WO2017206047A1

WO2017206047A1 - Translucent sunscreen composition with improved uv screening ability

Info

Publication number: WO2017206047A1
Application number: PCT/CN2016/084020
Authority: WO
Inventors: Runshuang LU; Zheng Chen; Yasuko NAGAMATSU
Original assignee: L'oreal
Priority date: 2016-05-31
Filing date: 2016-05-31
Publication date: 2017-12-07

Abstract

A composition in form of an oil-in-water emulsion comprising: a) a dispersed hydrophobic phase comprising at least one hydrophobic UV-screening agent; b) a continuous aqueous phase comprising at least one hydrophilic UV-screening agent; c) at least one hydrophobic particle selected from the group consisting of hydrophobic silicas, hydrophobic cellulose, starch, talc, silicone resin powders, hollow hemispherical silicone particles, polyamide powders, hydrophobic pigments, and any mixture thereof; and d) at least one amphiphilic agent selected from the group consisting of silicone comprising at least one oxyalkylenated chain, amphiphilic crosslinked copolymer, or a mixture thereof.

Description

TRANSLUCENT SUNSCREEN COMPOSITION WITH IMPROVED UV SCREENING ABILITY

TECHNICAL FIELD

The present invention relates to the field of cosmetics, and especially to the field of compositions for protecting the skin from UV radiation.

BACKGROUND ART

Whitening and brightening of the skin is always high interest of the consumers, especially those who have a dark or dull skin tone. Cosmetic compositions are used to meet the expectations of the consumers, from many different aspects, one of which is anti UV radiation. Many formulations have been developed to date to achieve this goal.

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

Besides, translucent or transparent UV products containing hydrophobic and/or hydrophilic UV-screening agents (or in other words UV filters) are known. These products are more and more favored by the consumers thanks to its ease of use and cosmetic pleasantness. Unlike the conventional UV products in forms of cream or milk, these UV products do not encompass greasy feelings after application on the skin, and do not have a white color, which is not attractive to the users.

However, these products are still not satisfying. Products with translucent or transparent appearance do not provide high UV-screening ability. The inventors found it difficult to improve the UV-screening ability, in particular UV-B screening ability, of a product, while maintaining the pleasant appearance.

Therefore it is necessary to formulate compositions with pleasant translucent or transparent appearance, while providing to the skin an improved UV-screening ability, in particular UV-B screening ability.

AIMS OF THE INVENTION

The present invention aims to provide a composition, in particular a sunscreen composition, having UV-screening agent (s) with an improved UV-screening ability, in particular, UV-B screening ability.

The present invention also aims to provide a transparent or translucent composition, in particular a sunscreen composition, presenting an improved UV-screening ability.

More particularly, the invention aims to provide a translucent or transparent sunscreen composition, having a fresh and hydration feeling on the skin, and presenting an improved UV-screening ability.

DISCLOSURE OF INVENTION

It is discovered, in accordance to the present invention, that the above recited technical problems may be solved by providing a composition in form of an oil-in-water emulsion comprising:

a) a dispersed hydrophobic phase comprising at least one hydrophobic UV-screening agent；

b) a continuous aqueous phase comprising at least one hydrophilic UV-screening agent；

c) at least one hydrophobic particle selected from the group consisting of hydrophobic silicas, hydrophobic cellulose, starch, talc, silicone resin powders, hollow hemispherical silicone particles, polyamide powders, hydrophobic pigments, and any mixture thereof； and

d) at least one amphiphilic agent selected from the group consisting of silicone comprising at least one oxyalkylenated chain, amphiphilic crosslinked copolymer, or a mixture thereof.

Such a composition is also known as a pickering emulsion. More particularly, the traditional sunblock emulsions comprising both hydrophobic and hydrophilic UV-screening agents result in a translucent or transparent product with relatively low UV-screening ability. It has been discovered that the emulsion according to the present invention, translucent or even transparent, and meanwhile presents an improved UV-screening ability (also known as anti UV radiation effect) .

By “UV-screening ability” , it is in particular meant that the SPF (Sun Protection Factor) and/or PPD (Persistent Pigment Darkening) value of a composition is sufficient to market such a composition as sunscreen composition.

The other subject of the present invention is a process for making up/caring for the keratin materials, for example the skin, in particular the face and the lips, by applying to the keratin materials the composition of the present invention.

The term “pickering emulsion” refers to an emulsion that is stabilized by solid particles (for example colloidal silica) which adsorb onto the interface between the two phases.

The term “keratin material” means the skin (of the body, face and around the eyes) , nails, lips or mucous membranes. In particular, it means the skin.

SPF is preferably measured according to International standard EN ISO 24444: 2010 Cosmetics ‐Sun protection test methods ‐In vivo determination of the sun protection factor (SPF) .

PPD is skin darkening that persists more than 2 h after the end of UVA exposure. It is determined according to ISO 24442: 2011 (en) Cosmetics -Sun protection test methods -In vivo determination of sunscreen UVA protection.

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

DETAILED DESCRIPTION OF THE INVENTION

The composition according to the present invention relates to a composition in form of an oil-in-water emulsion comprising:

Hydrophobic phase

According to the present invention, the composition comprises a dispersed hydrophobic phase.

