JP2015000864A - Cosmetic composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition which can protect the skin from ultraviolet rays effectively, whereas being able to hide a dermal defect, such as a wrinkle or a pore effectively.SOLUTION: A composition contains in a physiologically acceptable medium (A) at least one kind of organic ultraviolet shielding agents, (B) at least one kind of hydrophobic silica aerogel particles, (C) at least one kind of elastic silicon particles, (D) at least one kind of sebum absorbing particles different from (B) or (C), (E) at least one kind of semicrystallinity polymer which is a solid in ambient temperature, has a melting point of less than 70°C, comprises a) a polymer skeleton and b) at least one crystalline organicity side chain and/or at least one crystalline organicity block in the polymer skeleton, and has a number average molecular weight of 2000 or more, and (F) at least one kind of particles with a refractive index of 1.5 or more.

Description

  The present invention relates to a specific composition, in particular a skin cosmetic composition, as well as a cosmetic method using it.

  Many cosmetics contain one or more UV screening agents to shield UV light. In particular, skin cosmetics generally contain organic and / or inorganic UV screening agents to protect the skin from UV rays. The need for UV care cosmetics has increased further as the various damages to the skin, such as wrinkles, caused by ultraviolet radiation are now well known.

  On the other hand, visibility related to skin defects such as wrinkles and pores is also a major concern for users of skin cosmetics. Accordingly, many techniques for concealing skin defects have been developed for skin cosmetics such as foundations, concealers, and makeup bases. For example, JP-A-2004-285016 and JP-A-2007-269678 are respectively a specific composite powder or 1,1,3,5,5-pentaphenyl-1,3,5-trimethyltrisiloxane, spherical Disclosed is a technique for hiding skin roughness such as pores by using a powder, a combination of polyglyceryl triisostearate and / or polyglyceryl diisostearate, and an oily paste.

  However, there is no prior art that discloses a technique that enables both effective protection of the skin from ultraviolet light and effective masking of defects on the skin such as wrinkles and pores. In particular, many organic ultraviolet screening agents are usually fat-soluble and thus cause gloss on the skin. Glossy skin typically increases the visibility of skin defects such as wrinkles and pores. Therefore, there is a need for UV care cosmetics that can effectively protect the skin from ultraviolet rays with an organic ultraviolet shielding agent, while effectively hiding skin defects such as wrinkles and pores.

JP-A-2004-285016 JP-A-2007-269678 USP 5240975 EP-669,323 U.S. Pat.No. 2,463,264 U.S. Pat.No. 5,237,071 U.S. Pat.No. 5,166,355 GB-2,303,549 DE-197,26,184 EP-893,119 WO 93/04665 DE-19855649 US7470725 EP-A-295 886 JP-A-61-194009 EP-A-242219 EP-A-295886 EP-A-765656 U.S. Pat.No. 5,538,793 EP-A-0 951 897 US-A-5 156 911 WO-A-01 / 19333 US-A-5 736 125 US-A-5 519 063 EP-A-550 745 JP-A-09188830 JP-A-10158450 JP-A-10158541 JP-A-07258460 JP-A-05017710 JP2001-11340 WO99 / 36477 U.S. Patent No. 6,299,979 U.S. Patent No. 6,387,498 U.S. Pat.No. 5,825,643

Brinker C.J. and Scherer G.W., Sol-Gel Science, New York, Academic Press, 1990 The Journal of the American Chemical Society, 60, 309, February 1938 Van de Hulst, H.C., "Light Scattering by Small Particles", Chapters 9 and 10, Wiley, New York, 1957 S. Nojima, “Melting behavior of poly (e-caprolactone) -block-polybutadiene copolymers”, Macromolecules, 32, 3727-20, 3734 (1999) B. Boutevin et al., "Study of morphological and mechanical properties of PP / PBT", Polymer Bulletin, 34, 117-123 (1995) P. Rangarajan et al., "Morphology of semi-crystalline block copolymers of ethylene- (ethylene-alt-propylene)", Macromolecules, 26, 4640-4645 (1993). P. Richter et al., `` Polymer aggregates with crystalline cores: the system poly (ethylene) poly (ethylene-propylene) '', Macromolecules, 30, 1053-1068 (1997) General article `` Crystallization in block copolymers '' by I.W.Hamley, Advances in Polymer Science, 148, 113-137 (1999) A.C. Cooper, B.SC., A.R.I.C., `` The refractive index of organic pigments. Its determination and significance '', Journal of the oil & color chemists' association, September 1948, No. 339, Vol.XXXI

  An object of the present invention is to provide a composition that can effectively protect the skin from ultraviolet rays by using an organic ultraviolet screening agent, while effectively hiding skin defects such as wrinkles and pores.

The above objects of the present invention can be achieved by a composition comprising, in a physiologically acceptable medium, the following:
(A) at least one organic ultraviolet screening agent,
(B) at least one hydrophobic silica airgel particle,
(C) at least one elastic silicone particle,
(D) at least one sebum-absorbing particle different from (B) or (C),
(E) solid at ambient temperature, having a melting point of less than 70 ° C., a) a polymer backbone, and b) at least one crystalline organic side chain and / or at least one crystalline organic block in said polymer backbone At least one semi-crystalline polymer having a number average molecular weight of 2000 or more, and
(F) At least one particle having a refractive index of 1.5 or more.

The hydrophobic airgel particles of (B)
Per unit mass, 200~1500m ² / g, preferably 600~1200m ² / g, more preferably from 600~800m ² / g specific surface,
1-30 μm in terms of volume average diameter, preferably 5-25 μm, more preferably 5-20 μm, even more preferably 5-15 μm in size and / or 5 to 15 μg per gram measured by wet point It can have an oil absorption capacity in the range of 18 ml, preferably 6-15 ml, more preferably 8-12 ml.

  The hydrophobic silica airgel particles (B) are preferably surface-modified with trimethylsilyl groups.

  The organic ultraviolet shielding agent (A) may be oleophilic.

  The amount of the organic ultraviolet shielding agent (A) may be 3 to 50% by mass relative to the total mass of the composition.

  The amount of the hydrophobic silica airgel particles (B) may be 0.01 to 10% by mass relative to the total mass of the composition.

  The amount of the elastic silicone particles (C) may be 0.01 to 20% by mass relative to the total mass of the composition.

  Unlike (B) or (C), the sebum-absorbing particles (D) may be porous spherical particles.

  The amount of sebum-absorbing particles (D) may be 0.01 to 20% by mass relative to the total mass of the composition.

  The particles having a refractive index of (F) of 1.5 or more may have a white color.

  The particles having a refractive index of (F) of 1.5 or more may be titanium dioxide, boron nitride or zinc oxide.

  The particles having a refractive index of (F) of 1.5 or more may be titanium dioxide having an average particle size of more than 70 μm, preferably 100 μm to 500 μm, more preferably 120 μm to 300 μm.

  The amount of the particles (F) having a refractive index of 1.5 or more may be 0.01 to 20% by mass relative to the total mass of the composition.

  The composition according to the invention is preferably a cosmetic composition comprising a cosmetically acceptable medium.

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

  The present invention also relates to a cosmetic skin care process for reducing visible pores on the skin surface comprising the step of applying a composition according to the invention on the skin.

  The invention also relates to a non-therapeutic cosmetic method for treating skin aging comprising the step of applying a composition according to the invention on the skin.

  As a result of intensive studies, the present inventors contain at least one organic ultraviolet shielding agent that can effectively protect the skin from ultraviolet rays while effectively hiding skin defects such as wrinkles and pores. It has been discovered that a composition can be provided.

Therefore, the composition according to the invention comprises in a physiologically acceptable medium:
(A) at least one organic ultraviolet screening agent,
(B) at least one hydrophilic silica airgel particle,
(C) at least one elastic silicone particle,
(D) at least one sebum-absorbing particle different from (B) or (C),
(E) solid at ambient temperature, having a melting point of less than 70 ° C., a) a polymer backbone, and b) at least one crystalline organic side chain and / or at least one crystalline organic block in said polymer backbone At least one semi-crystalline polymer having a number average molecular weight of 2000 or more, and
(F) At least one particle having a refractive index of 1.5 or more.

  The composition, preferably the cosmetic composition according to the present invention, can exhibit an ultraviolet protection effect by the organic ultraviolet shielding agent (A), and also has an effect of concealing skin defects by a combination of components (B) to (F). Can also be demonstrated. Since the above-described composition is used in the cosmetic method or process according to the present invention, the cosmetic method or process according to the present invention can conceal pores on the skin as a result or treat skin aging. it can.

  In the following, the composition according to the invention and the cosmetic method or process according to the invention will be described in more detail below.

[Composition]
The composition according to the invention comprises in a physiologically acceptable medium:
(A) at least one organic ultraviolet screening agent,
(B) at least one hydrophilic silica airgel particle,
(C) at least one elastic silicone particle,
(D) at least one sebum-absorbing particle different from (B) or (C),
(E) solid at ambient temperature, having a melting point of less than 70 ° C., a) a polymer backbone, and b) at least one crystalline organic side chain and / or at least one crystalline organic block in said polymer backbone At least one semi-crystalline polymer having a number average molecular weight of 2000 or more,
(F) At least one particle having a refractive index of 1.5 or more.

