company SPCI, and "PUHP 3008" sold by the company Saint Gobain Ceramics;

- mica, or aluminosilicate, which may be chosen from muscovite, phlogopite, tiotite, sericite, lepidolite, paragonite, margarite, roscoelite, artificial or synthetic mica having a fluorine atom replacing the hydroxyl group of the natural mica, and the baked or calcined products of these micas. Micas generally exist in the form of scales having dimensions of 2 to 200 μιη, preferably 5-70 μηι and a thickness of 0.1 to 5 μηι, preferably of 0.2-3 μπι. As mica, it is possible, for example, to use those sold under the names "MICA SFG70" by the company ASPANGER, and "MICA CONCORD 1000" by the company SCIAMA;

- lamellar silica, such as in particular that sold under the names "SG Flake 3 M" by the company MAPRECOS, and "Chemicelen" by the company SUMITOMO;

- and mixtures thereof.

According to a preferred embodiment, the lamellar fillers are chosen from talc, mica, boron nitride, kaolin, and mixtures thereof.

According to a particular embodiment, the talc may be present in the composition according to the invention in an amount ranging from 0.01 to 8% by weight, preferably from 0.1 to 5% by weight, relative to the total weight of the composition. According to a particular embodiment, the boron nitride may be present in the composition according to the invention in an amount ranging from 0.1 to 8% by weight, preferably from 0.3 to 7% by weight, and more preferably 0.5 to 5% by weight, relative to the total weight of the composition. The lamellar particles may be chosen from lamellar reflecting particles.

The expression "reflecting particles" denotes particles whose size, structure, in particular the thickness of the layer(s) constituting it and their physical and chemical nature, and the surface state, allow them to reflect the incident light. This reflection may, where appropriate, have a sufficient intensity to create at the surface of the composition or of the mixture, when it is applied to the support to be made up, super bright spots which are visible to the naked eye, that is to say more luminous spots which contrast with their environment by appearing to shine. The lamellar reflecting particles may or may not have a multilayer structure and, in the case of a multilayer structure, for example, at least one layer with a uniform thickness, in particular a reflecting material.

When the reflecting particles have a multilayer structure, they may for example comprise a natural or synthetic substrate, in particular a synthetic substrate that is at least partially coated with at least one layer of a reflecting material, in particular with at least one metal or metallic material. This substrate may be monomaterial, multimaterial, organic, and/or inorganic.

More particularly, it may be chosen from glass, ceramics, graphite, metal oxides, alumina, silicas, silicates, in particular aluminosilicates and borosilicates, synthetic mica, and mixtures thereof, this list not being limiting.

The reflecting material may comprise a layer of metal or of a metallic material. Reflecting particles are described in particular in the documents JP-A-09188830,

JP-A-10158450, JP-A-10158541, JP-A-07258460, and JP-A-05017710.

Still by way of example of reflecting particles comprising an inorganic substrate coated with a metal layer, there may also be mentioned particles comprising a borosilicate substrate coated with silver.

Particles containing a glass substrate coated with silver, in the form of platelets, are sold under the name MICROGLASS METASHINE REFSX 2025 PS by the company TOYAL.

Particles containing a glass substrate coated with a nickel/chromium/molybdenum alloy are sold under the name CRYSTAL STAR GF 550, GF 2525 by the same company.

The lamellar reflecting particles may also be chosen from particles containing a synthetic substrate that is at least partially coated with at least one layer of at least one metallic material, in particular a metal oxide, chosen, for example, from titanium oxides, in particular Ti0 ₂ , iron oxides, in particular Fe ₂ 0 ₃ , tin oxides, chromium oxides, barium sulphate, and the following materials: MgF ₂ , CrF ₃ , ZnS, ZnSe, Si0 ₂ , A1 ₂ 0 ₃ , MgO, Y ₂ 0 ₃ , Se0 ₃ , SiO, Hf0 ₂ , Zr0 ₂ , Ce0 ₂ , Nb ₂ 0 ₅ , Ta ₂ 0 ₅ , MoS ₂ , and mixtures or alloys thereof.

By way of example of such particles, there may be mentioned, for example, particles comprising a synthetic mica substrate coated with titanium dioxide, or particles of glass coated either with brown iron oxide, titanium oxide, tin oxide, or mixtures thereof such as those sold under the trademark REFLECKS® by the company ENGELHARD.