In particular, the hydrophobic phase of the present invention is in form of droplets.

The hydrophobic phase may contain at least one oil.

The oil is selected from silicone oils, hydrocarbon-based oils, or a mixture thereof.

The term “silicone oil” is intended to mean an oil comprising at least one silicone atom, and in particular comprising Si-O group.

The term “hydrocarbon-based oil” (or “hydrocarbonated oil” , or “hydrocarbon oil” ) means an oil formed essentially from, or even constituted by, carbon and hydrogen atoms, and optionally oxygen and nitrogen atoms, and not containing any silicon or fluorine atoms. It may contain alcohol, ester, ether, carboxylic acid, amine and/or amide groups.

The oil can be volatile or non-volatile.

The term “volatile” means an oil that is capable of evaporating on contact with keratin materials in less than one hour, at room temperature (25℃) and atmospheric pressure (760 mmHg) . The volatile oil is a volatile cosmetic oil, which is liquid at room temperature, especially having a non zero vapour pressure, at room temperature and atmospheric pressure, in particular having a vapour pressure ranging from 0.13 Pa to 40 000 Pa (10^-3 to 300 mmHg) , preferably ranging from 1.3 Pa to 13 000 Pa (0.01 to 100 mmHg) and preferentially ranging from 1.3 Pa to 1300 Pa (0.1 to 10 mmHg) .

The term "non volatile" means an oil whose vapour pressure at room temperature and atmospheric pressure is non-zero and less than 0.02 mmHg (2.66 Pa) and better still less than 10^-3 mmHg (0.13 Pa) .

Preferably, the composition may comprise a hydrophobic phase present in the composition in a content ranging from 0.1％to 40％by weight, preferably from 1％to 30％by weight, and more preferably from 3％to 20％by weight relative to the total weight of the composition.

Aqueous phase

The composition according to the invention comprises a continuous aqueous phase.

The continuous aqueous phase comprises water.

The continuous aqueous phase may also comprise water-miscible organic solvents (at room temperature of 20-25℃) , for instance polyols especially containing from 2 to 20 carbon atoms, preferably containing from 2 to 10 carbon atoms and preferentially containing from 2 to 6 carbon atoms, such as glycerol, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, dipropylene glycol or diethylene glycol； glycol ethers (especially containing from 3 to 16 carbon atoms) such as mono-, di-or tripropylene glycol (C₁-C₄) alkyl ethers, mono-, di-or triethylene glycol (C₁-C₄) alkyl ethers, and mixtures thereof.

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

In particular, a composition of the invention may comprise an aqueous phase in an amount ranging from 55％to 94％by weight, especially from 60％to 90％and more particularly from 65％to 85％by weight relative to the total weight of the composition.

UV-screening agents

The compositions according to the invention comprise hydrophobic and hydrophilic UV-screening agents, also known as filtering agents or filters, filtering wavelengths within the UVA and/or UVB ranges, which are hydrophilic or lipophilic in routine cosmetic solvents.

Hydrophobic UV-screening agents

The composition of the present invention comprises, in the dispersed hydrophobic phase, at least one hydrophobic UV-screening agent.

The term "hydrophobic UV-screening agent" or "lipophilic screening agent" means any organic or mineral sunscreen agent which can be fully dissolved in molecular state in a liquid fatty phase or which can be dissolved in colloidal form (for example in micellar form) in a liquid fatty phase.

I/Hydrophobic UV-Ascreening agents

Dibenzoylmethane derivatives:

Isopropyl Dibenzoylmethane；

Aminobenzophenones:

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

1, 1'- (1, 4-piperazinediyl) bis [1- [2- [4- (diethylamino) -2-hydroxybenzoyl] phenyl] -methanone (CAS 919803-06-8) ；

Anthranilic derivatives:

Menthyl anthranilate particularly sold under the trade name "NEO HELIOPAN MA" by SYMRISE；

4, 4-diarylbutadiene derivatives:

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

Merocyanine derivatives:

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

II/Hydrophobic UV-B screening agents

Para-aminobenzoates:

Ethyl PABA；

Ethyl Dihydroxypropyl PABA；

Ethylhexyl Dimethyl PABA (ESCALOL 507 from ISP) ；

Salicylic derivatives:

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

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

Dipropyleneglycol Salicylate particularly sold under the name "DIPSAL" by SCHER；

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

Cinnamates:

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

Isopropyl Methoxy cinnamate；

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

Diisopropyl Methylcinnamate；

Cinnoxate:

Glyceryl Ethylhexanoate Dimethoxycinnamate；

β, β’ -diphenylacrylate derivatives:

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

Octoylcrylene, for example sold under the trade name “UVINUL N 539” by BASF；

Benzylidene camphor derivatives:

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

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

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

Triazine derivatives:

Ethylhexyl triazone particularly sold under the trade name "UVINUL T150" by BASF；

Diethylhexyl Butamido Triazone particularly sold under the trade name "UVASORB HEB" by SIGMA 3V；

2, 4, 6-tris (dineopentyl 4’ -amino benzalmalonate) -s-triazine；

2, 4, 6-tris (diisobutyl 4’ -amino benzalmalonate) -s-triazine；

2, 4-bis (dineopentyl 4’ -amino benzalmalonate) -6- (n-butyl 4’ -aminobenzoate) -s-triazine；