  More specifically, the composition according to the present invention is a cosmetic composition comprising a cosmetically acceptable medium.

  As used herein, “physiologically acceptable medium” is not toxic and can be applied to the skin, lips, hair, scalp, eyelashes, eyebrows, nails, or any other skin area of the body, In particular, it means a medium that can be rephrased as “cosmetically acceptable medium”.

  The components (A) to (F) will be described below.

(Organic UV screening agent)
The composition according to the invention comprises at least one organic UV screening agent. When two or more kinds of organic ultraviolet shielding agents are used, they may be the same or different, and are preferably the same.

  The organic ultraviolet screening agent used in the present invention may have activity in the UV-A and / or UV-B region. The organic ultraviolet shielding agent may be hydrophilic and / or lipophilic, and is preferably lipophilic.

  The organic ultraviolet screening agent may be solid or liquid. The terms “solid” and “liquid” mean solid and liquid at 25 ° C. under 1 atm, respectively.

  Organic UV screening agents include anthranyl compounds; dibenzoylmethane compounds; cinnamic compounds; salicylic acid compounds; camphor compounds; benzophenone compounds; β, β-diphenyl acrylate compounds; triazine compounds; benzotriazole compounds; Nate compound; benzimidazole compound; imidazoline compound; bis-benzoazolyl compound; p-aminobenzoic acid (PABA) compound; methylenebis (hydroxyphenylbenzotriazole) compound; benzoxazole compound; shielding polymer and shielding silicone; α-alkylstyrene It can be selected from the group consisting of derived dimers; 4,4-diarylbutadiene compounds; and mixtures thereof.

  Examples of the organic ultraviolet screening agent include those indicated by their INCI names and mixtures thereof.

-Anthranilate compound: Menthyl anthranilate marketed under the trademark "Neo Heliopan MA" by Haarmann and Reimer.
Dibenzoylmethane compounds: in particular butylmethoxydibenzoylmethane sold under the trademark “Parsol 1789” by Hoffmann-La Roche; and isopropyldibenzoylmethane.
-Cinnamic acid compounds: in particular ethylhexyl methoxycinnamate; isopropyl methoxycinnamate; isopropoxy methoxycinnamate; marketed by Hoffmann-La Roche under the trademark "Parsol MCX";"Neo Heliopan E" by Haarmann and Reimer Isoamyl methoxycinnamate commercially available under the trademark "1000"; sinoxate (2-ethoxyethyl 4-methoxycinnamate); DEA methoxycinnamate; diisopropyl methylcinnamate; and glyceryl ethyl hexamethoxycinnamate.
-Salicylic acid compounds: homosalate marketed under the trademark `` Eusolex HMS '' by Rona / EM Industries; homohexyl salicylate; ethylhexyl salicylate marketed under the trademark `` Neo Heliopan OS '' by Haarmann and Reimer; glycol salicylate; butyl salicylate Octyl; phenyl salicylate; dipropylene glycol salicylate sold under the trademark “Dipsal” by Scher; and TEA salicylic acid marketed under the trademark “Neo Heliopan TS” by Haarmann and Reimer.
-Camphor compounds, especially benzylidene camphor derivatives: 3-benzylidene camphor manufactured by Chimex under the trademark "Mexoryl SD"; 4-methylbenzylidene camphor marketed by Merck under the trademark "Eusolex 6300";"Mexoryl by Chimex Benzylidene camphor sulfonic acid manufactured under the trademark "SL"; camphorbenzalkonium methosulfate manufactured under the trademark "Mexoryl SO" by Chimex; terephthalylidene manufactured under the trademark "Mexoryl SX" by Chimex Dicamphor sulfonic acid; and polyacrylamidomethylbenzylidene camphor manufactured by Chimex under the trademark "Mexoryl SW".
-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 sold under the trademark "Uvinul M40" by BASF; benzophenone-4 (hydroxymethoxybenzophenone) marketed under the trademark "Uvinul MS40" by BASF Sulfonic acid); benzophenone-5 (sodium hydroxymethoxybenzophenone sulfonate); benzophenone-6 (dihydroxydimethoxybenzophenone) sold under the trademark `` Helisorb 11 '' by Norquay; `` Spectra-Sorb UV-24 '' by American Cyanamid Benzophenone-8 marketed under the trademark; "Uvinul DS- Benzophenone-9 (disodium dihydroxydimethoxybenzophenone disulfonate) commercially available under the trademark "49"; benzophenone-12, and n-hexyl 2- (4-diethylamino-2-hydroxybenzoyl) benzoate (UVINUL A + by BASF).
β, β-diphenyl acrylate compounds: in particular octocrylene marketed under the trademark “Uvinul N539” by BASF; and in particular ethocrylene marketed under the trademark “Uvinul N35” by BASF.
-Triazine compound: diethylhexylbutamide triazone marketed by Sigma 3V under the trademark "Uvasorb HEB"; 2,4,6-tris (dineopentyl 4'-aminobenzalmalonate) -s-triazine, Ciba Geigy Bis-ethylhexyloxyphenol methoxyphenyl triazine marketed under the trademark “TINOSORB S” by the company, and Ethylhexyl triazone marketed under the trademark “UVINUL T150” by BASF.
-Benzotriazole compounds, in particular phenylbenzotriazole derivatives: branched and straight chain 2- (2H-benzotriazol-2-yl) -6-dodecyl-4-methylpheno, and those described in USP 5240975.
Benzalmalonate compounds: 4'-methoxybenzalmalonate dineopentyl, and polyorganosiloxanes containing benzalmalonic acid functional groups, for example Polysilicone-15 marketed under the trademark "Parsol SLX" by Hoffmann-LaRoche.
-Benzimidazole compounds, especially phenyl benzimidazole derivatives: phenyl benzimidazole sulfonic acid marketed in particular under the trademark "Eusolex 232" by Merck and phenyl dibenzo marketed under the trademark "Neo Heliopan AP" by Haarmann and Reimer Disodium imidazole tetrasulfonate.
-Imidazoline compound: ethylhexyl dimethoxybenzylidene dioxoimidazoline propionate.
Bis-benzoazolyl compounds: derivatives as described in EP-669,323 and US Pat. No. 2,463,264.
-Para-aminobenzoic acid compounds: PABA (p-aminobenzoic acid), ethyl PABA, ethyldihydroxypropyl PABA, pentyldimethyl PABA, in particular ethylhexyldimethyl PABA, glyceryl PABA marketed under the trademark `` Escalol 507 '' by ISP, And PEG-25 PABA marketed under the trademark “Uvinul P25” by BASF.
A methylene bis (hydroxyphenylbenzotriazole) compound, such as 2,2′-methylenebis [6- (2H-benzotriazol-2-yl), sold in solid form under the trademark “Mixxim BB / 200” by Fairmount Chemical -4-methyl-phenol], 2,2′-methylenebis, marketed in micronized form in aqueous dispersion under the trademark “Tinosorb M” by BASF or “Mixxim BB / 100” by Fairmount Chemical [6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol] and US Pat. Nos. 5,237,071 and 5,166,355, GB-2,303,549, DE-197 , 26, 184 and EP-893, 119,
Drometrizole trisiloxane marketed under the trademark “Silatrizole” by Rhodia Chimie or “Mexoryl XL” by L'Oreal, as represented below.

-Benzoxazole compound: 2,4-bis [5-1 (dimethylpropyl) benzoxazol-2-yl- (4-phenyl) imino] -6- (2-) marketed under the trademark Uvasorb K2A by Sigma 3V Ethylhexyl) imino-1,3,5-triazine.
-Shielding polymer and shielding silicone: Silicone described in WO 93/04665.
-α-alkylstyrene-derived dimer: The dimer described in DE-19855649.
-4,4-diarylbutadiene compound: 1,1-dicarboxy (2,2'-dimethylpropyl) -4,4-diphenylbutadiene.

The organic UV screening agent is preferably selected from the group consisting of:
Butylmethoxydibenzoylmethane, ethylhexyl methoxycinnamate, homosalate, ethylhexyl salicylate, octocrylene, phenylbenzimidazolesulfonic acid, benzophenone-3, benzophenone-4, benzophenone-5, n-hexyl 2- (4-diethylamino-2-hydroxy Benzoyl) benzoate, 1,1 '-(1,4-piperazinediyl) bis [1- [2- [4- (diethylamino) -2-hydroxybenzoyl] phenyl] -methanone, 4-methylbenzylidene camphor, terephthalylidene Dicamphorsulfonic acid, disodium phenyldibenzimidazole tetrasulfonate, ethylhexyltriazone, bis-ethylhexyloxyphenol methoxyphenyltriazine, diethylhexylbutamide triazone, 2,4,6-tris (dineopentyl 4'-aminobenzalmalone -S-triazine, 2,4,6-tris (diisobutyl 4'-aminobenzalmalonate) -s-triazine, 2,4-bis- (n-butyl4'-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- (terphenyl) -triazine, methylenebis-benzotriazolyltetramethylbutylphenol, drometrizol trisiloxane, polysilicone-15, dineopentyl 4'-methoxybenzalmalonate, 1 , 1-Dicarboxy (2,2'-dimethylpropyl) -4,4-diphenylbutadiene, 2,4-bis [5-1 (dimethylpropyl) benzoxazol-2-yl- (4-phenyl) imino]- 6- (2-ethylhexyl) imino-1,3,5-triazine, camphorbenzirconium methosulphate and it Mixture of.