The reflecting particle(s) may be present in the composition according to the invention in an amount ranging from 0.01 to 5%, in particular from 0.05% to 3% by weight, and more preferably from 0.1 to 2% by weight, relative to the total weight of the composition.

According to a particular embodiment, the composition according to the invention may comprise at least two lamellar particles of a different nature.

According to a more preferred embodiment, the composition according to the invention may comprise at least two lamellar particles of a different nature, one of the lamellar particles being chosen from lamellar pearlescent agents, the other lamellar particle being chosen from lamellar fillers.

According to a further preferred embodiment, the composition according to the invention may comprise at least one lamellar pearlescent agent and at least two lamellar fillers.

The lamellar particle(s) may be present in the composition according to the invention in an amount ranging from 0.1 to 10% by weight, preferably from 0.3 to 8% by weight, and more preferably from 0.5 to 5% by weight, relative to the total weight of the composition.

According to a preferred embodiment, the lamellar particles and the pigments are present in the composition in an amount such that the weight ratio of the lamellar particles to the pigments ranges from 10 to 1000, preferably from 100 to 600, more preferably from 300 to 600.

It is preferable that the highly refractive particle be selected from the group consisting of boron nitride, titanium dioxide, zinc oxide, and mixtures thereof.

The composition according to the present invention may comprise the particle having a refractive index of 1.5 or more in an amount of from 0.1 to 10% by weight, preferably from 0.3 to 8% by weight, and more preferably from 0.5 to 5% by weight in relation to the total weight of the composition.

{SPF Booster}

The composition according to the present invention comprises at least one SPF booster. If two or more SPF boosters are used, they may be the same or different, preferably the same.

The term "SPF booster" means a compound or composition that, when used in a formulation in conjunction with a UV screening agent, increases the SPF value of the formulation without increasing the amount of the UV screening agent in the formulation. It is preferable that the SPF booster be in the form of a particle, more preferably a spherical particle. It is furthermore preferable that the SPF booster be selected from hollow particles, in particular hollow latex particles.

The hollow latex particles according to the invention have a particle size which ranges generally from 100 to 380 nm, preferably from 150 to 375 nm, more preferably from 190 to 350 nm, and more particularly from 251 to 325 nm, the particle size being a volume-average particle size measured by a Brookhaven BI-90 photon correlation spectrometer.

For a given particle size, the hollow latex particles according to the invention must in general possess a maximum hollow fraction. The hollow latex particles preferably contain a void fraction of 0.1 % to 50% and more preferably of 5% to 50%. The void fractions are determined by comparing the volume occupied by the latex particles after having been compacted from a diluted dispersion in a centrifuge, relative to the volume of non-void particles in the same composition.

Hollow latex particles according to the invention may be obtained from particles comprising at least one polymer for the core and at least one polymer for the shell. The core polymer and the shell polymer may be obtained from a single polymerization step or from a sequence of polymerization steps.

Typically, the hollow latex particles are provided as part of an aqueous dispersion that is generally stabilized with at least one emulsifier.

The hollow latex particles according to the invention may be prepared by the conventional techniques of emulsion polymerization. Such processes are described especially in patents US 4,427,836, US 4,469,825, US 4,594,363, US 4,677,003, US 4,920,160, and US 4,970,241 or by the conventional techniques of polymerization that are described in the following patents and patent applications: EP267726, EP331421, US 490,229, and US 5,157,084. The monomers used for the shell of the latex particles are preferably constituted of one or more unsaturated nonionic ethylenic units. Optionally one or more monoethylenically unsaturated monomers containing at least one carboxylic acid group may be polymerized in the shell. The monomers constituting the shell are selected such that they exhibit a glass transition temperature (Tg) which is sufficiently high to withstand the void of the hollow latex particle. Preferably the glass transition temperature is greater than 50°C, more preferably greater than 60°C, and more preferably still greater than 70°C. This temperature Tg may be determined by DSC (differential scanning calorimetry).

The monomers used in the emulsion polymerization in the core polymer of the latex particles of the invention are preferably constituted of one or more monoethylenically unsaturated monomers containing at least one carboxylic acid group. Preferably the core comprises at least 5% by weight of monoethylenically unsaturated monomer containing at least one carboxylic acid group, relative to the total weight of the core monomers.

