WO2014097972A1

WO2014097972A1 - Cosmetic photoprotective compositions

Info

Publication number: WO2014097972A1
Application number: PCT/JP2013/083405
Authority: WO
Inventors: Mutsue KOYAMA; Rena ROCHET; Tomomi HAMAZAKI
Original assignee: L'oreal
Priority date: 2012-12-18
Filing date: 2013-12-06
Publication date: 2014-06-26
Also published as: JP2016503006A; JP6438409B2

Abstract

The present invention concerns a composition containing in a cosmetically acceptable medium (A) at least one organic UV filter, (B) spherical composite particles with a mean size of from 1 to 20 μm comprising a matrix and an inorganic UV filter, (C) boron nitride particles and (D) spherical porous silica particles. The composition according to the present invention provides high UV protective effect (such as high SPF and PPD) and better usability such as less whitish look on the skin and less greasiness. The present invention concerns also a cosmetic process for the care and/or make-up of the keratinic materials which consists in applying on to the surface at least one composition process for the care and/or make-up of the keratinic materials which consists in applying on to the surface at least one composition as above defined.

Description

DESCRIPTION

COSMETIC PHOTOPROTECTIVE COMPOSITIONS

TECHNICAL FIELD

The present invention relates to a photoprotective composition based on the association of at least one organic UV filter, spherical composite particles, boron nitride particles and spherical porous silica particles. More particularly, the present invention relates to a cosmetic composition which achieves both high SPF PPD values and good usability.

BACKGROUND ART

It is known that light radiation with wavelengths of between 280 nm and 400 nm permits tanning of the human epidermis and that light rays with wavelengths more particularly between 280 and 320 nm, known as UV-B rays, cause skin burns and erythema which can harm the development of a natural tan. For these reasons, and also for aesthetic reasons, there is constant demand for means for controlling this natural tanning in order thus to control the colour of the skin; this UV-B radiation should thus be screened out.

It is also known that UV-A rays, with wavelengths between 320 and 400 nm, which cause tanning of the skin, are liable to induce adverse changes therein, in particular in the case of sensitive skin or skin that is continually exposed to solar radiation. UV-A rays cause in particular a loss of elasticity of the skin and the appearance of wrinkles leading to premature ageing of the skin. Thus, for aesthetic and cosmetic reasons, for instance conservation of the skin's natural elasticity, people increasingly wish to control the effect of UV-A rays on their skin. It is thus desirable also to screen out UV-A radiation.

For the purpose of protecting the skin against UV radiation, anti-UV compositions containing organic UV filters that are active both in the UV-A range and in the UV-B range are generally used. Further, there are many cosmetic products containing one or more inorganic and/or organic UV screening agents. In particular, cosmetic products intended to be applied to the skin often contain fine Titanium oxide particles to protect the skin from UV rays. These fine metal oxide particles generally have a mean elementary particle size of less than or equal to 0.1 um.

One of the major drawbacks of inorganic UV filters lies in the fact that conventional antisun formulations based on metal oxide pigments result, after application to the skin, in an uneven, inhomogeneous or even coarse distribution of the pigments on this skin, which may be detrimental to the quality of the overall photoprotective effect desired. This poor distribution of the screening metal oxide pigments that is observed at the surface of the skin is often linked to the fact that there is, in the initial composition itself (before application), a substantial lack of homogeneity (poor dispersion of the pigment in its support). Another drawback of suntan compositions based on inorganic screening agents and more particularly based on titanium oxide is that, once applied to the skin in the form of a film, they create, on the latter, a whitening effect which is cosmetically undesirable and is generally not much appreciated by the users. This effect is even more pronounced when the concentration of mineral screening agents in the composition is high. To avoid this problem, it would of course be possible to use reduced amounts of inorganic screening agent(s), but the resulting compositions, which would certainly result in films exhibiting an acceptable transparency on the skin, would then no longer offer suitable protection in the UV range, which greatly limits the advantage of such an option.

Finally, it is common to combine organic screening agents and inorganic pigments within sun protection compositions in order to broaden their spectrum of protection and consequently to improve the efficacy thereof. However, the use of certain sunscreens results in compositions that have a greasy and tacky feel that is not very pleasant. Therefore, there remains a need to have compositions containing pigments that are compatible with organic screening agents which do not have the respective drawbacks of pigments (dispersibility, homogeneity of the formulae, whitening) and of organic screening agents. This problem has advantageously been solved with the compositions according to the invention.

JP 2007-161648A discloses a micro-particle zinc oxide dispersion affording a natural finish feeling with transparency and having excellent ultraviolet protecting effects in both the UV-A and the UV-B regions and good stability. The micro-particle zinc oxide dispersion is characterized as dispersing micro-particle zinc oxide having 15-55 nm primary particle diameter into 70-140 nm average dispersed particle diameter in a hydrophobic dispersion medium.

However, use of nano material has been warned to raise risk.