  The composition according to the present invention comprises an organic UV screening agent in an amount of 3% to 50% by weight, preferably 5% to 40% by weight, more preferably 10% to 30% by weight, based on the total weight of the composition. Can be included in amounts.

(Hydrophobic silica airgel particles)
The composition according to the invention comprises at least one hydrophobic silica airgel particle. When two or more types of hydrophobic silica airgel particles are used, they may be the same or different and are preferably the same.

  Silica airgel is a porous material obtained by replacing (by drying) the liquid component of silica gel with air.

  These are generally synthesized in a liquid medium by a sol-gel process and then typically dried by extraction with a supercritical fluid (most commonly used is supercritical CO2). This type of drying can avoid pore shrinkage and material shrinkage. The sol-gel process and various drying operations are described in detail in Brinker C.J. and Scherer G.W., Sol-Gel Science, New York, Academic Press, 1990.

The hydrophobic silica airgel particles used in the present invention are:
Per unit mass, 500 to 1500 ² / g, preferably 600~1200m ² / g, more is the specific surface area preferably in the range of 600~800m ² / g (SW), and / or volume-average diameter (D [0.5] 1) to 1500 μm, preferably 1 to 1000 μm, more preferably 1 to 100 μm, particularly 1 to 30 μm, more preferably 5 to 25 μm, more preferably 5 to 20 μm, and even more preferably 5 to 15 μm. A range size can be indicated.

  According to one embodiment, the hydrophobic silica airgel particles used in the present invention have a volume average diameter (D [0.5]) of 1 to 30 μm, preferably 5 to 25 μm, more preferably 5 to 20 μm, More preferably, the size is in the range of 5 to 15 μm.

  Specific surface area per unit mass is BET (Brunauer-Emmett-Teller) described in The Journal of the American Chemical Society, Volume 60, page 309, February 1938, which corresponds to the international standard ISO 5794/1 (Appendix D). It can be determined by the nitrogen absorption method known as the method. The BET specific surface area corresponds to the total specific surface area of the particles under consideration.

  The size of the silica airgel particles can be measured by static light scattering using a commercially available particle size analyzer, MasterSizer 2000 model from Malvern. Data is processed based on Mie scattering theory. This theory, rigorous for isotropic particles, makes it possible to determine an “effective” particle size in the case of non-spherical particles. This theory is described in particular in a publication by Van de Hulst, H.C., “Light Scattering by Small Particles”, chapters 9 and 10, Wiley, New York, 1957.

According to an advantageous embodiment, the hydrophobic silica airgel particles used in the present invention have a specific surface area (SW) and volume average diameter (D [0.5]) ranging from 600 to 800 m ² / g per unit mass. It represents a size that is in the range of 5-20 μm, preferably 5-15 μm.

Silica airgel particles used in the present invention is ^{advantageously, 0.04g / cm 3 ~0.10g / cm} 3, preferably a packing density in the range of 0.05g / cm ³ ~0.08g / cm ³ and (r) Can show.

In the context of the present invention, the density known as packing density can be evaluated according to the following protocol:
Pour 40 g of powder into a graduated graduated cylinder;
The graduated cylinder is then placed on a Stav 2003 device made by Stampf Volumeter;
Subsequently, subject the graduated cylinder to 2500 packing operations (this operation is repeated until the volume difference between the two subsequent tests is less than 2%),
The final volume Vf of the filled powder is then measured directly on the graduated cylinder. The packing density is determined by the w / Vf ratio (Vf is expressed in cm ³ and w is expressed in g), in this case 40 / Vf.

According to one embodiment, the hydrophobic silica airgel particles used in the present invention are 5-60 m ² / cm ³ , preferably 10-50 m ² / cm ³ , more preferably 15-40 m ² / cm per unit volume. Specific surface area SV that is in the range of ³ is shown.

The specific surface area per unit volume is given by the relation: S _v = S _w xρ
(Wherein, [rho is the packing density expressed in g / cm ^3, S _w is the specific surface area per unit mass represented by m ² / g as described above).

Preferably, the hydrophobic silica airgel particles according to the present invention have an oil-absorbing capacity that is in the range of 5-18 ml / g, preferably 6-15 ml / g, more preferably 8-12 ml / g, measured by wet point. .

The absorbency measured at the wet point, expressed as W _p , corresponds to the amount of oil that needs to be added to 100 g of particles in order to obtain a uniform paste.

This is measured according to the “wet point” method or the determination method for oil uptake of powders as described in standard NF T 30-022. This corresponds to the amount of oil adsorbed on the vacant surface of the powder and / or the amount of oil absorbed by the powder, as determined by the wet point:
An amount of w = 2 g of powder is placed on a glass plate and then oil (isononyl isononanoate) is added dropwise. After adding 4-5 drops of oil to the powder, mix using a spatula and continue adding oil until an oil and powder aggregate is formed. From this point, the oil is added drop by drop followed by grinding the mixture with a spatula. Stop oil addition when a smooth, firm paste is obtained. This paste must be able to be spread on a glass plate without cracking or forming lumps. Then write down the volume of oil used, Vs (expressed in ml).

  Oil uptake corresponds to the Vs / w ratio.

  The airgel used according to the present invention is a hydrophobic silica airgel, preferably a silylated silica (INCI name: silica silylate) airgel.

  The term “hydrophobic silica” refers to the treatment of OH groups with a silyl group Si by treating the surface with a silylating agent such as a halogenated silane such as alkylchlorosilane, a siloxane, in particular dimethylsiloxane such as hexamethyldisiloxane, or silazane. -Rn is understood to mean any silica functionalized with, for example, a trimethylsilyl group.

  For the preparation of hydrophobic silica airgel particles surface-modified by silylation, see the document US7470725.

  In particular, hydrophobic silica airgel particles surface modified with trimethylsilyl groups will be used.

Hydrophobic silica aerogels that can be used in the present invention can include, for example, aerogels commercially available from Dow Corning under the name VM-2260 (INCI name: silica silylate), which particles are about 1000 microns. Mean surface area and specific surface area in the range of 600 to 800 m ² / g per unit mass.

  There may also be mentioned aerogels commercially available from Cabot under the reference names Aerogel TLD201, Aerogel OGD201, Aerogel TLD203, EnovaR Aerogel MT1100 and Enova Aerogel MT1200.

In particular, an airgel marketed by Dow Corning under the name VM-2270 (INCI name: silica silylate) is used, the particles having an average size ranging from 5 to 15 microns and 600-800 m ² / g per unit mass. The specific surface area which is the range of is shown.

  Hydrophobic silica airgel particles, in the composition according to the present invention, as an active substance, are 0.01% by mass to 10% by mass, preferably 0.05% by mass to 10% by mass, more preferably 0.1% by mass relative to the total mass of the composition. It can be present in a content ranging from 5% to 5% by weight, even more preferably from 0.5% to 3% by weight.

(Elastic silicone particles)
The composition according to the invention comprises at least one elastic silicone particle. When two or more kinds of elastic silicone particles are used, they may be the same or different and are preferably the same.

  The elastic silicone (or organopolysiloxane) particles may be spherical, for example.

  Elastic silicone particles may be crosslinked, for example, diorganopolysiloxane containing at least one hydrogen bonded to silicon and diorganopolysiloxane containing ethylenically unsaturated groups bonded to silicon, for example Cross-linking addition reaction in the presence of a platinum catalyst or diorganopolysiloxane containing hydroxyl end groups and diorganopolysiloxane containing at least one hydrogen bonded to silicon, for example, the presence of organotin A dehydrogenative crosslinking condensation reaction, or a diorganopolysiloxane containing a hydroxyl end group and a hydrolyzable organopolysilane, or an organopolysiloxane, for example, of an organic peroxide catalyst. Thermally crosslinks in the presence, or organopolysiloxanes, gamma rays, purple It can be obtained by crosslinking linear or by high energy radiation such as electron beams.

  In one embodiment, the elastic silicone particles are cross-linked, for example as described in patent application EP-A-295 886, for example, (A2) in the presence of a platinum catalyst, (A2) each bonded to silicon at least It is obtained by a cross-linking addition reaction between a diorganopolysiloxane containing two hydrogens and (B2) a diorganopolysiloxane containing at least two ethylenically unsaturated groups bonded to silicon.

  For example, silicones can be obtained via reaction of dimethylpolysiloxane containing dimethylvinylsiloxy end groups with methylhydrogen polysiloxane containing trimethylsiloxy end groups in the presence of a platinum catalyst.

  Compound (A2) is a base reagent for the formation of elastic silicone, and crosslinking is carried out via an addition reaction between compound (A2) and compound (B2) in the presence of catalyst (C2).