The core polymer may for example be obtained by emulsion homopolymerization of the monoethylenically unsaturated monomer containing at least one acid group or by

copolymerization of two or three monoethylenically unsaturated monomers containing at least one acid group. Preferably the monoethylenically unsaturated monomer containing at least one acid group is copolymerized with one or more ethylenically unsaturated nonionic monomers.

The core polymer or the shell polymer may contain from 0.1% to 20% by weight, preferably from 0.1% to 3% by weight, of polyethylenically unsaturated monomers such as ethylene glycol di(meth)acrylate, allyl (meth)acrylate, 1 ,3-butanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, or divinylbenzene, relative to the total weight of the core monomers. Alternatively the core polymer or the shell polymer may optionally contain from 0.1% to 60% by weight of butadiene, relative to the total weight of the core monomers.

The monoethylenically unsaturated monomers containing at least one carboxylic acid group include, for example: acrylic acid, methacrylic acid, acryloyloxypropionic acid,

(meth)acryloyloxypropionic acid, itaconic acid, aconitic acid, maleic acid or maleic anhydride, fumaric acid, crotonic acid, monomethyl maleate, monomethyl fumarate, and monomethyl itaconate.

In an embodiment, the monomer is selected from acrylic acid and methacrylic acid. The monoethylenically unsaturated nonionic monomers include, for example: styrene, vinyl toluene, vinyl acetate, vinyl chloride, vinylidene chloride, acrylonitrile, (meth)acrylamide, C!-C2o alkyl esters of (meth)acrylic acid, and (C ₃ -C ₂₀ ) alkenyl esters of (meth)acrylic acid, such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, benzyl (meth)acrylate, lauryl (mefh)acrylate, oleyl (meth)acrylate, palmityl (meth)acrylate, and stearyl (meth)acrylate. According to the invention, the term

(meth)acrylic will denote the general expression encompassing both methacrylic or acrylic. The term (meth)acrylate will denote the general expression encompassing both methacrylate or acrylate. .

The void part of the core of the latex particles is preferably produced by swelling the core with a swelling agent comprising one or more volatile compounds. The agent penetrates the shell in order to swell the core. The volatile components of the swelling agent may be subsequently removed by drying the latex particles, thus creating a void within the particles. The agent is preferably an aqueous base. Mention may be made, for example, of ammonia, ammonium hydroxide, alkali metal hydroxides such as sodium hydroxide, and volatile amines such as trimethylamine or triethylamine.

The hollow latex particles may be introduced into the composition of the invention with the swelling agent. In that case the volatile compounds are removed when the composition is dried. The hollow latex particles may also be added to the composition after the volatile compounds of the swelling agent have been removed.

The hollow latex particles which can be used according to the invention are those described in patent US 5,663,213 and patent application EP1092421.

According to one particular embodiment of the invention, the hollow latex particles used will be those constituted of a copolymer of styrene and (meth)acrylic acid or one of its

alkyl esters under the INCI name Styrene/Acrylates Copolymer, such as the product sold under the trade name Sunspheres™ Powder by the company Rohm & Haas, which is an aqueous dispersion containing 86% of Styrene/Acrylates Copolymer in a mixture of 11 % of PEG-8 Laurate, 2.5% of water, and 0.5% of Sodium Dodecylbenzenesulfonate.

Another example of the SPF booster, which is typically capable of reflecting UV light, is glass microspheres. Typically, the glass microspheres used in the compositions of the invention are essentially homogeneous and essentially uniform in sphericity and have a mean particle size of between about 5 μηι and 70 μιη, such as from about 10 μηι to 20 μηι. Glass microspheres useful in the present invention include hollow microspheres of calcium aluminum borosilicate (commercially available from Presperse Inc. under the trade name LUXSIL®), sodium borosilicate particulates (commercially available from PQ Corporation under the trade name Q-CEL 570), and calcium/sodium borosilicate hollow microspheres (commercially available from 3M under the trade names ES 22 and IK), calcium/sodium borosilicate microspheres (commercially available from 3M's under the trade name

Scotchlite™ K ₂₀ product). Another example of the SPF booster is porous silica in the form of microparticles, in particular, spherical microparticles. The spherical microparticles of porous silica in accordance with the invention preferably have a mean particle size ranging from 0.5 to 20 μπι and more particularly from 3 to 15 μπι. They preferably have a specific surface ranging from 50 to 1 000 m ² /g and more particularly from 150 to 800 m ² /g.

They preferably have a specific pore volume ranging from 0.5 to 5 ml/g and more particularly from 1 to 2 ml/g.