JP 2000-63238A discloses an emulsified cosmetic composition containing (A) titanium oxide-coated mica with an average particle size of equal to or less than 30 μπι and (B) a silicone suspension of microparticle titanium oxide and/or microparticle zinc oxide, whose primary particle diameter is from 0.001 to 1 μηι. It allegedly provides natural transparency, non-whitish finish, high UV-blocking ability, and a makeup finish with emphasizing 3D effect (highlight effect).

JP 2004-323473A discloses to a cosmetic composition containing a white inorganic pigment with the mean particle diameter of from 0.12 to 1.0 μπι and a spherical complex polymer particle whose mean particle diameter is less than 5 μιη. It allegedly provides natural and transparent finish. But it does not teach UV protecting effect.

To achieve high protection from UV-A and UV-B, UV filters/absorbers are formulated in sunscreen products. However, usability has been often sacrificed by high concentration of UV filters/absorbers in order to achieve high UV protection effect, and such formula may result in too white and greasy finish on the skin.

Therefore, there remains a need to have UV protection compositions that are effective in photoprotection and that do not have the drawbacks presented above. Unexpectedly and advantageously, the inventors have shown that this need could be met by means of the compositions according to the present invention.

DISCLOSURE OF THE INVENTION

Thus, one of the objectives of the present invention is to achieve both high SPF/PPD values and good usability. The present inventors have energetically made efforts to find that the above objectives can be achieved by a composition containing in a cosmetically acceptable medium:

(A) at least one organic UV filter,

(B) spherical composite particles with a mean size of from 1.0 to 20.0 μπι comprising a matrix and an inorganic UV filter,

(C) boron nitride and

(D) spherical porous silica particles.

In one embodiment, the composition contains the (C) boron nitride in a platelet shape. In one embodiment, the inorganic UV filter of the (B) spherical composite particles is titanium oxide, and/or zinc oxide, and more preferably titanium dioxide.

In one embodiment, the inorganic material used in the matrix of the (B) spherical composite particles is selected from the group consisting of silica, mica, talc, iron oxide, aluminium oxide and glass.

In one embodiment, the matrix of the (B) spherical composite particles comprises organic materials selected from the group consisting of poly(meth)acrylates, polyamides, silicones, polyurethanes, polyethylenes, polypropylenes, polystyrenes, polycaprolactams, polysaccharides, polypeptides, polyvinyl derivatives, waxes, polyesters and polyethers.

In one embodiment, the matrix of the (B) spherical composite particles is silica and the inorganic UV filter is titanium dioxide.

In one embodiment, the amount of the inorganic UV filter is from 1 to 50%, preferably from 2 to 40% and more preferably from 2 to 30% by weight relative to the total weight of the (B) spherical composite particles.

In one embodiment, the amount of the (A) organic UV filter relative to the total weight of the cosmetic composition is from 1 to 50 %, preferably from 5 to 35 %, and more preferably from 10 to 30 % by weight.

In one embodiment, the amount of the (B) spherical composite particles relative to the total weight of the cosmetic composition is from 0.1 to 15 %, preferably from 1 to 12 %, and more preferably from 2 to 10 % by weight.

In one embodiment, the (C) boron nitride particles have a particle size distribution such that the value of D₅₀ (50 percent of the particles have a diameter lower this value) is from 2 to 12 μπι.

In one embodiment, the amount of the (C) boron nitride particle relative to the total weight of the cosmetic composition is from 0.01 to 10%, preferably from 0.1 to 5%, and more preferably from 0.5 to 3% by weight.

In one embodiment, the (D) spherical porous silica particles have a distribution mean size from 0.5 to 20 μπι and more preferably 2 to 9 μπι.

In one embodiment, the (D) spherical porous silica particles have a specific surface ranging from 50 to 1,000 m²/g, and more preferably from 150 to 800 m²/g.

In one embodiment, the (D) spherical porous silica particles have have a specific pore volume ranging from 0.5 to 5 ml/g, and more preferably from 1 to 2 ml/g.

In one embodiment, the amount of the (D) spherical porous silica particles relative to the total weight of the composition is from 0.01 to 10% by weight.

EFFECT OF THE INVENTION

The cosmetic composition according to the present invention is effective in photoprotection. Moreover, the cosmetic composition according to the present invention provides a high value of SPF and PPD. At the same time, the cosmetic composition according to the present invention does not generate a white deposit on the skin when it is applied to the skin. Moreover, it is highly satisfactory in terms of cosmeticity: it has a non-greasy, non-tacky feel. The following description and examples present other advantages, aspects and properties of the present invention.

DEFINITIONS

The following definitions are used in the present invention. The cosmetic compositions according to the present invention are photoprotective compositions intended to screen UV radiation; these compositions are also known as anti-sun compositions or sun protection compositions.

The expression "mean size" of the particles is understood to mean the parameter D_[4j3] measured using a "Mastersizer 2000" particle size analyser (Malvern). The light intensity scattered by the particles as a function of the angle at which they are lit is converted to size distribution according to Mie theory. The parameter D_[4i3] is measured; this is the mean diameter of the sphere having the same volume as the particle. For a spherical particle or a platelet particle, reference will often be made to the "mean diameter". The term "cosmetically acceptable medium" means a medium compatible with the skin and/or its integuments or mucous membranes, having a pleasant colour, odour and feel and not causing any unacceptable discomfort (stinging, tautness or redness) liable to discourage the consumer from using this composition.