Compound (A2) may be, for example, a diorganopolysiloxane containing at least two lower alkenyl groups (for example, C _{2 to} C ₄ ), and the lower alkenyl group is selected from a vinyl group, an allyl group, and a propenyl group. Can do. These lower alkenyl groups can be located at any position of the organopolysiloxane molecule, but in one embodiment are located at the ends of the organopolysiloxane molecule. The organopolysiloxane (A2) can have a branched, linear, cyclic or network structure, and in one embodiment, a linear structure can be used. Compound (A2) can have a viscosity ranging from the liquid state to the gum state. For example, compound (A2) can have a viscosity of at least 100 centistokes at 25 ° C.

  Organopolysiloxane (A2) is methylvinylsiloxane, methylvinylsiloxane-dimethylsiloxane copolymer, dimethylpolysiloxane containing dimethylvinylsiloxy end groups, dimethylsiloxane-methylphenylsiloxane copolymer containing dimethylvinylsiloxy end groups, dimethylvinylsiloxy end Dimethylsiloxane-diphenylsiloxane-methylvinylsiloxane copolymer containing dimethylsiloxane, dimethylsiloxane-methylvinylsiloxane copolymer containing trimethylsiloxy end groups, dimethylsiloxane-methylphenylsiloxane-methylvinylsiloxane copolymer containing trimethylsiloxy end groups, dimethylvinylsiloxy Methyl (3,3,3-trifluoropropyl) polysiloxane containing end groups and dimethylvinylsiloxy end groups No dimethylsiloxane - may be selected from methyl (3,3,3-trifluoropropyl) siloxane copolymers.

  Compound (B2) may be, for example, an organopolysiloxane containing at least two hydrogens linked to silicon in each molecule and is therefore a cross-linking agent for compound (A2).

  In one embodiment, the sum of the number of ethylenic groups per molecule in compound (A2) and the number of hydrogen atoms linked to silicon per molecule in compound (B2) is at least 4.

  Compound (B2) may have any molecular structure. In one embodiment, compound (B2) is a linear or branched structure or a ring structure.

  Compound (B2) can have good miscibility with compound (A), for example, by having a viscosity in the range of 1 to 50,000 centistokes at 25 ° C.

  In one embodiment, the compound (B2) has a molecular ratio of 1 between the total amount of hydrogen atoms linked to silicon in the compound (B2) and the total amount of all ethylenically unsaturated groups in the compound (A2). Can be added in an amount such that it is within the range of 1: 1 to 20: 1.

  Compound (B2) can be selected from methylhydrogenpolysiloxanes containing trimethylsiloxy end groups, dimethylsiloxane-methylhydrogensiloxane copolymers containing trimethylsiloxy end groups, and cyclic dimethylsiloxane-methylhydrogensiloxane copolymers .

  Compound (C2) is a crosslinking reaction catalyst, for example, selected from chloroplatinic acid, chloroplatinic acid-olefin complex, chloroplatinic acid-alkenylsiloxane complex, chloroplatinic acid-diketone complex, platinum black, and platinum on a support. can do.

  The catalyst (C2) is added, for example, as a clean platinum metal in an amount in the range of 0.1 to 1000 parts by weight, for example, 1 to 100 parts by weight per 1000 parts by weight of the total amount of the compounds (A2) and (B2). be able to.

  Other organic groups may be linked to silicon in the aforementioned organopolysiloxanes (A2) and (B2), for example, alkyl groups such as methyl, ethyl, propyl, butyl or octyl; 2-phenylethyl, Substituted alkyl groups such as 2-phenylpropyl or 3,3,3-tri-fluoropropyl; aryl groups such as phenyl, tolyl or xylyl; substituted aryl groups such as phenylethyl; and epoxy groups, carboxylate groups or mercapto groups A monovalent carbon-hydrogen group which is substituted.

  In some embodiments, the elastic silicone particles can be selected from, for example, non-emulsifiable elastomers. As used herein, the term “non-emulsifying” means an organopolysiloxane elastomer that does not contain hydrophilic chains, such as polyoxyalkylene units or polyglycerolated units.

  Spherical elastic silicones are described, for example, in patent applications JP-A-61-194009, EP-A-242219, EP-A-295886 and EP-A-765656, the contents of which are incorporated by reference.

  Elastic silicone particles that can be used include those marketed by the company Dow Corning under the names `` Dow Corning 9505 Powder '' and `` Dow Corning 9506 Powder '', these powders have the INCI name: Dimethicone / Has vinyl dimethicone crosspolymer.

  The elastic silicone particles are selected from elastic organopolysiloxane powders coated with a silicone resin, such as a silsesquioxane resin, for example, as described in US Pat. No. 5,538,793, the contents of which are incorporated by reference. be able to. These elastic powders are marketed by Shin-Etsu under the names “KSP-100”, “KSP-101”, “KSP-102”, “KSP-103”, “KSP-104” and “KSP-105”. INCI name: Vinyl Dimethicone / Methicone Silsesquioxane Crosspolymer.

  Other elastic silicone particles, preferably in spherical powder form, are, for example, hybrid silicone powders functionalized with fluoroalkyl groups, marketed by the company Shin-Etsu under the name “KSP-200”, and for example It may also be a hybrid silicone powder functionalized with phenyl groups, marketed by the company Shin-Etsu under the name “KSP-300”.

  Elastic silicone particles, in the composition according to the present invention, as an active substance, 0.01% to 20% by weight, preferably 0.1% to 10% by weight, more preferably 0.5% by weight, relative to the total weight of the composition. Can be present in a content ranging from 1.0% to 3% by weight, even more preferably from 1.0% to 3% by weight.

  In one embodiment, the composition comprises at least two elastic silicones selected from, for example, elastic organopolysiloxane powders coated with a silicone resin, such as a silsesquioxane resin, as previously described. Particles can be included.

  Elastic silicone particles, which may be spherical in some embodiments, such as at least one non-emulsifying elastic silicone particle, are 0.01% to 20% by weight relative to the total weight of the composition in the composition. %, For example, 0.1% to 10% by weight, further 0.5% to 10% by weight, preferably 0.5% to 5% by weight, more preferably 1.0% to 3% by weight. it can.

  In some embodiments, the compositions disclosed herein comprise at least one elastic silicone particle selected from an elastic organopolysiloxane powder coated with a silicone resin, such as a silsesquioxane resin. , Relative to the total weight of the composition, 0.01% to 20% by weight, for example, 0.1% to 10% by weight, further, for example, 0.5% to 5% by weight, and further, for example, 1.0% to It can be included in an amount in the range of 3% by weight.

  The composition disclosed herein comprises a mixture of elastic silicone particles selected from an elastic organopolysiloxane powder coated with a silicone resin, such as a silsesquioxane resin, and an uncoated elastic organopolysiloxane powder. Can be included. In such a mixture, the elastic organopolysiloxane powder coated with a silicone resin, for example a silsesquioxane resin, is in the range of 0.1% to 10% by weight, for example 0.5% by weight, relative to the total weight of the composition. Can be present in an amount ranging from 1.0% to 3% by weight, for example, 1.0% to 3% by weight, and the uncoated elastic organopolysiloxane powder can be from 0.1% by weight to the total weight of the composition. It can be present in an amount in the range of 10% by weight, for example in the range of 0.5% to 5% by weight, further in the range of, for example, 1.0% to 3% by weight.

(Sebum-absorbing particles)
The composition according to the present invention comprises sebum-absorbing particles, ie at least one compound in the form of particles that absorb sebum, which may be referred to as “sebum pump”. As used herein, the expression “compound that absorbs sebum” is understood to mean a compound capable of absorbing and / or adsorbing sebum. When two or more kinds of sebum-absorbing particles are used, they may be the same or different and are preferably the same. The sebum-absorbing particles are different from the above component (B) or (C).

  Generally, this type of compound is provided in powder form that incorporates sebum. For example, the amount of sebum uptake of the particles can be 1 ml / g or more, such as 1 ml / g to 15 ml / g, such as 1 ml / g to 20 ml / g. This can be, for example, 1.5 ml / g or more, such as 1.5 ml / g to 15 ml / g, such as 1.5 ml / g to 20 ml / g. According to another variant of the present disclosure, the amount of sebum uptake of the particles can be 2 ml / g or more, for example in the range of 2 ml / g to 20 ml / g, such as 2 ml / g to 15 ml / g.

  The sebum uptake amount of the sebum-absorbing particles can be measured according to the method for determining the oil uptake amount of the powder described in the NFT 30-022 standard. This corresponds to the amount of sebum adsorbed on the vacant surface of the powder and / or the amount of sebum absorbed by the powder, as determined by the wet point:

Place an amount of m (gram) particles (this amount depends on the density of the particles) ranging from 0.5g to 5.0g on a glass plate and then drop artificial sebum maintained at a temperature of 29 ° C. But this has the following composition:
It contains 29.00 wt% triolein, 28.50 wt% oleic acid, 18.50 wt% oleyl oleate, 14.00 wt% squalene, 7.00 wt% cholesterol, and 3.00 wt% cholesterol palmitate.