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

the symmetrical triazine filters described in the patent US 6,225,467, the application WO 2004/085412 (see compounds 6 and 9) or the document "Symmetrical Triazine Derivatives" IP. COM Journal, IP. COM INC WEST HENRIETTA, NY, US (September 20, 2004) particularly 2, 4, 6-tris- (biphenyl) -1, 3, 5-triazine (particularly 2, 4, 6-tris (biphenyl-4-yl-1, 3, 5-triazine) and 2, 4, 6-tris (terphenyl) -1, 3, 5-triazine, the latter two filters being described in the BEIERSDORF applications WO 06/035000, WO 06/034982, WO 06/034991, WO 06/035007, WO 2006/034992, WO 2006/034985) ；

Imidazoline derivatives:

Ethylhexyl Dimethoxybenzylidene Dioxoimidazoline Propionate；

Benzalmalonate derivatives:

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

Di-neopentyl 4’ -methoxybenzalmalonate.

Within the scope of the invention, and according to one particular embodiment, the following hydrophobic UV-B screening agents are used in the composition according to the invention: Cinnamates；

β, β’ -diphenylacrylate derivatives.

More particularly, the composition of the present invention comprises at least one hydrophobic UV-screening agent, selected from the group consisting of Ethylhexyl Methoxycinnamate, Octocrylene, or a mixture thereof.

III/Combined hydrophobic UVA and UVB screening agents

Benzophenone derivatives

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

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

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

Benzophenone-6 particularly sold under the trade name "Helisorb 11" by Norquay；

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

Benzophenone-10；

Benzophenone-11；

Benzophenone-12；

Phenyl benzotriazole derivatives:

Drometrizole Trisiloxane particularly sold under the name "Silatrizole" by RHODIA CHIMIE or manufactured under the name "Meroxyl XL" by CHIMEX；

Methylene bis-Benzotriazolyl Tetramethylbutylphenol, sold in solid form particularly under the trade name "MIXXIM BB/100" by FAIRMOUNT CHEMICAL or in micronized form in aqueous dispersion particularly under the trade name "TINOSORB M" by CIBA SPECIALTY CHEMICALS；

Benzoxazole derivatives:

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

The preferential hydrophobic UVA and UVB screening agents are selected from Phenyl benzotriazole derivatives, and more particularly Drometrizole Trisiloxane.

More preferably, the composition comprises, in a dispersed hydrophobic phase, at least one hydrophobic UV-screening agent selected from the group consisting of cinnamates, β, β’ -diphenylacrylate derivatives, Phenyl benzotriazole derivatives, or a mixture thereof.

According to a preferred embodiment, the composition of the present invention comprises, in a dispersed hydrophobic phase, at least one hydrophobic UV-screening agent selected from the group consisting of Ethylhexyl Methoxycinnamate, Octocrylene, Drometrizole Trisiloxane, or a mixture thereof.

Preferably, the hydrophobic UV-screening agent is present in the composition of the present invention in an amount ranging from 0.01％to 20％by weight, more preferably from 0.1％to 20％by weight, and even more preferably from 1％to 10％by weight, relative to the total weight of the composition.

Hydrophilic UV-screening agents

The composition of the present invention comprises, in the continuous aqueous phase, at least one hydrophilic UV-screening agent.

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

IV/Hydrophilic UV-Ascreening agents

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

The preferred hydrophilic UVA screening agent is Terephthalylidene Dicamphor Sulfonic Acid, which is in particular available under the trade name

SX sold by the company CHIMEX.

V/Hydrophilic UV-B screening agents

The following p-aminobenzoic acid (PABA) derivatives:

PABA,

Glyceryl PABA, and

PEG-25 PABA particularly sold under the trade name "UVINUL P25" by BASF,

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

ferulic acid,

salicylic acid,

DEA methoxycinnamate,

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

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

The preferred hydrophilic UVB screening agent is Terephthalylidene Dicamphor Sulfonic Acid, Phenylbenzimidazole Sulfonic Acid, or a mixture thereof.

VI/Combined hydrophilic UVA and UVB screening agents

Benzophenone derivatives comprising at least one sulfonic radical such as

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

Benzophenone-5, and

Benzophenone-9.

More preferably, the composition comprises, in a continuous aqueous phase, at least one hydrophilic UV-screening agent selected from the group consisting of Terephthalylidene Dicamphor Sulfonic Acid, Phenylbenzimidazole Sulfonic Acid, or a mixture thereof.

Preferably, the hydrophilic UV-screening agent is present in the composition of the present invention, in an amount ranging from 1％to 40％by weight, more preferably from 5％to 20％by weight, relative to the total weight of the composition.

Hydrophobic particles

A composition according to the present invention comprises at least one hydrophobic particle.

For the purpose of the invention, these particles adsorb onto the interface between the hydrophobic phase and aqueous phase, so as to stabilize the emulsion.

Moreover, these particles enables the oil droplets of the present invention, which are visible, to be dispersed into the aqueous phase in a long-term, for example for one month, or for example for two months.

The particles may be mineral or organic, and may be in form of spherical particles, or lamellar particles.