DETAILED DESCRIPTION OF THE INVENTION

(A) ORGANIC V FILTER The composition according to the present invention contains at least one organic UV filter. The organic UV filters may be hydrophobic or water-soluble. The organic UV filters may be UV-A screening agents and/or UV-B screening agents. The organic UV filters may be hydrophobic or water-soluble mixed UV-A and UV-B screening agents.

The expression "hydrophobic UV filter" is understood to mean any UV screening agent susceptible to be insoluble or hardly soluble in water and susceptible to be totally dissolved at the molecular state in a liquid fatty phase or to be solubilzed under a colloidal form (for example under micellar form) in a liquid fatty phase. According to another embodiment, a hydrophobic UV screening agent may be insoluble in a liquid fatty phase.

The expression "water-soluble UV filter" is understood to mean any UV screening agent susceptible to be totally dissolved at the molecular state in a liquid aqueous phase or to be solubilized under a colloidal form (for example under micellar form) in a liquid aqueous phase.

The organic UV filters are not limited specially, but the following species are preferably used depending on the purposes. 1) Hydrophobic UV-A screening agents

Dibenzoylmethane derivatives:

Butyl methoxydibenzoylmethane sold in particular under the trade name Parsol 1789 by DSM Nutritional Products, Inc.;

Isopropyl dibenzoylmethane.

Aminobenzophenones:

n-Hexyl 2-(4-diethylamino-2-hydroxybenzoyl)benzoate sold in particular under the trade name Uvinul A+ by BASF;

1 , -( 1 ,4-Piperazinediyl)bis[ 1 -[2-[4-(diethylamino)-2-hydroxybenzoyl]phenyl]methanone (CAS 919803-06-8). Anthranilic derivatives:

Menthyl anthranilate sold in particular under the trade name Neo Heliopan MA by Symrise.

4.4-Diarylbutadiene derivatives:

1,1 -Dicarboxy-(2,2 '-dimethylpropyl)-4,4-diphenylbutadiene.

Merocyanine derivatives:

Octyl 5-N,N-diethylamino-2-phenylsulphonyl-2,4-pentadienoate. Preferred Hydrophobic UV-A screening agents are butyl methoxydibenzoylmetliane, and/or n-Hexyl 2-(4-diethylamino-2-hydroxybenzoyl)benzoate.

2) Water-soluble UV-A screening agents

Terephthalylidene dicamphor sulphonic acid manufactured under the name Mexoryl SX by Chimex.

Bis-benzazolyl derivatives as described in patents EP 669 323, and US 2,463,264 and more particularly the disodium phenyl dibenzimidazotetrasulphonate compound sold under the trade name Neo Heliopan AP by Symrise.

Preferred water-soluble UV-A screening agent is terephthalylidene dicamphor sulphonic acid.

3) Hydrophobic UV-B screening agents

■Para-aminobenzoates:

Ethyl PABA;

Ethyl dihydroxypropyl PABA;

Ethylhexyl dimethyl PABA (Escalol 507 from ISP).

Salicylic derivatives:

Homosalate sold in particular under the name Eusolex HMS by Rona/EM Industries;

Ethylhexyl salicylate sold in particular under the name Neo Heliopan OS by Symrise;

Dipropylene glycol salicylate sold in particular under the name Dipsal by Scher;

TEA salicylate sold under the name Neo Heliopan TS by Symrise.

Cinnamates

Ethylhexyl methoxycinnamate sold in particular under the trade name Parsol MCX by DSM Nutritional Products, Inc.;

Isopropyl methoxycinnamate; Isoamyl methoxycinnamate sold in particular under the trade name Neo Heliopan E 1000 by Symrise;

Diisopropyl methylcinnamate;

Cinnoxate;

Glyceryl ethylhexanoate dimethoxycinnamate. β, β'-Diphenylacrylate derivatives:

Octocrylene sold in particular under the trade name Uvinul N539 by BASF;

Etocrylene sold in particular under the trade name Uvinul N35 by BASF.

Benzylidene camphor derivatives:

3-Benzylidene camphor manufactured under the name Mexoryl SD by Chimex;

Methylbenzylidene camphor sold in particular under the name Eusolex 6300 by Merck;

Polyacrylamidomethylbenzylidene camphor manufactured under the name Mexoryl SW by Chimex.