  After adding 4 to 5 drops of artificial sebum, artificial sebum is introduced into the particles using a spatula, and the artificial sebum is continuously added until an aggregate of artificial sebum and particles is formed. From this point, artificial sebum is added drop by drop, and the mixture is then ground with a spatula. Stop adding artificial sebum once a smooth, firm paste is obtained. This paste must be able to be spread on a glass plate without cracking or forming lumps. Next, write down the volume Vs (expressed in ml) of the artificial sebum used. The amount of sebum uptake corresponds to the Vs / m ratio.

  The sebum-absorbing particles are preferably porous particles, particularly porous spherical particles.

According to another aspect of the present disclosure, the sebum-absorbing particles can have a BET specific surface area of 500 m ² / g or more, such as 300 m ² / g or more, such as 600 m ² / g or more and 1500 m ² / g or less.

  Sebum-absorbing particles may be of inorganic or organic origin. These include, for example, silica, polyamide powder [nylon®], acrylic polymer powders such as polymethyl methacrylate, polymethyl methacrylate / ethylene glycol dimethacrylate, polyallyl methacrylate / ethylene glycol dimethacrylate, ethylene glycol dimethacrylate / It can be selected from powders of lauryl methacrylate copolymer and polyethylene, for example polyethylene / acrylic acid. The material for the sebum-absorbing particles may be cross-linked.

  The sebum-absorbing particles may be surface-treated with at least one hydrophobic treatment agent as appropriate.

This hydrophobic treating agent can be selected, for example, from:
-Silicone, such as methicone, dimethicone,
-Fatty acids such as stearic acid,
-Metal soap, such as aluminum dimyristic acid, aluminum salt of hydrogenated tallow glutamic acid,
-Perfluoroalkyl phosphate esters, perfluoroalkyl silanes, perfluoroalkylsilazanes, hexafluoropropylene polyoxides, polyorganosiloxanes containing perfluoroalkyl perfluoropolyether groups,
-Amino acids, N-acylated amino acids and their salts,
-Lecithin, isopropyl triisostearyl titanate, and
-A mixture of them.

  As used herein, the term “alkyl” referred to in the above-cited compounds refers to straight, branched or cyclic alkyl containing 1 to 30 atoms, for example 5 to 16 carbon atoms. It is understood to mean a group.

  N-acylated amino acids can include acyl groups containing 8 to 22 carbon atoms, such as 2-ethylhexanoyl, caproyl, lauroyl, myristoyl, palmitoyl, stearoyl and cocoyl groups. The salt of these components may be an aluminum salt, magnesium salt, calcium salt, zirconium salt, zinc salt, sodium salt, or potassium salt. The amino acid may be, for example, lysine, glutamic acid, or alanine.

Non-limiting examples of sebum absorbing particles according to the present disclosure can include the following:
-Silica powder, for example, porous silica microspheres commercially available under the name `` SILICA BEADS SB-700 '' from Miyoshi Kasei Co., Ltd., `` SUNSPHERE (registered trademark) H51 '', `` SUNSPHERE (registered trademark) commercially available from Asahi Glass ) H33 '' and `` SUNSPHERE (registered trademark) H53 ''; and polydimethylsiloxane commercially available under the names `` SA SUNSPHERE (registered trademark) H-33 '' and `` SA SUNSPHERE (registered trademark) H-53 '' from Asahi Glass Co., Ltd. Coated amorphous silica microspheres,
-Polyamide powder [nylon (registered trademark)], for example, "ORGASOL (registered trademark) 4000" or "ORGASOL (registered trademark) 2002 EXTRA D NAT COS" commercially available from Atochem,
-Acrylic polymer powder, eg polymethyl methacrylate powder, eg “COVABEAD® LH85” sold by Wackherr; polymethyl methacrylate / ethylene glycol dimethacrylate powder, eg sold by Dow Corning `` DOW CORNING 5640 MICROSPONGE (registered trademark) SKIN OIL ADSORBER '', or `` GANZPEARL (registered trademark) GMP-0820 '' sold by Ganz Chemical Company; polyallyl methacrylate / ethylene glycol dimethacrylate powder, for example, “POLY-PORE® L200” or “POLY-PORE® E200” sold by AMCOL; an ethylene glycol dimethacrylate / lauryl methacrylate copolymer powder, for example, sold by Dow Corning “POLYTRAP® 6603”; as well as polyethylene powder, eg Sumitomo Therefore Flobeads (TM) polyethylene / powder acrylic acid commercially available under the trade name.

  According to another variant of the present disclosure, the at least one compound that absorbs and / or adsorbs sebum is of mineral origin.

  According to another variant of the present disclosure, the particles of at least one compound that absorbs and / or adsorbs sebum are selected from silica particles, polyethylene particles, polyamide powder and mixtures thereof. For example, the particles of at least one compound that absorbs and / or adsorbs sebum are silica particles. The silica may have, for example, the above-mentioned characteristics, and can have a sebum uptake amount of 2 ml / g or more, for example, a range of 2 ml / g to 20 ml / g. Such silica particles are commercially available, for example, under the names “SUNSPHERE (registered trademark) H33” and “SUNSPHERE (registered trademark) H53” from Asahi Glass Co., Ltd.

  Sebum-absorbing particles, as an active substance in the composition according to the present invention, are 0.01% by mass to 20% by mass, preferably 0.1% by mass to 10% by mass, more preferably 0.5% by mass relative to the total mass of the composition. It can be present in a content ranging from% to 5% by weight, even more preferably from 1.0% to 3% by weight.

(Semicrystalline polymer)
The composition according to the invention comprises at least one specific semicrystalline polymer. When two or more specific semicrystalline polymers are used, they may be the same or different and are preferably the same.

  The semi-crystalline polymer used in the composition of the present invention is generally introduced into the fatty phase of the composition when the fatty phase is present.

  Within the meaning of the present invention, the term “polymer” is understood to mean a compound comprising at least 2 repeating units, preferably at least 3 repeating units, more particularly at least 10 repeating units. Is done.

  The term “semicrystalline polymer” means a crystalline part, ie a crystalline block in the backbone and / or terminal and / or a crystalline pendant chain and / or terminal chain and an amorphous part in the backbone. And a polymer exhibiting a first order reversible phase transition temperature, in particular a melting point (solid-liquid transition). If the crystalline part is in the form of a crystalline block of the polymer backbone, the amorphous part of the polymer is in the form of an amorphous block, in which case the semicrystalline polymer is, for example, at least one crystalline block And a block copolymer of diblock, triblock or multiblock type comprising at least one amorphous block. The term “block” is generally understood to mean at least 5 identical repeating units. As such, the one or more crystalline blocks have different chemical properties than the one or more amorphous blocks.

  According to a particular embodiment, the one or more semi-crystalline polymers used in the composition according to the invention exhibit a melting point Mp of less than 70 ° C., preferably less than 50 ° C. At least equal to the temperature of the keratin substrate that needs to be received by the composition. Thus, the one or more semi-crystalline polymers can have a melting point M.p. such that 25 ° C. ≦ M.p. <70 ° C., preferably 30 ° C. ≦ M.p. <50 ° C. This melting point is the primary state change temperature.

  The melting point can be measured by any known method, in particular using a differential scanning calorimeter (DSC).

  Advantageously, the one or more semicrystalline polymers of the composition according to the invention have a number average molecular weight Mn of 2000 to 800 000, preferably 3000 to 500 000, more preferably 4000 to 150 000, in particular less than 100 000. Even more preferably, it is in the range of 4000 to 99 000. Preferably, the polymer has a number average molecular weight greater than 5600, such as in the range 5700-99 000. In the composition according to the invention, the semi-crystalline polymer is advantageously soluble in the fatty phase at a temperature above their melting point, at least 1% by weight.

  Blocks of the polymer other than the crystalline chains or blocks are amorphous. Within the meaning of the present invention, the expression “crystalline chain or block”, when used alone, reversibly changes from an amorphous state to a crystalline state depending on whether the temperature is above or below the melting point. It is understood to mean a changing chain or block. Within the meaning of the present invention, a “chain” is a group of atoms that are pendant or lateral to the polymer backbone. A block is a group of atoms belonging to the skeleton, and this group constitutes one of the repeating units of the polymer. Advantageously, the “pendant crystalline chain” may be a chain containing at least 6 carbon atoms.

  Preferably, the crystalline one or more blocks or one or more chains of the semicrystalline polymer comprise at least 30%, preferably at least 40% of the total mass of each polymer. The semi-crystalline polymer of the present invention containing a crystalline block is a block polymer or a multi-block polymer. These can be obtained by polymerization of monomers containing reactive double bonds (or ethylene bonds) or by polycondensation. If the polymers according to the invention are polymers containing crystalline side chains, these side chains are advantageously in random or statistical form. Preferably, the semicrystalline polymers of the present invention are of synthetic origin. In addition, they do not contain a polysaccharide backbone. In general, the crystalline units (chains or blocks) of the semicrystalline polymers according to the invention originate from monomers containing crystalline blocks or chains that are used to produce semicrystalline polymers.