In the present patent application, the term "spherical particles" means particles in the form or substantially in the form of a sphere, which are insoluble in the medium of the composition according to the invention, even at the melting point of the medium (about 100℃) .

The term "lamellar particles" means herein particles of parallelepipedal shape (rectangular or square surface) , discoid shape (circular surface) or ellipsoid shape (oval surface) , characterized by three dimensions: a length, a width and a height, these particles being insoluble in the medium of the composition according to the invention, even at the melting point of the medium (about 100℃) .

More particularly, the hydrophobic particles are chosen from:

- hydrophobic silica,

The term "hydrophobic silica" is understood to mean, in the context of the present invention, both pure hydrophobic silica and particles coated with hydrophobic silica.

According to a specific embodiment, the hydrophobic silica which can be used in the composition of the invention are amorphous and of fumed origin. They are preferably provided in the pulverulent form.

The amorphous hydrophobic silica of fumed origin are obtained from hydrophilic silica. The latter are obtained by pyrolysis of silicon tetrachloride (SiCl₄) in a continuous flame at 1000℃in the presence of hydrogen and oxygen. They are subsequently rendered hydrophobic by treatment with halogenated silanes, alkoxysilanes or silazanes. The hydrophobic silica differ from the starting hydrophilic silica, inter alia, in a lower density of silanol groups and in a smaller adsorption of water vapour.

Use will in particular be made of aerogel particles of hydrophobic silica modified at the surface with trimethylsilyl groups (trimethylsiloxylated silica) .

Mention may be made, as hydrophobic silica aerogels which can be used in the invention, for example, of the aerogel sold under the name VM-2260 (INCI name: Silica silylate) by Dow Corning, the particles of which exhibit an average size of approximately 1000 microns and a specific surface per unit of weight ranging from 600 to 800 m²/g.

Mention may also be made of the aerogels sold by Cabot under the references Aerogel TLD 201, Aerogel OGD 201 and Aerogel TLD 203.

Use will more particularly be made of the aerogel sold under the name VM-2270 (INCI name: Silica silylate) by Dow Corning, the particles of which exhibit an average size ranging from 5 to 15 microns and a specific surface per unit of weight ranging from 600 to 800 m²/g.

- hydrophobic cellulose, for example alkyl cellulose； mentions may be made of the product ethyl cellulose sold under the trade name Ethocel^TM Standard 200 Industrial Etnylcellulose from Dow Chemicals,

- starches,

All the starches and flours are suitable for use herein and may be derived from any native source. Preferably mention may be made of hydrophobic or hydrophobically modified starches. Also suitable are starches and flours derived from a plant obtained by standard breeding techniques including crossbreeding, translocation, inversion, transformation or any other method of gene or chromosome engineering to include variations thereof. In addition, starch or flours derived from a plant grown from artificial mutations and variations of the above generic composition which may be produced by known standard methods of mutation breeding are also suitable herein. Typical sources for the starches and flours are cereals, tubers, roots, legumes and fruits. The native source can be corn, pea, potato, sweet potato, banana, barley, wheat, rice, sago, amaranth, tapioca, arrowroot, canna, sorghum, and waxy or high amylose varieties thereof.

In particular, hydrophobically modified starches according to the present invention are preferred. Such starches include, for example, aluminum starch octenylsuccinate. Aluminum starch octenylsuccinate is commonly sold under the tradename DRY-FLO PURE by the company Akzo Nobel.

Typically, the modified starches are powders at room temperature and atmospheric pressure. The modified starch powders are fine-grained. Further, the modified starch of the present invention has a particle size distribution of 5-30 microns and an average particle size of 15 microns. Moreover, the refractive index of the modified starch is measured to be between 1.50 and 1.60 at 25℃, preferably 1.52.

- talc

The hydrophobic particle may be chosen from talc.

More particularly, the talc is micro-talc (for instance Micro Ace P3 by Nippon Talc.

Micro-talc particle sizes preferably range from 1 to 300 μm； most preferably ranging from 2 to 15 μm. The talc particles may be used alone or in combination. Hybrid powders may be employed, including talc in combination with titanium dioxide, aluminum oxide, and silicon (for instance Coverleaf AR80 from Presperse LLC) , talc in combination with aluminum oxide and silicone dioxide (for instance Coverleaf AR100) .

Other hybrid powder contemplated include zinc oxide on mica-barium sulfate (for instance Shadeleaf A from Merck) , titanium dioxide on mica (for instance Blancsealer from Merck) , titanium dioxide on silica (for instance NL T30H2WA from Nippon Sheet Glass) , and titanium dioxide on mica-barium sulfate (for instance Naturaleaf powder from Merck) .

Micro-talc is preferred in accordance to the present invention.

- Silicone resin powders,

The preferred silicone resin powder is, for instance the silicone resin with the INCI name polymethylsilsesquioxane sold under the trade name Tospearl 145A by the company GE Silicone, with a mean size of 4.5 microns.