Triazine derivatives:

Ethylhexyl triazone sold in particular under the trade name Uvinul T 150 by BASF;

Diethylhexyl butamidotriazone sold in particular under the trade name Uvasorb HEB by Sigma 3 V;

2,4,6-Tris(dineopentyl 4'-aminobenzalmalonate)-s-triazine;

2,4,6-Tris(diisobutyl 4'-aminobenzalmalonate)-s-triazine;

2,4-Bis(dineopentyl 4'-aminobenzalmalonate)-6-(n-butyl 4'-aminobenzoate)-s-triazine;

2,4-Bis(n-butyl 4'-aminobenzoate)-6-(aminopropyltrisiloxane)-s-triazine; the symmetrical triazine screening agents described in patent US 6,225,467, patent 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 (20 September 2004), especially

2,4,6-tris(biphenyl)-l,3,5-triazines (in particular 2,4,6- tris(biphenyl-4-yl-l,3,5-triazine) and

2,4,6-tris(terphenyl)-l,3,5-triazine, the latter two screening agents being described in Beiersdorf patent applications WO 06/035000, WO 06/034982, WO 06/034991, WO 06/035007, WO

2006/034992 and WO 2006/034985).

Imidazoline derivatives:

Ethylhexyl dimethoxybenzylidene dioxoimidazoline propionate.

Benzalmalonate derivatives: Polyorganosiloxanes containing benzalmalonate functions, for instance Polysilicone-15, sold in particular under the trade name Parsol SLX by DSM Nutritional Products, Inc.; Dineopentyl 4'-methoxybenzalmalonate. Preferred hydrophobic UV-B screening agents are:

Ethylhexyl salicylate; Octocrylene; and Ethylhexyl triazone.

4) Water-soluble UV-B screening agents

The following p-aminobenzoic acid (PABA) derivatives:

PABA,

Glyceryl PABA and

PEG-25 PABA sold in particular under the trade name Uvinul P25 by BASF.

Phenylbenzimidazole sulphonic acid sold in particular under the trade name Eusolex 232 by Merck,

ferulic acid,

salicylic acid,

DEA methoxycinnamate,

benzylidene camphor sulphonic acid manufactured under the name Mexoryl SL by Chimex, camphor benzalkonium methosulphate manufactured under the name Mexoryl SO by Chimex. The preferred water-soluble UVB screening agent is phenylbenzimidazole sulphonic acid.

5) Mixed UV-A and UV-B hydrophobic screening agents

Benzophenone derivatives:

Benzophenone-1 sold in particular under the trade name Uvinul 400 by BASF;

Benzophenone-2 sold in particular under the trade name Uvinul D50 by BASF;

Benzophenone-3 or oxybenzone sold in particular under the trade name Uvinul M40 by BASF;

Benzophenone-6 sold in particular under the trade name Helisorb 11 by Norquay;

Benzophenone-8 sold in particular under the trade name Spectra-Sorb UV-24 by American

Cyanamid;

Benzophenone- 10;

Benzophenone- 11;

Benzophenone- 12.

Phenyl benzotriazole derivatives:

Drometrizole trisiloxane sold in particular under the name Silatrizole by Rhodia Chimie or manufactured under the name Meroxyl XL by the company Chimex;

Methylene bis-benzotriazolyl tetramethylbutylphenol sold in solid form in particular under the trade name Mixxim BB/100 by Fairmount Chemical, or in micronized form as an aqueous dispersion in particular under the trade name Tinosorb M by Ciba Specialty Chemicals.

Bis-resorcinyl triazine derivatives:

Bis-ethylhexyloxyphenol methoxyphenyl triazine sold in particular under the trade name Tinosorb S by Ciba Specialty Chemicals y.

Benzoxazole derivatives:

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

Preferred UV-A and UV-B hydrophobic organic screening agents are: Drometrizole trisiloxane; Methylene bis-benzotriazolyl tetramethylbutylphenol; and Bis-ethylhexyloxyphenol methoxyphenyl triazine. 6) Mixed UV-A and UV-B water-soluble screening agents

Benzophenone derivatives comprising at least one sulphonic radical, such as

Benzophenone-4 sold in particular under the trade name Uvinul MS 40 by BASF,

Benzophenone-5 and

Benzophenone-9.

The amount of the organic UV filters, namely UV-A and/or UV-B organic screening agents in the cosmetic composition according to the present invention may be from 1 to 50 % by weight and preferably from 5 to 35 % by weight, and more preferably from 10 to 30 % relative to the total weight of the cosmetic composition. (B) SPHERICAL COMPOSITE PARTICLES

The composition according to the present invention contains (B) spherical composite particles containing a matrix and an inorganic UV filter.

The inorganic UV filter is generally metal oxides, preferably titanium oxides, zinc oxides or mixtures thereof, and more preferably titanium dioxide (Ti0₂).

These metal oxides may be in the form of particles with a mean size generally of less than 0.2 μπι. Advantageously, the metal oxide particles used have a mean elementary size of less than or equal to 0.1 μπι.

These metal oxides may also be in the form of layers, preferably multilayers with a mean thickness generally of less than 0.2 μιη.

The amount of inorganic UV filter is preferably from 1 to 50% by weight and more 2013/083405

preferably from 2 to 40% and particularily from 2 to 30% by weight relative to the total weight of the spherical composite particle.

The inorganic materials that may be used in the matrix of the spherical composite particles according to the present invention may be selected from the group consisting of silica, mica, talc, iron oxide, aluminium oxide and glass.