  According to the invention, the semicrystalline polymer is a block copolymer comprising at least one crystalline block and at least one amorphous block, homopolymers and copolymers having at least one crystalline side chain per repeat unit. As well as mixtures thereof.

Semicrystalline polymers that can be used in the present invention are in particular:
-Block copolymers of polyolefins with controlled crystallization, in particular those whose monomers are described in EP-A-0 951 897,
-Especially polycondensates of aliphatic or aromatic polyester type, or aliphatic / aromatic copolyester type,
A homopolymer or copolymer having at least one crystalline side chain, and a homopolymer or copolymer having at least one crystalline block in the backbone, such as those described in patent document US-A-5 156 911,
-Homopolymers or copolymers having at least one crystalline side chain, in particular containing fluorine groups, as described in patent document WO-A-01 / 19333, and
-A mixture of them.

  In the last two cases, the crystalline one or more side chains or the one or more blocks are hydrophobic.

a) Semicrystalline polymers containing crystalline side chains In particular, mention may be made of those defined in patent documents US-A-5 156 911 and WO-A-01 / 19333. These are homopolymers or copolymers containing from 50% by mass to 100% by mass of units obtained by polymerizing one or more monomers having crystalline and hydrophobic side chains.

  These homopolymers or copolymers have arbitrary properties but satisfy the aforementioned conditions.

They are,
-By polymerization of one or more monomers containing reactive or ethylenic double bonds associated with the polymerization, i.e. vinyl, (meth) acryl or allyl groups, in particular radical polymerization and / or
-Obtained by polycondensation of one or more monomers having a co-reactive group (carboxylic acid, sulfonic acid, alcohol, amine or isocyanate), for example polyester, polyurethane, polyether, polyurea or polyamide.

  In general, these polymers are selected in particular from homopolymers and copolymers obtained by the polymerization of at least one monomer containing a crystalline chain which can be represented by formula (I).

In the formula, M represents an atom of the polymer skeleton, S represents a spacer, and C represents a crystalline group.

The crystalline chain “—SC” may be aliphatic or aromatic and may be optionally fluorinated or fully fluorinated. “S” represents a (CH ₂ ) _n or (CH ₂ CH ₂ O) _n or (CH ₂ O) group which may in particular be linear or branched or cyclic, where n is from 0 to 22 It is an integer. Preferably, “S” is a linear group. Preferably “S” and “C” are different.

When the crystalline chain “—SC” is an aliphatic hydrocarbon chain, the chain is an alkyl hydrocarbon containing at least 11 carbon atoms, no more than 40 carbon atoms, preferably no more than 24 carbon atoms. Contains chains. This chain is in particular an aliphatic chain or an alkyl chain containing at least 12 carbon atoms, preferably a C ₁₄ -C ₂₄ alkyl chain.

  When the chain is a fluoroalkyl or perfluoroalkyl chain, it contains at least 6 fluorinated carbon atoms, in particular at least 6 carbon atoms that are fluorinated.

Examples of semicrystalline polymer or copolymer having a crystallinity chains include those derived from one or more of the polymerization of the following monomers: saturated alkyl with C ₁₄ -C ₂₄ alkyl group (meth) Acrylates, C ₁₁ -C ₁₅ perfluoroalkyl (meth) acrylates with perfluoroalkyl groups, C ₁₄ -C ₂₄ alkyl groups with or without fluorine atoms, N-alkyl (meth) acrylamides, C ₁₄ -C ₂₄ alkyl or (having perfluoroalkyl chains per one least 6 fluorine atoms) perfluoro (alkyl) vinyl esters containing a chain of at least six C ₁₄ -C ₂₄ alkyl and perfluoroalkyl chains per one having an alkyl group alkyl or perfluoro (alkyl) vinylether containing chain, C ₁₄ ~C ₂₄ α- o having the a fluorine atom Fins, for example octadecene, para having an alkyl group containing 12 to 24 carbon atoms - alkylstyrene, and mixtures thereof.

  If the polymer is obtained from polycondensation, the previously defined hydrocarbon-based chains and / or fluorinated chains are supported by monomers which may be diacids, diols, diamines or diisocyanates.

When the polymers that are the subject of the present invention are copolymers, these polymers additionally contain 0% to 50% of Y or Z groups resulting from the following copolymerization.
a) Copolymerization of Y, which is a polar or nonpolar monomer, or a mixture of the two:
-When Y is a polar monomer, Y is a monomer carrying a polyoxyalkylenated group (especially an oxyethylenated group and / or an oxypropylenated group), a hydroxyalkyl (meth) acrylate such as hydroxyethyl acrylate, ( (Meth) acrylamide, N-alkyl (meth) acrylamide, N, N-dialkyl (meth) acrylamide, for example, N, N-diisopropylacrylamide, N-vinylpyrrolidone (NVP) or N-vinylcaprolactam, at least one carboxylic acid group Either a monomer carrying (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid or fumaric acid, or a monomer carrying a carboxylic anhydride group, such as maleic anhydride, and mixtures thereof. If -Y is a non-polar monomers, Y is a straight-chain, branched or cyclic alkyl (meth) acrylate type esters, vinyl esters, alkyl vinyl ethers, alpha-olefin, styrene, or C ₁ -C ₁₀ alkyl group It can be a substituted styrene, for example α-methylstyrene. The term “alkyl” is understood within the meaning of the invention to mean a saturated group, in particular a C _{8 to} C ₂₄ group, and better still a C _{14 to} C ₂₄ group, unless otherwise specified. The
b) Copolymerization of Z which is a polar monomer or polar monomer mixture. In this case, Z has the same definition as the “polarity Y” defined above.

Preferably, the semicrystalline polymers containing crystallizable side chains are alkyl groups as defined above, the alkyl (meth) acrylate or alkyl (meth) acrylamide homopolymers, especially having a C ₁₄ -C ₂₄ alkyl group, these monomers And preferably a copolymer of (meth) acrylic acid with a hydrophilic monomer having a different property, such as N-vinylpyrrolidone or hydroxyethyl (meth) acrylate, and mixtures thereof.

b) Polymers carrying at least one crystalline block in the backbone These polymers are in particular block copolymers consisting of at least two blocks with different chemical properties, one being crystallizable.

-Block polymers as defined in patent document US-A-5 156 911 can be used.
-Block copolymers of olefins or cycloolefins containing crystalline chains, for example
Cyclobutene, cyclohexene, cyclooctene, norbornene (ie bicyclo (2,2,1) -2-heptene), 5-methylnorbornene, 5-ethylnorbornene, 5,6-dimethylnorbornene, 5,5,6-trimethylnorbornene , 5-ethylidene norbornene, 5-phenyl norbornene, 5-benzyl norbornene, 5-vinyl norbornene, 1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene Dicyclopentadiene or a mixture thereof;
Obtained from block polymerization with ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-eicosene, or mixtures thereof What
Especially block copoly (ethylene / norbornene) and (ethylene / propylene / ethylidene norbornene) block terpolymers. Those obtained from block copolymerization of at least two C ₂ -C ₁₆ , such as those mentioned above, better C ₂ -C ₁₂ , even better still C ₄ -C ₁₂ α-olefins, especially ethylene and 1 -Block bipolymers with octene can also be used.

The copolymer may be a copolymer exhibiting at least one crystalline block in which the copolymer residue is amorphous (at ambient temperature). These copolymers can further exhibit two crystalline blocks with different chemical properties. Preferred copolymers are those that simultaneously contain crystalline and amorphous blocks at ambient temperature, both of which are hydrophobic and lipophilic and are continuously distributed, for example: Mention may be made of polymers containing one of the crystalline blocks and one of the amorphous blocks:
A) a crystalline block of the nature of polyester, such as poly (alkylene terephthalate), b) a crystalline block of the nature of polyolefin, such as polyethylene or polypropylene,
Amorphous and lipophilic blocks, such as amorphous polyolefins or copoly (olefins) such as poly (isobutylene), hydrogenated polybutadiene or hydrogenated poly (isoprene).

For example, mention may be made of such copolymers containing the following distinct crystalline blocks and distinct amorphous blocks:
α) preferably a hydrogenated poly (ε-caprolactone) -β-poly (butadiene) block copolymer, for example, the article by S. Nojima `` Melting behavior of poly (e-caprolactone) -block-polybutadiene copolymers '', Macromolecules, 32, 3727-20, 3734 (1999),
(beta) Poly (B) Boutevin et al., `` Study of morphological and mechanical properties of PP / PBT '', Polymer Bulletin, 34, 117-123 (1995). Butylene terephthalate) -b-poly (isoprene) block copolymer,
γ) P. Rangarajan et al., `` Morphology of semi-crystalline block copolymer of ethylene- (ethylene-alt-propylene) '', Macromolecules, 26, 4640-4645 (1993) and P. Richter et al., `` Polymer aggregates ''. with crystalline cores: the system poly (ethylene) -poly (ethylene-propylene) '', Macromolecules, 30, 1053-1068 (1997), poly (ethylene) -β-copoly (ethylene / propylene) Block copolymer,
δ) Poly (ethylene) -β-poly (ethylethylene) block copolymer cited in the general article “Crystallization in block copolymers” by IW Hamley, Advances in Polymer Science, 148, 113-137 (1999).