- hollow hemispherical silicone particles, for instance methylsilanol/silicate crosspolymer sold under the trade name NLK 500, NLK 506 and NLK 510 by the company Takemoto Oil and Fat,

- polyamide

powders, for instance Nylon 12 particles of the SP-500 from Toray Industries,

- hydrophobic pigments,

The hydrophobic pigments of the present invention may be hydrophobic or hydrophobic coated pigments. The hydrophobic coated pigments present in the emulsion according to the invention are pigments which are surface-treated with a hydrophobic agent. These treated pigments are well dispersed in the hydrophobic phase.

As hydrophobic pigments, it is possible to use metal oxides such as iron oxides (in particular those which are yellow, red, brown or black in colour) , titanium dioxides, cerium oxide, zirconium oxide, chromium oxide； manganese violet, ultramarine blue, Prussian blue, ferric blue, bismuth oxychloride, pearl, mica coated with titanium dioxyde or with bismuth oxychloride, coloured pearlescent pigments such as mica-titanium with iron oxides, mica-titanium with in particular ferric blue or chromium oxide, mica-titanium with an organic pigment of the abovementioned type and pearlescent pigments based on bismuth oxychloride, and mixtures thereof.

Hydrophobic pigments of iron oxides or of titanium dioxide are preferably used.

The hydrophobic treatment agent may be chosen from silicones such as methicones, dimethicones, perfluoroalkylsilanes； fatty acids such as stearic acid； metal soaps such as aluminium dimyristate, the aluminium salt of hydrogenated tallow glutamate, perfluoroalkyl phosphates, perfluoroalkylsilanes, perfluoroalkylsilazanes, polyhexafluoropropylene oxides, polyorganosiloxanes comprising perfluoroalkyl perfluoropolyether groups, amino acids； N-acylated amino acids or their salts； lecithin, isopropyl triisostearyl titanate, and mixtures thereof.

Preferably, fatty acids, such as stearic acid, are used as the hydrophobic treatment agent (s) .

Mentions may be made of the hydrophobic coated pigment, such as metal oxides coated with fatty acids, for example titanium dioxide and aluminum hydroxide coated with stearic acid, which is sold under the tradename Micro Titanium Dioxide MT-100 T V by the company Tayca.

- or a mixture thereof.

According to one embodiment, the composition of the present invention comprises at least onehydrophobic particle chosen from hydrophobic silica, starches, hydrophobic pigments, or a mixture thereof.

More preferably, the composition of the present invention comprises at least one hydrophobic particle chosen from hydrophobic fumed silica treated at the surface with a dimethylsiloxane, aerogel particles of hydrophobic silica exhibiting a specific surface per unit of weight (SW) ranging from 500 to 1500 m²/g and a size, expressed as volume-average diameter (D [0.5] , also known as median particle size by volume Dv50) , ranging from 1 to 1500 μm, hydrophobic cellulose such as ethyl cellulose, hydrophobically modified starches, hydrophobic pigments, or a mixture thereof.

According to one embodiment, the hydrophobic particle is selected from the group consisting of particle comprising or made by silica dimethyl silylate, silica silylate, hydrophobic alkyl cellulose, aluminum starch octenylsuccinate, micro-talc, polymethylsilsesquioxane, methylsilanol/silicate crosspolymer, nylon-12, metal oxides, metal oxides coated with fatty acids, and any mixture thereof； more preferably, the hydrophobic particle comprises or is made by ethyl cellulose.

Even more preferably, the composition of the present invention comprises at least one hydrophobic particle chosen from silica dimethyl silylate, silica silylate, alkyl cellulose such as ethyl cellulose, aluminum starch octenylsuccinate, pigments of iron oxides or of titanium dioxide, pigments of metal oxides coated with fatty acids such as stearic acid, or a mixture thereof.

Preferably, the hydrophobic particles are present in an amount in the composition of the present invention ranging from 0.001％to 5％by weight, preferably from 0.05％to 2％by weight, relative to the total weight of the composition.

Amphiphilic agent (s)

The composition of the present invention comprises at least one amphiphilic agent, selected from the group consisting of silicones comprising at least one oxyalkylenated chain, amphiphilic crosslinked copolymer, or a mixture thereof.

The term “amphiphilic agent” according to the present invention refers to the agents has, in its structure, both hydrophobic group and hydrophilic group. Thanks to the amphiphilic structure of these agents, it is possible to form a homogenous film of the composition of the present invention on keratin materials, in particular the skin.

According to the present invention, the amphiphilic agent is selected from silicones comprising at least one oxyalkylenated chain.

The term "silicone comprising at least one oxyalkylenated chain" is intended to mean a polydimethylsiloxanes comprising at least one oxyalkylenated chain, in particular comprising at least one oxyethylenated (-OCH₂CH₂-) and/or oxypropylenated (-OCH₂CH₂CH₂-) chain.

Examples of polydimethylsiloxanes comprising at least one oxyethylenated (-OCH₂CH₂-) chain are PEG-10 dimethicone, such as those under the trade name KF-6017 sold by the company SHIN ETSU； PEG-12 dimethicone, such as those under the trade name DOW CORNING 193 FLUID sold by the company DOW CORNING； PEG-14 dimethicone, such as those under the trade name ABIL B8842 sold by the company EVONIK GOLDSCHMIDT.

Preferably, the suitable amphiphilic agent of this type according to the invention is polydi-methylsiloxanes comprising an oxyethylenated (-OCH₂CH₂-) chain of from 8 to 12 PEG units.