By way of example of microbeads of porous silica, it is possible to use the following commercial products:

Silica Beads SB 150 from Myoshi,

Sunsphere H-51 from Asahi Glass,

Sunsil 130 from Sunjin, Spherica P-1500 from Ikeda Corporation, and

Sylosphere from Fuji Silysia.

It is preferable that the SPF booster be made from at least one material selected from the group consisting of (co)polymers of (meth)acrylic acid, (meth)acrylates, and/or styrene; glass; silica; and mixtures thereof. As the (co)polymers of (meth)acrylic acid, (meth)acrylates, and/or styrene, mention may be made of poly(meth)acrylates such as PMMA, a copolymer of (meth)acrylic acid and (meth)acrylates, and a copolymer of (meth)acrylic acid,

(meth)acrylates, and styrene.

The composition according to the present invention may comprise the SPF booster in an amount of from 0.1 to 10% by weight, preferably from 0.3 to 8% by weight, and more preferably from 0.5 to 5% by weight in relation to the total weight of the composition. It has been discovered that, when the (c) SPF booster(s) such as hollow particles are employed in combination with the (a) UV filter(s) in the compositions of the present invention, it is possible to achieve broad spectrum UVB/UVA protection and a very desirable SPF, e.g., in the range of from about 15 to about 70, while employing a minimal amount of the (a) UV filter®.

In the composition of the present invention, the (c) SPF booster may be employed in an amount equal to, or smaller than, the amount of the (a) UV filter present in the composition.

Typically, the ratio of the (c) SPF booster to the (a) UV filter is in the range of from about 0.5 :about 1 to about 1 :about 20, such as from about 0.1 :about 1 to about 1 :about 15.

(Aqueous Phase)

The composition according to the present invention may include at least one aqueous phase.

The aqueous phase includes water. The amount of water may be equal to or more than 10% by weight, preferably 20% by weight or more, more preferably 30% by weight or more, and even more preferably 40% by weight or more, in relation to the total weight of the

composition. For example, the amount of water may be 10% to 90% by weight, preferably 20% to 80% by weight, more preferably 30% to 70% by weight, and even more preferably 40%) to 60%) by weight, in relation to the total weight of the composition.

The aqueous phase may include at least one polyol that is miscible with water at room temperature (25 °C) chosen especially from polyols especially containing from 2 to 20 carbon atoms, preferably containing from 2 to 10 carbon atoms, and preferentially containing from 2 to 6 carbon atoms, such as glycerol, ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, dipropylene glycol, or diethylene glycol; glycol ethers (especially containing from 3 to 16 carbon atoms) such as mono-, di-, or tripropylene glycol (C ₁ -C ₄ )alkyl ethers, mono-, di-, or triethylene glycol (CrC ₄ )alkyl ethers; and mixtures thereof. Such a polyol or polyols may promote the moisturization of the surface of the skin on which the composition is applied.

The aqueous phase may include at least one monoalcohol that is miscible with water at room temperature (25°C) chosen especially from monoalcohols containing from 2 to 10 carbon atoms, preferably containing from 2 to 6 carbon atoms, such as ethanol and isopropanol. The pH of the aqueous phase is not limited, but is generally between about 3 and 12, preferably between about 5 and 1 1, and even more particularly from 6 to 8.5.

The pH of the aqueous phase may be controlled by the presence or absence of at least one acidifying agent and/or at least one basifying agent.

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

Among the basifying agents, examples that may be mentioned include aqueous ammonia, alkali metal carbonates, alkanolamines such as mono-, di-, and triethanolamines and derivatives thereof, sodium hydroxide, potassium hydroxide, and the compounds of the formula below: in which W is a propylene residue optionally substituted with a hydroxyl group or a C C ₄ alkyl radical; and R _a , R _b , Rc, and Rd, which may be identical or different, represent a hydrogen atom, or a Ci-C ₄ alkyl or Ci-C ₄ hydroxyalkyl radical.

The amount of the aqueous phase may be equal to or more than 20% by weight, preferably 30% by weight or more, more preferably 40% by weight or more, and even more preferably 50% by weight or more, in relation to the total weight of the composition. For example, the amount of the aqueous phase may be 20% to 80% by weight, preferably 30% to 70% by weight, more preferably 40% to 60% by weight, and even more preferably 45% to 55% by weight, in relation to the total weight of the composition.