  The semicrystalline polymer of the composition of the present invention is partially crosslinked, provided that the degree of crosslinking does not interfere with the dissolution or dispersion of the polymer in the liquid fatty phase by heating above the melting point of the polymer. Or it may not be crosslinked. Moreover, crosslinking can be chemical crosslinking that occurs by reacting with a polyfunctional monomer during polymerization. The cross-linking can also be a physical cross-linking, in which case the cross-linking is a hydrogen bond or dipole type bond between groups carried by the polymer, e.g. dipole interactions between carboxylate ionomers (these Interaction may be less, either due to the establishment of (supported by the polymer backbone) or phase separation between the crystalline and amorphous blocks supported by the polymer.

  Preferably, the semicrystalline polymer of the composition according to the invention is not crosslinked.

According to one particular embodiment of the invention, the polymer is saturated C ₁₄ -C ₂₄ alkyl (meth) acrylate, C ₁₁ -C ₁₅ perfluoroalkyl (meth) acrylate, N- (C ₁₄ -C ₂₄ alkyl) (meth) acrylamides, C ₁₄ -C ₂₄ alkyl chain or vinyl esters containing perfluoroalkyl chains, vinyl ethers containing C ₁₄ -C ₂₄ alkyl chains or perfluoroalkyl chains, C ₁₄ -C ₂₄ alpha An olefin, at least one monomer containing a crystalline chain selected from para-alkylstyrenes having an alkyl group containing 12 to 24 carbon atoms, and represented by the following formula (w): It is selected from a copolymer obtained by polymerization of a C ₁ -C ₁₀ monocarboxylic acid ester or amide is fluorinated by one case.

Wherein R ₁ is H or CH ₃ , R represents an optionally fluorinated C ₁ -C ₁₀ alkyl group, X represents O, NH or NR ₂ , R ₂ is when representing a C ₁ -C ₁₀ alkyl group is fluorinated by.

According to a more particular embodiment of the present invention, the polymer is a crystalline, selected from saturated C ₁₄ -C ₂₂ alkyl (meth) acrylates, more particularly poly (stearyl acrylate) and poly (behenyl acrylate). Derived from monomers containing chains.

  Specific examples of structured semi-crystalline polymers that can be used in the composition according to the invention include polymers having the INCI name `` Poly C10-30 alkyl acrylate '', e.g. Intelimer® products from Air Products, e.g. poly Mention may be made of the product Intelimer® IPA 13-1, which is stearyl acrylate, or the product 30 Intelimer® IPA 13-6, which is a behenyl polymer.

Semicrystalline polymers are in particular
Copolymerization of acrylic acid and C ₅ -C ₁₆ alkyl (meth) acrylate, more specifically,
-Copolymerization of acrylic acid with a mass ratio of 1/16/3, hexadecyl acrylate and isodecyl acrylate,
-Copolymerization of 1/19 mass ratio of acrylic acid and pentadecyl acrylate,
-Copolymerization of acrylic acid with mass ratio 2.5 / 76.5 / 20, hexadecyl acrylate and ethyl acrylate,
-Copolymerization of acrylic acid with a mass ratio of 5/85/10, hexadecyl acrylate and methyl acrylate,
-Copolymerization of acrylic acid with a mass ratio of 2.5 / 97.5 and octadecyl methacrylate,
-Hexadecyl acrylate with a mass ratio of 8.5 / 1 / 0.5, polyethylene glycol methacrylate monomethyl ether with 8 ethylene glycol units,
It may also be the one described in Examples 3, 4, 5, 7, 9, and 13 of patent document US-A-5 156 911, having a —COOH group, obtained by copolymerization of acrylic acid.

  For example, the polymer of National Starch structure “O” having a melting point of 44 ° C. as described in patent document US-A-5 736 125, and examples 1, 4, 6, 7 of patent document WO-A-01 / 19333, for example. It is also possible to use semicrystalline polymers with crystalline pendant chains containing fluorine groups, as described in 1 and 8.

  For example, use of semi-crystalline polymer obtained by copolymerization of stearyl acrylate and acrylic acid or NVP having melting points of 40 ° C. and 38 ° C., respectively, as described in patent document US-A-5519 063 or EP-A-550 745 It is also possible to do.

  For example, as described in patent documents US-A-5 519 063 and EP-A-550 745, semi-crystalline polymers obtained by copolymerization of behenyl acrylate and acrylic acid or NVP having melting points of 60 ° C. and 58 ° C., respectively. It is also possible to use it.

  Preferably, the semicrystalline polymer does not contain carboxylic acid groups.

  The one or more semi-crystalline polymers in the composition are from 0.01% to 20% by weight, preferably from 0.5% to 10% by weight, and better still 1.0% by weight, based on the total weight of the composition. May be present in amounts of active substance ranging from 5 to 5% by weight.

(Particles having a refractive index of 1.5 or more)
The composition according to the invention may comprise at least one particle having a refractive index of 1.5 or higher. When two or more kinds of particles are used, they may be the same or different and are preferably the same.

  The particles used should be adapted for use in cosmetics and can persist in physiologically acceptable media, for example not dissolve in said media or in any case not completely soluble Must.

These particles can be selected from:
-Particles having a natural or synthetic substrate at least partially coated with at least one layer of at least one metal;
-Particles having a natural or synthetic substrate at least partially coated with at least one layer of at least one metal compound, for example a metal oxide,
-A large amount of particles formed of at least two layers of different refractive indices, for example two layers of polymer, and
-Metal oxide particles.

  The substrate can include at least one material and may be solid or hollow. The substrate may be organic or inorganic. The substrate may be natural or synthetic. In at least one embodiment, the substrate can be selected from synthetic substrates.

  Non-limiting examples of suitable substrates include glass, ceramic, graphite, metal oxides, alumina, silica, silicates such as aluminosilicates and borosilicates, and synthetic mica.

  The substrate is preferably a metal oxide, more preferably titanium dioxide, boron nitride or zinc oxide.

  In one embodiment, the particles having a refractive index of 1.5 or more may contain a layer of metal or metal compound.

  The metal or metal compound layer may or may not cover the entire surface of the substrate, and the metal or metal compound layer may be at least partially a layer of another material, such as a transparent material. It may be coated. In at least one embodiment, the layer of metal or metal compound may cover the substrate entirely, directly or indirectly, i.e. by intervening at least one metal or non-metal interlayer. Good.

  The metal may be selected from, for example, Ag, Au, Cu, Al, Ni, Sn, Mg, Cr, Mo, Ti, Pt, Va, Rb, W, Zn, Ge, Te, Se, and alloys thereof. it can. In at least one embodiment, the metal can be selected from Ag, Au, Al, Zn, Ni, Mo, Cr, Cu, and alloys thereof (eg, bronze and brass).

  The metal layer can be present in an amount ranging from 0.1 to 50%, for example 1 to 20% of the total mass of the particles, for example in the case of particles having a substrate coated with silver or gold.

  The glass particles coated with the metal layer can have dimensions that range, for example, from 10 μm to 300 μm, or from 25 μm to 150 μm. If these particles are in the shape of a wafer, the thickness may range from, for example, 0.1 μm to 25 μm, such as 0.5 μm to 10 μm, or 0.5 μm to 5 μm. If these particles are spherical in shape, they may have dimensions that range, for example, from about 10 μm to 100 μm.

  Glass particles coated with a metal layer are described in, for example, Japanese Patent JP-A-09188830, JP-A-10158450, JP-A-10158541, JP-A-07258460, and JP-A-05017710. .

  Another non-limiting example of a particle having an inorganic substrate coated with a metal layer with a refractive index of 1.5 or higher is a silver-coated borosilicate substrate, also called a “white pearlescent product”. Particles.

  Wafer-shaped particles having a glass substrate coated with silver are commercially available, for example, under the name MICROGLASS METASHINE REFSX 2025 PS by Toyal. Particles having a glass substrate coated with a nickel / chromium / molybdenum alloy are marketed, for example, by Toyal under the names CRYSTAL STAR GF 550 and GF 2525.

Regardless of these shapes, particles having a refractive index of 1.5 or more are at least one layer of at least one metal compound, for example, titanium oxide such as TiO ₂ , iron oxide such as Fe ₂ O ₃ , tin oxide, and metal oxide selected from chromium oxide, barium _{sulfate, MgF 2, CeF 3, ZnS} , ZnSe, SiO 2, Al 2 O 3, MgO, Y 2 O 3, SeO 3, SiO, HfO 2, ZrO 2, CeO ₂ , Nb ₂ O ₅ , Ta ₂ O ₅ , MoS ₂ , and particles having a synthetic substrate that is at least partially coated with a mixture or alloy thereof.

  Examples of such particles include, but are not limited to, particles having a synthetic mica substrate coated with titanium dioxide and glass particles coated with brown iron oxide, titanium oxide and / or tin oxide, For example, particles marketed under the trademark REFLECKS® by Engelhard.