Examples of polydimethylsiloxanes comprising at least one oxypropylenated (-OCH₂CH₂CH₂-) chain are PPG-12 dimethicone, such as those under the trade name SILSOFT 900 sold by the company MOMENTIVE PERFORMANCE MATERIALS.

Polydimethylsiloxanes comprising both oxyethylenated groups and oxypropylenated groups are also useful in the present invention. Mention may, for example, be made of the polydimethylsiloxane with an oxyethylene/oxypropylene ending sold as a mixture with caprylic/capric acid triglycerides under the name Abil care 85 by the company Goldschmidt (INCI name: BIS-PEG/PPG-16/16 PEG/PPG-16/16 Dimethicone/Caprylic/Capric Triglyceride) , the polydimethylsiloxane comprising an alpha-omega polyether group (OE/OP: 40/60) , sold under the name Abil B8832 by the company Goldschmidt (INCI name: BIS-PEG/PPG-20/20 Dimethicone) , the oxyethylenated oxypropylenated polydimethylsiloxane sold under the name Abil B88184 by the company Goldschmidt (INCI name: PEG/PPG-20/6 Dimethicone) and the oxyethylenated oxypropylenated polydimethyl/methylsiloxane sold under the name Abil B8852 by the company Goldschmidt (INCI name: PEG/PPG-4/12 Dimethicone) , and mixtures thereof.

According to a preferred embodiment of the invention, the amphiphilic agent of the present invention is polydimethylsiloxanes comprising at least one oxyethylenated (-OCH₂CH₂-) chain, more preferably is polydimethylsiloxanes comprising an oxyethylenated (-OCH₂CH₂-) chain of from 8 to 12 PEG units, and even more preferably is PEG-12 dimethicone.

According to another embodiment, the amphiphilic agent of the present invention is selected from amphiphilic crosslinked copolymers.

Preferably, the amphiphilic crosslinked copolymer comprises at least one unit of an unsaturated olefinic carboxylic acid, and at least one hydrophobic unit of a (C₁₀-C₃₀) alkyl ester of unsaturated carboxylic acid.

In particular, the unsaturated olefinic carboxylic acid unit is a hydrophilic unit.

In particular, the (C₁₀-C₃₀) alkyl ester of unsaturated carboxylic acid unit is a hydrophobic unit.

Thus, such crosslinked copolymer may comprise at least one hydrophilic unit of the olefinic unsaturated carboxylic acid type and at least one hydrophobic unit of (C₁₀-C₃₀) alkyl ester of unsaturated carboxylic acid type. As used herein, “at least one crosslinked copolymer” means one crosslinked copolymer or a mixture of copolymers.

In one embodiment, said copolymer is a block copolymer.

As used herein, the term (C₁₀-C₃₀) alkyl means an alkyl group, linear or branched, comprising from 10 to 30 carbon atoms.

In one embodiment, the molecular weight of the above-mentioned copolymer is of at least 50 kD.

In one embodiment, the above-mentioned crosslinked copolymer is chosen from those comprising:

- at least one unit derived from olefinic unsaturated carboxylic acid monomers of formula (I):

wherein R₁ is selected from the group consisting of : H, CH₃, and C₂H₅, (which corresponds respectively to acrylic acid, methacrylic acid and ethacrylic acid units) , and

- at least one unit derived from (C₁₀-C₃₀) alkyl esters of unsaturated carboxylic acid monomers of formula (II) :

wherein R₂ is selected from the group consisting of: H, CH₃, and C₂H₅ (which corresponds respectively to acrylate, methacrylate and ethacrylate units) , and R₃ is a saturated or unsaturated, branched or unbranched (C₁₀-C₃₀) alkyl group.

As used herein, the term “at least one unit derived from olefinic unsaturated carboxylic acid monomers of formula (I) ” means that said unit is formed from the monomers of formula (I) , for example by polymerization of the monomers of formula (I) .

In one embodiment, for example, R₂ is chosen from H (acrylate units) and CH₃ (methacrylate units) and R₃ is chosen from (C₁₂-C₂₂) alkyl groups.

(C₁₀-C₃₀) alkyl esters of unsaturated carboxylic acids in accordance with the invention include for example lauryl acrylate, stearyl acrylate, decyl acrylate, isodecyl acrylate, dodecyl acrylate, lauryl methacrylate, stearyl methacrylate, decyl methacrylate, isodecyl methacrylate, and dodecyl methacrylate.

Crosslinked copolymer of this type are for example described and prepared according to U.S. Pat. Nos. 3,915,921 and 4,509,949, the disclosures of which are incorporated by reference herein.

In one embodiment, the crosslinked copolymer that can be used include those formed from a mixture of monomers comprising:

· (a) acrylic acid,

· (b) at least one ester of formula (II) described above wherein R₂ is chosen from H and CH₃, and R₃ is chosen from alkyl groups comprising from 12 to 22 carbon atoms, and

· (c) at least one crosslinking agent chosen from copolymerizable polyethylenic unsaturated monomers such as diallyl phthalate, allyl (meth) acrylate, divinylbenzene, (poly) ethylene glycol dimethacrylate and methylenebisacrylamide.