(Optional Ingredients)

The compositions in accordance with the present invention may also comprise one or more standard cosmetic adjuvants chosen from oils, waxes, organic solvents, fillers, ionic or nonionic, hydrophilic or lipophilic thickeners, softeners, humectants, opacifiers, stabilizers, emollients, silicones, antifoams, fragrances, preserving agents, surfactants, active agents, colouring agents, cationic polymers, propellants, or any other ingredient usually used in cosmetics and/or dermatology.

Needless to say, a person skilled in the art will take care to select the optional adjuvant(s) added to the composition according to the invention such that the advantageous properties intrinsically associated with the composition in accordance with the invention are not, or are not substantially, adversely affected by the envisaged addition.

Hydrophilic thickeners that may be mentioned include carboxyvinyl polymers such as the Carbopol products (carbomers) and the Pemulen products (acrylate/C10-C30-alkyl acrylate copolymer); polyacrylamides, for instance the crosslinked copolymers sold under the names Sepigel 305 (CTFA name: polyacrylamide/C13-C14 isoparaffin/Laureth 7) or Simulgel 600 (CTFA name: acrylamide/sodium acryloyldimethyl taurate

copolymer/isohexadecane/polysorbate 80) by the company SEPPIC; 2-acrylamido-2-methylpropanesulfonic acid polymers and copolymers, optionally crosslinked and/or neutralized, for instance poly(2-acrylamido-2-methylpropanesulfonic acid) sold by the company Clariant under the trade name Hostacerin AMPS (CTFA name: ammonium polyacryloyldimethyl taurate) or Simulgel 800 sold by the company SEPPIC (CTFA name: sodium polyacryloyldimethyl taurate/polysorbate 80/sorbitan oleate); copolymers of

2-acrylamido-2-methylpropanesulfonic acid and of hydroxyethyl acrylate, for instance Simulgel NS and Sepinov EMT 10 sold by the company SEPPIC; cellulose derivatives such as hydroxyethyl cellulose; polysaccharides and especially gums such as xanthan gum; and mixtures thereof.

Lipophilic thickeners that may be mentioned include synthetic polymers such as

poly(C10-C30 alkyl acrylates) sold under the name Intelimer IPA 13-1 and Intelimer IPA 13-6 by the company Landec, or modified clays such as hectorite and its derivatives, for instance the products sold under the name Bentone.

The compositions according to the invention may also furthermore comprise additional cosmetic and dermatological active agents.

Mention may be made, among active agents, of:

- vitamins (A, C, E, K, PP, and the like) and their derivatives or precursors, alone or as mixtures;

- antioxidants;

- free-radical scavengers;

- antiglycation agents;

- soothing agents;

- NO-synthase inhibitors;

- agents which stimulate the synthesis of dermal or epidermal macromolecules and/or which prevent their decomposition;

- agents which stimulate the proliferation of fibroblasts;

- agents which stimulate the proliferation of keratinocytes;

- muscle relaxants;

- tensioning agents;

- mattifying agents;

- keratolytic agents;

- desquamating agents;

- moisturizers, for instance polyols such as glycerol, butylene glycol, or propylene glycol;

- anti-inflammatory agents;

- agents which act on the energy metabolism of cells;

- insect repellents;

- substance P antagonists or CGRP antagonists;

- agents for combating hair loss and/or for restoring the hair;

- anti- wrinkle agents; and

- additional inorganic and organic UV-screening agents such as those previously mentioned. Needless to say, those skilled in the art will take care to select the optional additional compound(s) mentioned above and/or the amounts thereof such that the advantageous properties intrinsically associated with the compositions in accordance with the invention are not, or are not substantially, adversely affected by the envisaged addition(s). Those skilled in the art will choose said active agent(s) according to the desired effect on the skin, hair, eyelashes, eyebrows, or nails.

(Galenical Forms) The compositions according to the invention can be prepared according to the techniques well known to those skilled in the art for preparing O/W or W/O emulsions. They may be in the form of a milk, of a cream, or of a cream gel. They may optionally be packaged as an aerosol and may be in the form of a spray. The emulsification processes that may be used are of paddle or impeller, rotor-stator ,and high-pressure homogenizer (HPH) type.

To obtain stable emulsions with a low content of emulsifying compounds (oil/emulsifier ratio > 25), it is possible to make the dispersion in the concentrated phase and then to dilute the dispersion with the rest of the aqueous phase.