The organic materials that may be used to form the matrix are chosen from the group formed by poly(meth)acrylates, polyamides, silicones, polyurethanes, polyethylenes, poly- propylenes, polystyrenes, polycaprolactams, polysaccharides, polypeptides, polyvinyl derivatives, waxes, polyesters and polyethers, and mixtures thereof.

Preferably, the matrix of the spherical composite particle contains a material or mixture of materials chosen from:

- Si0₂,

- polymethyl methacrylate,

- copolymers of styrene and of a C1/C5 alkyl (meth)acrylate derivative,

- polyamides, such as nylon.

More preferably, the matrix of the spherical composite particles will be constituted by silica.

The spherical composite particles are characterized by a mean size (diameter) from 1.0 to 20.0 μιη and more preferably from 1.2 to 15.0 μπι, advantageously from 1.5 to 10.0 μπι and more preferably from 2.0 to 9.0 μπι.

According to a first variant, the spherical composite particles contain a matrix comprising an organic and/or inorganic material, in which matrix particles of inorganic

UV-screening agent are included.

According to this first variant, the particles of inorganic UV filters are characterized by a mean elementary size generally of less than 200 nm. Advantageously, the metal oxide particles used have a mean elementary size of less than or equal to 0.1 μιη.

As spherical composite particles corresponding to this variant, mention may be made of the products Sunsil ΤΓΝ 50 and Sunsil ΤΓΝ 40 sold by the company Sunjin Chemical. These spherical composite particles with a mean size of from 2 to 7 μπι are formed from Ti02 encapsulated in a silica matrix.

Mention may also be made of the following particles:

- spherical composite particles with a mean size from 4 to 8 μηι, containing Ti02 and Si02, having the trade name Eospoly TR sold by the company Creations Couleurs,

- composite particles containing Ti02 and a styrene/alkyl acrylate copolymer matrix sold under the name Eospoly UV TR22 HB 50 by the company Creations Couleurs,

- composite particles containing Ti02 and ZnO and a PMMA matrix, having the trade name Sun PMMA-T50 sold by the company Sunjin Chemical.

According to a second variant, the spherical composite particles contain a matrix made of an organic and/or inorganic material, covered with at least one layer of inorganic

UV-screening agent connected to the matrix by means of a binder.

According to this second variant, the mean thickness of the layer of inorganic

UV-screening agent is advantageously from 0.001 to 0.2 μπι and preferably from 0.01 to 0.1 μιη.

Among the spherical composite particles that may be used according to the invention, mention may also be made of spherical composite particles containing Ti0₂ and Si0₂, having the trade name STM ACS-0050510, supplied by the company JGC Catalysts and Chemical.

According to a third variant, the spherical composite particles contain an inorganic UV filters covered with at least one layer of an organic and/or inorganic material. According to this third variant, the particles of inorganic UV filters are characterized by a mean elementary size generally of from 0.001 to 0.2 μπι. Advantageously, the metal oxide particles used have a mean elementary size of from 0.01 to 0.1 μπι.

Preferred spherical composite will be used which are formed from Ti02 encapsulated in a silica matrix and with a mean size of from 1 to 20 μιη as the commercial products Sunsil TIN 50 and Sunsil TIN 40 sold by the company Sunjin Chemical.

The amount of spherical composite particle according to the invention used may be from 0.1 to 15 % by weight, preferably from 1 to 12 % by weight, and more preferably from 2 to 10 % by weight, relative to the total weight of the cosmetic composition according to the present invention.

(C) BORON NITRIDE PARTICLES

The cosmetic composition according to the present invention contains (C) boron nitride particles. The boron nitride particles may possess a distribution of mean particle sizes of from 2 to 12 μπι, preferably from 3 to 9 μπι, and more preferably from 3.5 to 7.5 μιη.

Preferably, the boron nitride particles according to the invention have a particle size distribution such that the value of D₅₀ (50 percent of the particles have a diameter lower this value) is from 2 to 9 μπι. Boron nitride particles used according to the invention are particularly available to the Company Mizushima Ferroalloy under the trade name White Ceram 1 (R), from the company Saint-Gobain Ceramics in the commercial denominations PUHP 3008 (R) and PUH 1030 L (R), or from the company General Advanced Materials under the trade name Boron nitride Powder Soft Touch CC6058 (R). The amount of the boron nitride particle according to the invention used may be from 0.01 to 10 % by weight, preferably from 0.1 to 5 % by weight, and more preferably from 0.5 to 3 % by weight, relative to the total weight of the cosmetic composition according to the present invention. The shape of the boron nitride used for the cosmetic composition is not specifically limited, and for example, platelet, spherical or oblong-shape is preferable, and platelet shape is more preferable.

(D) SPHERICAL POROUS SILICA PARTICLES

The cosmetic composition according to the present invention contains (D) spherical porous silica particles, as agent to increase the sun protection factor (SPF).

The spherical porous silica particles according to the present invention preferably have a mean particle size from 0.5 to 20 μιη and more preferably from 2 to 9 μπι. They preferably have a specific surface ranging from 50 to 1,000 m²/g and more particularly from 150 to

800 m²/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 spherical porous silica particles, 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; Sylosphere from Fuji Silysia; and

SUNSPHERE H-33 from Asahi Glass.