In one embodiment, the crosslinked copolymers of the invention that can be used include (％being given with respect to the total weight of the respective copolymers) :

-copolymers comprising from 95％to 60％by weight of acrylic acid (hydrophilic unit) , from 4％to 40％by weight of C₁₀-C₃₀ alkyl acrylate (hydrophobic unit) , and from 0％to 6％by weight of crosslinking polymerizable monomer, and

-copolymers comprising from 98％to 96％by weight of acrylic acid (hydrophilic unit) , from 1％to 4％by weight of C₁₀-C₃₀ alkyl acrylate (hydrophobic unit) and from 0.1％to 0.6％by weight of crosslinking polymerizable monomer such as those described above.

Among the above crosslinked copolymers, the products sold by the company Lubrizol under the trade names PEM U LEN

PEM U LEN

and CARBOPOL

can be used.

Preferably, the crosslinked copolymer used in the present invention is PEMULEN

which is an acrylates/C₁₀-C₃₀ alkyl acrylate crosspolymer.

Preferably, the amphiphilic agent is present in the composition of the present invention ranging from 0.001％to 5％by weight, preferably from 0.05％to 2％by weight, relative to the total weight of the composition.

Additives

In a particular embodiment, a composition according to the invention further comprises at least one compound chosen from hydrophilic solvents, lipophilic solvents, additional oils, additional UV-screening agents, and mixtures thereof.

A cosmetic composition according to the invention may also comprise any additive usually used in the field under consideration, chosen, for example, from fillers or viscosity increasing agents, additional gelling agents, gums, resins, thickening agents, structuring agents such as waxes, dispersants, antioxidants, essential oils, preserving agents, fragrances, neutralizers, antiseptics, cosmetic active agents, such as vitamins, moisturizers, emollients or collagen-protecting agents, and mixtures thereof.

Suitable fillers and/or viscosity increasing agents include silicate clays such as, for example, silicate clays containing at least one cation which may be chosen from calcium, magnesium, aluminium, sodium, potassium, and lithium cations, and mixtures thereof. Non-limiting examples of such products include smectite clays such as montmorillonites, hectorites, bentonites, beidellites, saponites, vermiculites, stevensite, and chlorites. Preferred examples of silicate clays which may be used in the present invention are chosen from lithium magnesium silicate, aluminum calcium sodium silicate, calcium magnesium silicate, sodium magnesium silicate, calcium aluminum borosilicate, magnesium aluminum silicate, sodium potassium aluminum silicate, and sodium silver aluminum silicate.

It is a matter of routine operations for a person skilled in the art to adjust the nature and amount of the additives present in the compositions in accordance with the invention such that the desired cosmetic properties and stability properties thereof are not thereby affected. If present, the fillers and/or viscosity increasing agents are present in an amount ranging from 0.05％to 10％by weight, preferably from 0.1％to 5％by weight, relative to the total weight of the composition.

Galenic form

The composition according to the invention is in form of an oil-in-water emulsion.

In particular, according to an embodiment, the composition of the present invention is in form of an oil-in-water Pickering emulsion.

More particularly, the composition of the present invention has a hydrophobic phase in form of droplets.

According to an embodiment, the composition of the present invention is a gel.

In one embodiment, said aqueous phase is translucent or transparent.

Advantageously, the composition of the present invention has the appearance of a gel, particularly a translucent gel.

More preferably, the composition contains an aqueous gel.

The term “aqueous gel” means a composition containing a continuous aqueous phase containing a viscoelastic mass formed from colloidal suspensions. The viscosity of a gel according to the invention is measured at 25℃. using a ProRheo R180 machine (rotor 2) from the company Prorheo, and its value is generally at least 20 DU (Deviation Units) with the rotor 2.

The gels in accordance with the present invention comprise an aqueous phase generally in a proportion of greater than or equal to 70％by weight, preferably greater than or equal to 80％by weight and more particularly greater than or equal to 90％by weight relative to the total weight of the gel.

The term “translucent” means which allows light to pass through without making it possible to distinguish alphanumeric characters using 5 mm thick samples.

The term “transparent” means which allows light to pass through, and makes it possible to distinguish alphanumeric characters using 5 mm thick samples.

Method and use

The present invention also relates to a use of the composition according to the present invention, as it is or in cosmetic product for making up/caring for/cleansing/make up removing products for the skin, especially for the face and the lips.

The present invention relates to a non-therapeutic cosmetic process for caring for and/or making up a keratin material, comprising the application, to the surface of the said keratin material, of at least one composition of the invention.

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

The examples that follow are aimed at illustrating the compositions and processes according to this invention, but are not in any way a limitation of the scope of the invention.

EXAMPLES

Example 1: formulation example

The formula invention formulas A, B, and comparative formulas A, B, and B’ were prepared:

Comparative formula A and B do not contain the amphiphilic agent as claimed；

Comparative formula B’ contains CETYL DIMETHICONE, which is not amphiphilic agent according to the invention.

The formulas were prepared following the steps of:

PHENYLBENZIMIDAZOLE SULFONIC ACID and/or TEREPHTHALYLIDENE DICAMPHOR SULFONIC ACID, when existing, were neutralized by TRIETHANOLAMINE and TROMETHAMINE to PH at 7.0 in water at 25℃. They were then added to the phase Q at 25℃, and mixed until homogeneous. Then PEG-12 Dimethicone and/or ACRYLATES/C10-30 ALKYL ACRYLATE CROSSPOLYMER were added in the phase Q. The mixture were stirred until homogeneous at 25℃.