It is also possible, via HPH (between 50 and 800 bar), to obtain stable dispersions with drop sizes which can fall to 100 nm. The emulsions generally comprise at least one emulsifier chosen from amphoteric, anionic, cationic, or non-ionic emulsifiers, used alone or as a mixture. The emulsifiers are appropriately chosen according to the type of the emulsion to be obtained. The emulsions may also contain stabilizers of other types, for instance fillers, or gelling or thickening polymers.

For the O/W and W/O emulsions, examples of emulsifiers that may be mentioned include non-ionic emulsifiers such as oxyalkylenated (more particularly polyoxyethylenated) esters of fatty acids and of glycerol; oxyalkylenated esters of fatty acids and of sorbitan;

oxyalkylenated (oxyethylenated and/or oxypropylenated) esters of fatty acids, such as the PEG- 100 stearate/glyceryl stearate mixture sold, for example, by ICI under the name Arlacel 165; oxyalkylenated (oxyethylenated and/or oxypropylenated) ethers of fatty alcohols; esters of sugars, such as sucrose stearate; or ethers of fatty alcohol and of sugar, in particular alkyl polyglucosides (APGs), such as decyl glucoside and lauryl glucoside, sold, for example, by the company Henkel under the respective names Plantaren 2000 and Plantaren 1200, cetostearyl glucoside, optionally as a mixture with cetostearyl alcohol, sold, for example, under the name Montanov 68 by the company SEPPIC, under the name Tegocare CG90 by the company Goldschmidt, and under the name Emulgade KE3302 by the company Henkel, and also arachidyl glucoside, for example, in the form of the mixture of arachidyl alcohol, behenyl alcohol, and arachidyl glucoside, sold under the name Montanov 202 by the company SEPPIC. According to one particular embodiment of the invention, the mixture of the alkylpolyglucoside as defined above with the corresponding fatty alcohol can be in the form of a self-emulsifying composition, for example, as described in document WO-A-92/06778.

Among the other emulsion stabilizers, use may also be made of isophthalic acid or

sulfoisophthalic acid polymers, and in particular phthalate/sulfoisophthalate/glycol copolymers, for example, the diethylene glycol/phthalate/isophthalate/1,4- cyclohexanedimethanol copolymer (INCI name: Polyester-5) sold under the names Eastman AQ Polymer (AQ35S, AQ38S, AQ55S, and AQ48 Ultra) by the company Eastman Chemical. Among the other emulsion stabilizers, mention may also be made of hydrophobically modified 2-acrylamido-2-methylpropanesulfonic acid polymers such as those described in patent application EP 1 069 142.

The aqueous phase of the latter can comprise a non-ionic vesicular dispersion prepared according to known processes (Bangham, Standish and Watkins, J. Mol. Biol., 13, 238 (1965), FR 2 315 991, and FR 2 416 008).

[Cosmetic Method or Process] The compositions according to the invention have applications in a great number of treatments, in particular cosmetic treatments, of the skin, lips, and hair, including the scalp.

Another subject of the present invention is constituted of the use of the compositions according to the invention as defined above in the manufacture of products for the cosmetic treatment of the skin, lips, nails, hair, eyelashes, eyebrows, and/or scalp, in particular care products, anti-sun products, and make-up products.

The compositions according to the invention can be used, for example, as make-up products. The compositions according to the invention may be used, for example, as care products and/or anti-sun protection products and/or make-up products, for the face and/or the body, of liquid to semi-liquid consistency, such as milks, more or less rich creams, cream-gels and pastes. They may optionally be packaged in aerosol form and may be in the form of a mousse or a spray.

The compositions according to the invention in the form of vaporizable fluid lotions in accordance with the invention are applied to the skin or the hair in the form of fine particles by means of pressurization devices. The devices in accordance with the invention are well known to those skilled in the art and comprise non-aerosol pumps or "atomizers", aerosol containers comprising a propellant, and aerosol pumps using compressed air as propellant. These devices are described in patents US 4 077 441 and US 4 850 517.

The compositions packaged as an aerosol in accordance with the invention generally comprise conventional propellants, such as, for example, hydrofluorinated compounds,

dichlorodifluoromethane, difluoroethane, dimethyl ether, isobutane, n-butane, propane, or trichlorofluoromethane. They are preferably present in amounts ranging from 15% to 50% by weight relative to the total weight of the composition.