The amount of the (D) spherical porous silica particles according to the present invention is preferably from 0.01 to 10 % and more particularly from 0.1 to 5 % by weight, relative to the total weight of the cosmetic composition.

ADDITIVES

The compositions according to the present invention may also contain standard cosmetic additives selected especially from water, organic solvents, ionic or nonionic, thickeners, softeners, humectants, opacifiers, stabilizers, emollients, silicones, antifoaming agents, fragrances, preserving agents, anionic, cationic, nonionic, zwitterionic or amphoteric surfactants, fillers, polymers, propellants, basifying or acidifying agents or any other ingredient commonly used in the cosmetics and/or dermatological field.

Among the organic solvents that may be mentioned are lower alcohols and polyols. The latter can be chosen from glycols and glycol ethers, such as ethylene glycol, propylene glycol, butylene glycol, dipropylene glycol or diethylene glycol.

Thickeners that may be mentioned include carboxyvinyl polymers, such as Carbopols

(Carbomers) and the Pemulens (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- methylpropanesulphonic acid polymers and copolymers, optionally crosslinked and/or neutralized, for instance

poly(2-acrylamido-2-methylpropanesulphonic 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 -methylpropanesulphonic 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.

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

PREPARATION

The cosmetic compositions according to the invention may be prepared according to the techniques that are well known to those skilled in the art. They may contain an aqueous phase and a fatty phase and may be in the form of a simple or complex emulsion (O/W, W/O, 0/W/O or W/O/W) such as a milk, a cream or a cream gel. They may optionally be packaged as an aerosol and may be in the form of a spray. The compositions according to the invention are preferably in the form of an O W or W/O emulsion, more preferably O/W emulsions. 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 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 that may be as small as 100 nm.

For the O/W emulsions, examples of emulsifiers that may be mentioned include nonionic 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 a 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 alkyl polyglucoside 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.

COSMETIC USES The compositions according to the invention find their application in a large number of treatments, especially cosmetic treatments, of the skin, the lips and the hair, including the scalp, especially for protecting and/or caring for the skin, the lips and/or the hair, and/or for making up the skin and/or the lips. Another object of the present invention consists of the use of the compositions according to the invention as defined above for the manufacture of cosmetic products for treating the skin, the lips, the nails, the hair, the eyelashes, the eyebrows and/or the scalp, especially care products, antisun protection products and makeup products. The cosmetic compositions according to the invention may be used, for example, as makeup products.

The present invention concerns also a cosmetic process for the care and/or make-up of the keratinic materials which consists in applying on to the surface at least one composition as above defined.

The term "keratinic materials" includes the skin, the scalp, the hair, eyelashes, eyebrows and nails.

EXAMPLES

The present invention will be described in more detail by way of examples, which however should not be construed as limiting the scope of the present invention.

EXAMPLE 1

The following composition is in accordance with the invention. The ingredients are given as weight percentages of active material relative to the total weight of the composition.

CROSSPOLYMER (CARBOPOL ULTREZ 20 POLYMER

® BY LUBRIZOL)

D WATER 4.00

PHENYLBENZIMIDAZOLE SULFONIC ACID

2.00

(EUSOLEX 232 ® by MERCK)

TROMETHAMINE 1.248

E ALCOHOL 7.00

Evaluation

SPF 45

PPD 19 (PA++++)

Non Greasy sensation (score) 5.0

Natural whitish color (score) 5.0

PREPARATION OF THE COMPOSITION (EXAMPLE 1

The above component was prepared with normal procedure for o/w emulsion containing powder. The oily phase Al and the aqueous phase B were respectively prepared by mixing the raw materials, with mechanical stirring, at 80 degrees Centigrade. The obtained mixtures were macroscopically homogeneous. The powder phase A2 was added into the oily phase Al . The oily phase mixture (A1+A2) was slowly introduced into the aqueous phase B using a homogenizer at a stirring speed of 5000 rpm for 10 minutes at 65 degrees Centigrade. To the obtained emulsion (A1+A2+B) was added the phase C using a homogenizer at a stirring speed of 5000 rpm for 10 minutes. The obtained emulsion (A1+A2+B+C) was cooled to room temperature with stirring. To the emulsion was added the phase D with stirring. The obtained emulsion (A1+A2+B+C+D) was cooled to room temperature with gentle stirring, and thereto was added the phase E, to give the composition. The composition according to Example 1 was an o/w cream-type emulsion.

PROTOCOL FOR EVALUATION OF COMPOSITIONS

(1) Skin Appearance after Application The evaluation was conducted by cosmetic professional panelists (n=6). Proper amount (pearl size) of the formula was applied on a forearm of each panelist, and evaluated by themselves. Application and appearance after application was evaluated and scored among 1 (very bad), 2 (bad), 3(moderate), 4 (good) and 5 (very good). Criteria for the evaluation are as follows. (1) Non-greasy sensation: when cosmetic composition was applied on the skin, skin appearance was graded on a five-point scale, from very greasy (score 1) to no greasy (score 5).