Ethyl cellulose was melted by 6％by weight of alcohol, relative to the total weight of the alcohol, then water was added to the melted solution by stirring to form oil globules. The mixture containing oil globules were then added to the mixture obtained above. Phase Q was added at last and oil droplets were formed during stirring.

All the amounts are by active matters and the quantities of ingredients are expressed by weight percent relative to the total weight of the composition.

QS : Quantity sufficient to 100％

It was observed that the invention formulas A and B, and comparative formulas A, B, and B’ resulted in translucent sunscreen compositions.

It was also observed that, comparing to the Comparative formulas A, B, and B’ , the invention formulas A and B presented an improved UV-screening ability. In particular, the UV-screening ability is UV-B screening ability.

Claims

A composition in form of an oil-in-water emulsion comprising:

a) a dispersed hydrophobic phase comprising at least one hydrophobic UV-screening agent；

b) a continuous aqueous phase comprising at least one hydrophilic UV-screening agent；

c) at least one hydrophobic particle selected from the group consisting of hydrophobic silicas, hydrophobic cellulose, starch, talc, silicone resin powders, hollow hemispherical silicone particles, polyamide powders, hydrophobic pigments, and any mixture thereof； and

d) at least one amphiphilic agent selected from the group consisting of silicone comprising at least one oxyalkylenated chain, amphiphilic crosslinked copolymer, or a mixture thereof.
The composition of claim 1 is a translucent gel.
The composition of claim 1 or 2, wherein the hydrophobic UV-screening agent is selected from the group consisting of cinnamates, β, β’ -diphenylacrylate derivatives, phenyl benzotriazole derivatives, or a mixture thereof； preferably selected from the group consisting of Ethylhexyl Methoxycinnamate, Octocrylene, Drometrizole Trisiloxane, or a mixture thereof.
The composition of any one of the preceding claims 1 to 3, wherein the hydrophobic UV-screening agent is present in an amount ranging from 0.01％ to 20％ by weight, more preferably from 0.1％ to 20％ by weight, and even more preferably from 1％ to 10％ by weight, relative to the total weight of the composition.
The composition of any one of the preceding claims 1 to 4, wherein the hydrophilic UV-screening agent is selected from the group consisting of terephthalylidene dicamphor sulfonic acid, phenylbenzimidazole sulfonic acid, or a mixture thereof.
The composition of any one of the preceding claims 1 to 5, wherein the hydrophilic UV-screening agent is present in an amount ranging from 1％ to 40％ by weight, more preferably from 5％ to 20％ by weight, relative to the total weight of the composition.
The composition according to any one of claims 1 to 6, wherein the hydrophobic particle is selected from the group consisting of particle comprising or made by silica dimethyl silylate, silica silylate, hydrophobic alkyl cellulose, aluminum starch octenylsuccinate, micro-talc, polymethylsilsesquioxane, methylsilanol/silicate crosspolymer, nylon-12, metal oxides, metal oxides coated with fatty acids, and any mixture thereof； more preferably, the hydrophobic particle comprises or is made by ethyl cellulose.
The composition according to any one of claims 1 to 7, wherein the hydrophobic particle is present in an amount ranging from 0.001％ to 5％, preferably from 0.05 to 2％, by weight relative to the total weight of the composition.
The composition of any one of the preceding claims 1 to 8, wherein the amphiphilic agent is selected from the group consisting of polydimethylsiloxanes comprising at least one oxyethylenated (-OCH₂CH₂-) chain, amphiphilic crosslinked copolymers comprising at least one unit of an unsaturated olefinic carboxylic acid, and at least one hydrophobic unit of a (C₁₀-C₃₀) alkyl ester of unsaturated carboxylic acid； preferably selected from the group consisting of polydimethylsiloxanes comprising an oxyethylenated (-OCH₂CH₂-) chain of from 8 to 12 PEG units, crosslinked copolymer formed from a mixture of monomers comprising (a) acrylic acid, (b) at least one ester of formula (II)

wherein R₂ is selected from the group consisting of: H, CH₃, and

R₃ is a alkyl group comprising from 12 to 22 carbon atoms, and (c) at least one crosslinking agent chosen from copolymerizable polyethylenic unsaturated monomers such as diallyl phthalate, allyl (meth) acrylate, divinylbenzene, (poly) ethylene glycol dimethacrylate and methylenebisacrylamide； more preferably selected from the group consisting of PEG-12 dimethicone, acrylates/C₁₀-C₃₀ alkyl acrylate crosspolymer, or a mixture thereof.
The composition of any one of the preceding claims 1 to 9, wherein the amphiphilic agent is present in the composition of the present invention ranging from 0.001％ to 5％ by weight, preferably from 0.05％ to 2％ by weight, relative to the total weight of the composition.
A non-therapeutic cosmetic process for caring for and/or making up a keratin material, comprising the application, to the surface of the said keratin material, of at least one composition according to any one of the previous claims 1 to 10.