The present invention also relates to a cosmetic method, in particular, a non-therapeutic cosmetic method for caring for and/or making up the skin, as well as a cosmetic skincare process for providing immediate optical effect on the surface of the skin. Each possible non-therapeutic cosmetic method includes applying the composition according to the present invention onto the skin. The cosmetic method or cosmetic skincare process according to the present invention can provide cosmetic effects to the skin, such as the skin of the face, by the UV-filtering effects provided by the (a) UV filter(s) in the composition used in the present invention.

According to the present invention, the UV-shielding effects of the (a) UV filter(s) in the composition used in the present invention are enhanced by the (c) SPF booster. Therefore, a high UV-shielding effect can be provided. In addition, due to the combination of the (b) particle having a refractive index of 1.5 or more and the (c) SPF booster, the composition according to the present invention can provide immediate optical effects as well as good sensorial texture. The UV-filtering effects as well as the immediate optical effects and good sensorial texture can be the basis of caring for and/or making up the skin.

The cosmetic effects provided by the composition according to the present invention can include limiting the darkening of the skin, improving the color and uniformity of the complexion, and/or treating aging of the skin.

Thus, the present invention also relates to a non-therapeutic cosmetic method for treating aging of the skin, comprising applying the composition according to the present invention.

It is preferable to form a substantially even film on the skin of the composition according to the present invention. The formation of a substantially even or homogeneous film on the skin can provide even or uniform UV-filtering effects and/or immediate optical effects.

EXAMPLES The present invention will be described in a more detailed manner by way of examples. However, these examples should not be construed as limiting the scope of the present invention.

Example 1 and Comparative Examples 1 and 2

[Preparations]

The following cosmetic compositions according to Example 1 and Comparative Examples 1 and 2, shown in Table 1 , were prepared by mixing the components shown in Table 1. The numerical values for the amounts of the components shown in the tables are all based on "% by weight" as active raw materials.

The ingredients (a) to (c) in Table 1 correspond to the following. (a): UV filter

(b) : Particle having a refractive index of 1.5 or more

(c) : SPF booster

[Evaluations]

(Immediate Optical Effects)

0.2 g of each composition according to Example 1 and Comparative Examples 1 and 2 was applied onto half of the face of each of 6 panelists, and just after the application, the immediate optical effects (brightened skin color tone, evener skin color, less distinct spots, and/or less distinct pores) of the composition were visually evaluated in accordance with the following score system.

4: unmistakable optical effects were observed

3: optical effects were observed 2: slight optical effects were observed

1 : very slight optical effects were observed

0: same as bare skin

-1 : little worse than bare skin

-2: worse than bare skin

The average scores for Example 1 and Comparative Examples 1 and 2 are shown in Table 1.

(Sensorial Texture)

0.2 g of each composition according to Example 1 and Comparative Examples 1 and 2 was applied onto half of the face of each of 4 panelists, and the sensorial texture (spreadability, formation of noodles (no formation of noodles is preferable), moisturizing feeling, shiny skin (it is preferable that there be no shiny skin), and/or filmy feeling (it is preferable that there be no filmy feeling) was evaluated in accordance with the following score system.

0: Very Poor

l : Poor

2: Fair

3: Good

4: Very Good

The average scores for Example 1 and Comparative Examples 1 and 2 are shown in Table 1. (UV Transmittance)

Each composition according to Example 1 and Comparative Examples 1 and 2 was applied onto a PMMA plate in an amount of 0.9 mg/cm ² , and the UV transmittance of each composition was determined with a UV transmittance analyzer (Labsphere UV-2000) at a wavelength range of 310 nm.

The measured UV transmittance values for Example 1 and Comparative Examples 1 and 2 are shown in Table 1. The lower is the UV transmittance, the better is the UV-shielding effect.

Table 1

Example 1 shows that a combination of the (a) UV filters, the (b) particle having a refractive index of 1.5 or more, and the (c) SPF booster can provide all of the immediate optical effects, good sensorial texture, and lower UV-transmittance.

Comparative Example 1 lacks the (b) particle having a refractive index of 1.5 or more, and therefore, the immediate optical effects and sensorial texture are deteriorated.

Comparative Example 2 lacks the (c) SPF booster, and therefore, it cannot provide immediate optical effects and leads to a higher UV-transmittance.

Accordingly, only Example 1 according to the invention could provide all of the immediate optical effects, good sensorial texture, and better UV-shielding effects, amongst Example 1 and Comparative Examples 1 and 2.