(2) Natural whitish look: when cosmetic composition is applied on the skin, the skin appearance was graded on a five-point scale, from unnatural white (score 1), to natural white (score 5).

Then, the averaged score was graded on a four-point scale, according to the following criteria: Excellent: 5.0-4.0, Fair: 3.9-3.0, Not fair or poor: 2.9-2.0 and Poor: 1.9-1.0.

(2) SPF and PPD measurement The sun protection factor (SPF) is expressed mathematically as the ratio of the irradiation time necessary to reach the erythema-forming threshold with the UV-screening agent (UV filter) to the time necessary to reach the erythema-forming threshold without UV-screening agent. It is evaluated in vivo especially according to the international method published by Colipa / CTFA SA / JCIA (May 2006). To characterize the protection with respect to UV-A, the PPD (persistent pigment darkening) method, which measures the skin color observed 2 to 4 hours after exposure of the skin to UV-A, is particularly recommended and used. This method has been adopted since 1996 by the Japanese Cosmetic Industry Association (JCIA) for the UV-A labelling of products and is frequently used by test laboratories in Europe and the United States (Japan Cosmetic Industry Association Technical Bulletin. Measurement Standards for UVA protection efficacy. Issued November 21, 1995 and effective as of January 1, 1996).

EXAMPLES 2 and 3

The following components were prepared in the same manner as EXAMPLE 1.

SILICA (and) TITANIUM DIOXIDE (SUNSIL TIN 50

6.00 6.00 by SUNJIN CHEMICAL)

BORON NITRIDE (PUHP 1030L by SAINT GOBAIN

1.00

CERAMICS)

A2

BORON NITRIDE (SHP 3 MIZUSHIMA by

1.00 FERROALLOY)

SILICA (SUNSPHERE H-33 by AGC SI-TECH) 0.50 0.50

WATER qs 100 qs 100

EDTA 0.05 0.05

GLYCERIN 3.00 3.00

PROPYLENE GLYCOL 8.00 8.00

B

PPG-5-CETETH-20 0.40 0.40

POTASSIUM CETYL PHOSPHATE 1.50 1.50

TEREPHTHALYLIDENE DICAMPHOR SULFONIC

12.00 12.00 ACID 33% solution

TRIETHANOLAMINE 2.48 2.48

AMMONIUM POLYACRYLOYLDIMETHYL

0.20 0.20 TAURATE

C

ACRYLATES/ClO-30 ALKYL ACRYLATE

0.21 0.21 CROSSPOLYMER

WATER 4.00 4.00

PHENYLBENZIMIDAZOLE SULFONIC ACID

D 2.00 2.00

TROMETHAMINE 1.248 1.248

E ALCOHOL 7.00 7.00

Evaluation (Score)

Non-greasy sensation 4.0 4.2

Natural whitish look 4.0 4.2

COMPARATIVE EXAMPLES 1-5

The following components were prepared in the same manner as EXAMPLE 1.

GLYCERYL STEARATE (and)

1.50 1.50 1.50 1.50 1.50 PEG- 100 STEARATE

STEARIC ACID 2.00 2.00 2.00 2.00 2.00

CETYL ALCOHOL 0.40 0.40 0.40 0.40 0.40

PRESERVING AGENT 0.70 0.70 0.70 0.70 0.70

Al

ETHYLHEXYL SALICYLATE 5.00 5.00 5.00 5.00 5.00

ETHYLHEXYL TRIAZONE 1.50 1.50 1.50 1.50 1.50

DROMETRIZOLE

3.00 3.00 3.00 3.00 3.00 TRISILOXANE

DIMETHICONE 4.50 4.50 4.50 4.50 0.50

SILICA (and) TITANIUM

DIOXIDE (SUNSIL TIN 50 by 6.00 6.00

SUNJIN CHEMICAL)

TALC (and) SILICA (and)

ALUMINA (and) TITANIUM

DIOXIDE (COVERLEAF 6.00

AR-80 by JGC CATALYSTS

AND CHEMICALS)

TITANRJM DIOXIDE (and)

A2

SILICA (and) ALUMINA

(SYMPHOLIGHT WW by JGC 6.00 CATALYSTS AND CHEMICALS )

BORON NITRIDE (Softtouch

CC6058 Powder by 1.00 1.00 1.00 1.00 MOMENTIVE)

SILICA (SUNSPHERE H-33 by

0.50 0.50 0.50 0.50 AGC SI-TECH)

WATER qs 100 qs 100 qs 100 qs 100 qs 100

EDTA 0.05 0.05 0.05 0.05 0.05

GLYCERIN 3.00 3.00 3.00 3.00 3.00

B PROPYLENE GLYCOL 8.00 - 8.00 8.00 8.00 8.00

PPG-5-CETETH-20 0.40 0.40 0.40 0.40 0.40

POTASSIUM CETYL

1.50 1.50 1.50 1.50 1.50 PHOSPHATE TEREPHTHALYLIDENE

DICAMPHOR SULFONIC 12.00 12.00 12.00 12.00 12.00 ACID (33% aqueous solution)

TRIETHANOLAMINE 2.48 2.48 2.48 2.48 2.48

AMMONIUM POLYACRYLOYLDIMETHY 0.20 0.20 0.20 0.20 0.20 L TAURATE

c

ACRYLATES/C 10-30 ALKYL

ACRYLATE 0.21 0.21 0.21 0.21 0.21 CROSSPOLYMER

WATER 4.00 4.00 4.00 4.00 4.00

D PHENYLBENZIMIDAZOLE

2.00 2.00 2.00 2.00 2.00 SULFONIC ACID

TROMETHAMINE 1.248 1.248 1.248 1.248 1.248

E ALCOHOL 7.00 7.00 7.00 7.00 7.00

Evaluation (Score)

Non-greasy sensation 3.8 2.7 1.8 2.5 2.8

Natural whitish look 3.2 3.5 2.7 2.8 1.0

Powder shape and size

SILICA (and) ALUMINA CATALYSTS AND CHEMICALS

Note: Powder shape was determined with an electric microscope. Mean size was quoted from the supplier materials. From the experiment, it was proved that the formula according to the present invention showed less greasy sensation, high defect-hiding effect and transparent look, which was not achieved by the formulas according to comparative examples.

Claims

CLAIM What is claimed is:

1. A composition comprising in a cosmetically acceptable medium

(A) at least one organic UV filter,

(B) spherical composite particles with a mean size of from 1 to 20 μπι comprising a matrix and an inorganic UV filter;

(C) boron nitride particles, and

(D) spherical porous silica particles.

2. The composition according to claim 1, wherein the (C) boron nitride has a platelet shape.

3. The composition according to Claim 1 or 2, wherein the inorganic UV filter of the (B) spherical composite particles is titanium oxide, and/or zinc oxide, and more preferably titanium dioxide.

4. The composition according to any one of Claims 1 to 3, wherein the inorganic material used in the matrix of the (B) spherical composite particles is selected from the group consisting of silica, mica, talc, iron oxide, aluminium oxide and glass.

5. The composition according to any one of Claims 1 to 3, wherein the matrix of the (B) spherical composite particles comprises organic materials selected from the group consisting of poly(meth)acrylates, polyamides, silicones, polyurethanes, polyethylenes, polypropylenes, polystyrenes, polycaprolactams, polysaccharides, polypeptides, polyvinyl derivatives, waxes, polyesters and polyethers.

6. The composition according to any one of Claims 1 to 5, wherein the matrix of the (B) spherical composite particles is silica and the inorganic UV filter is titanium dioxide.

7. The composition according to any one of Claims 1 to 6, wherein the amount of the inorganic UV filter is from 1 to 50%, preferably from 2 to 40% and more preferably from 2 to

30% by weight relative to the total weight of the (B) spherical composite particles.

8. The composition according to any one of claims 1 to 7, wherein the amount of the (A) organic UV filter relative to the total weight of the cosmetic composition is from 1 to 50 %, preferably from 5 to 35 %, and more preferably from 10 to 30 % by weight.

9. The composition according to any one of claims 1 to 8, wherein the amount of the (B) spherical composite particles relative to the total weight of the cosmetic composition is from 0.1 to 15 %, preferably from 1 to 12 %, and more preferably from 2 to 10 % by weight.

10. The composition according to any one of claims 1 to 9, wherein the (C) boron nitride particles have a particle size distribution such that the value of D₅₀ (50 percent of the particles have a diameter lower this value) is from 2 to 12 μπι.

11. The cosmetic composition according to any one of claims 1 to 10, wherein the amount of the (C) boron nitride particle relative to the total weight of the cosmetic composition is from 0.01 to 10%, preferably from 0.1 to 5%, and more preferably from 0.5 to 3% by weight.

12. The composition according to any one of claims 1 to 11, wherein the (D) spherical porous silica particles have a distribution mean size from 0.5 to 20 μπι and more preferably 2 to 9 μηι.

13. The composition according to any one of claims 1 to 12, wherein the (D) spherical porous silica particles have a specific surface ranging from 50 to 1,000 m /g, and more preferably from 150 to 800 m²/g.

14. The composition according to any one of claims 1 to 13, wherein the (D) spherical porous silica particles have have a specific pore volume ranging from 0.5 to 5 ml/g, and more preferably from 1 to 2 ml/g.

15. The cosmetic composition according to any one of claims 1 to 14, wherein the amount of the (D) spherical porous silica particles relative to the total weight of the composition is from 0.01 to 10% by weight.

16. Use of composition according to any one of claims 1 to 10 for the manufacture of cosmetic products for treating the skin, the lips, the nails, the hair, the eyelashes, the eyebrows and/or the scalp, especially care products, antisun protection products and makeup products.

17. A cosmetic process for the care and/or make-up of the keratinic materials which consists in applying on to the surface at least one composition according to any one of claims 1 to 14.