Other pigments suitable for use in accordance with the present disclosure include those of the METASHINE class, such as the reference names MC1120, 1080, 1040, 1020, ME2040, and MC2080 sold by Nippon Sheet Glass Co., Ltd. For example, these pigments described in Japanese Patent Application JP2001-11340 are C-GLASS wafers containing 65-72% SiO ₂ and coated with a layer of rutile titanium oxide (TiO ₂ ). These glass wafers have an average thickness of 1 micron and an average size of 80 microns, ie an average size / average thickness ratio of 80. They exhibit a gloss colored blue, green, yellow or silver according to the thickness of the TiO ₂ layer.

  Other suitable particles include, but are not limited to, synthetic mica substrates (fluorophlogopite mica) that have a size in the range of 80-100 μm and are coated with titanium dioxide that accounts for 12% of the total mass of the particles. ), For example, those sold under the name PROMINENCE by NIHON KOKEN.

  The particles having a refractive index of 1.5 or more can also be selected from a large amount of particles formed from at least two layers having different refractive indexes. These layers can have polymeric or metallic properties and can include at least one polymer layer. Therefore, the particles having a refractive index of 1.5 or more may be particles derived from a multilayer polymer film. Such particles are described, for example, in International Patent Application Publication No. WO99 / 36477 and US Pat. Nos. 6,299,979 and 6,387,498.

  Non-limiting examples of materials consisting of a multilayer structure of different layers include polyethylene naphthalate (PEN) and its isomers, such as 2,6-, 1,4-, 1,5-, 2,7, and 2, 3-PEN; polyalkylene terephthalate, polyimide; polyetherimide; atactic polystyrene; polycarbonate; polyalkyl methacrylate; polyalkyl acrylate; syndiotactic polystyrene (sPS), syndiotactic poly-α-methylstyrene, syndiotactic poly Dichlorostyrene and copolymers and mixtures of these polystyrenes; cellulose derivatives; polyalkylene polymers; fluorinated polymers; chlorinated polymers; polysulfones; polyethersulfones; polyacrylonitrile; polyamides; silicone resins; epoxy resins; Amide; Ionomer resin; Elast Chromatography; and polyurethanes. Copolymers, such as PEN copolymers (e.g. naphthalene-2,6-, -1,4-, -1,5-, -2,7- and / or -2,3-dicarboxylic acid or esters thereof; a) terephthalic acid or its ester, (b) isophthalic acid or its ester, (c) phthalic acid or its ester, (d) alkane glycol, (e) cycloalkane glycol (e.g., cyclohexanedimethanol diol), (f) Alkanedicarboxylic acids and / or (g) copolymers with cycloalkanedicarboxylic acids), polyalkylene terephthalate copolymers, and styrene copolymers may also be used. In at least one embodiment, each individual layer can contain a mixture of two or more of the above polymers or copolymers.

  Materials intended to constitute a multi-layer structure of different layers may be selected to impart the desired reflective appearance to the particles formed.

  Particles containing a large amount of at least two layers of polymers are commercially available, for example, under the name MIRROR GLITTER from 3M. These particles contain each layer of 2,6-PEN and polymethylmethacrylate in a mass ratio of 80/20. Such particles are described, for example, in US Pat. No. 5,825,643.

  These particles are preferably selected from metal oxides, more preferably titanium dioxide, boron nitride or zinc oxide. Even more preferably, the particles having a refractive index of 1.5 or more are composed of titanium oxide.

  The metal oxide, preferably titanium dioxide, may have an average particle size greater than 70um, preferably 100um to 500um, more preferably 120um to 300um. The metal oxide, preferably titanium oxide, may have at least one coating of the above metals or metal compounds.

  The particles having a refractive index of 1.5 or more are preferably white.

  White glossy particles that can be used in the present invention are capable of reflecting light in all components in the visible region, for example, without significantly absorbing one or more wavelengths. The spectral reflectance of these reflective particles may be, for example, greater than 70% in the 400-700 nm region (visible region), such as at least 80%, at least 90%, or at least 95%.

  The reflective particles preferably have a refractive index of 1.5 or more, more preferably 1.6 or more, and even more preferably 1.7 or more.

  The refractive index of the particles can be measured according to a known method for measuring these refractive indexes. In the case of organic pigments, the refractive index is `` The refractive index of organic pigments. Its determination and significance '' by AC Cooper, B.SC., ARIC, Journal of the oil & color chemists' association, September 1948, It can be measured according to the method described in the article No. 339, Vol. XXXI.

  The one or more particles having a refractive index of 1.5 or more in the composition are 0.01% by mass to 20% by mass, preferably 0.1% by mass to 10% by mass, and more preferably, relative to the total mass of the composition. May be present in an amount of active substance ranging from 0.5% to 5% by weight.

(Additional ingredients)
The composition according to the present invention may comprise at least one inorganic UV screening agent.

  The inorganic ultraviolet shielding agent used in the present invention may have activity in the UV-A and / or UV-B region. The inorganic ultraviolet shielding agent may be hydrophilic and / or lipophilic. The inorganic ultraviolet shielding agent is preferably insoluble in solvents generally used in cosmetics such as water and ethanol.

  The inorganic ultraviolet shielding agent is preferably in the form of fine particles having an average (primary) particle size in the range of 1 nm to 50 nm, preferably 5 nm to 40 nm, more preferably 10 nm to 30 nm. The average (primary) particle size or average (primary) particle size herein is the arithmetic average diameter.

  The inorganic UV screening agent may be selected from the group consisting of silicon carbide, metal oxides that may or may not be coated, and mixtures thereof.

  Preferably, the inorganic UV screening agent is a pigment composed of a metal oxide (average primary particle size: generally 5 nm to 50 nm, preferably 10 nm to 50 nm), for example, UV protection agents that are all well known per se. It is selected from certain pigments composed of titanium oxide (amorphous or rutile and / or anatase crystalline), iron oxide, zinc oxide, zirconium oxide, or cerium oxide. Preferably, the inorganic ultraviolet shielding agent is selected from titanium oxide and zinc oxide, and more preferably titanium oxide.

  The inorganic ultraviolet shielding agent may be either coated or uncoated. The inorganic ultraviolet shielding agent may have at least one coating. Coating is alumina, silica, aluminum hydroxide, silicone, silane, fatty acid or salt thereof (sodium salt, potassium salt, zinc salt, iron salt or aluminum salt, etc.), fatty alcohol, lecithin, amino acid, polysaccharide, protein, alkanolamine And at least one compound selected from the group consisting of waxes such as beeswax, (meth) acrylic polymers, organic UV-screening agents, and (per) fluoro compounds.

  The coating preferably contains at least one organic ultraviolet shielding agent. 2,2'-methylenebis [6- (2H-benzotriazole-), a dibenzoylmethane derivative such as butylmethoxydibenzoylmethane (Avobenzone), and BASF's TINOSORB M 2-yl) -4- (1,1,3,3-tetramethyl-butyl) phenol] (methylenebis-benzotriazolyl tetramethylbutylphenol) may be preferred.

  As is known, the silicone in the coating is obtained by polymerization and / or polycondensation of suitable functional silanes, in which silicon atoms are bonded to one another via oxygen atoms (siloxane bonds) and optionally substituted carbonized. Includes linear or cyclic and branched or bridged structures of indeterminate molecular weight, consisting essentially of major repeating units, in which the hydrogen group is directly bonded to the silicon atom via a carbon atom It may be an organosilicon polymer or oligomer.

  The term “silicone” also includes the silanes required for their preparation, especially alkyl silanes.

  The silicone used in the coating can preferably be selected from the group consisting of alkylsilanes, polydialkylsiloxanes and polyalkylhydrosiloxanes. Even more preferably, the silicone is selected from the group consisting of octyltrimethylsilane, polydimethylsiloxane, and polymethylhydrosiloxane.

  Inorganic UV screening agents composed of metal oxides naturally have other surface treatment agents, especially cerium oxide, alumina, silica, aluminum compounds, silicon compounds, or these before being treated with silicone. May be treated with a mixture of

  The coated inorganic ultraviolet shielding agent comprises an inorganic ultraviolet shielding agent, one or more surface treatment agents having chemical, electronic, mechanochemical and / or mechanical properties and any of the above compounds, and polyethylene, metal alkoxide. (Titanium or aluminum alkoxide), metal oxides, sodium hexametaphosphate, and may be prepared by exposure to, for example, those shown in Cosmetics & Toiletries, February 1990, 105, 53-64.

The coated inorganic UV screening agent
Titanium oxide coated with silica, such as "Sunveil" from Ikeda Bussan Co., Ltd .;
Titanium oxide coated with silica and iron oxide, such as "Sunveil F" from Ikeda Bussan Co., Ltd .;
Takeda's "Microtitanium Dioxide MT 500 SA", Tioxide's "Tioveil", Rhodia's "Mirasun TiW 60", etc., titanium oxide coated with silica and alumina,
Titanium oxide coated with alumina, such as “Tipaque TTO-55 (B)” and “Tipaque TTO-55 (A)” from Ishihara Sangyo, “UVT 14/4” from Kemira,
Takeka's products "Microtitanium Dioxide MT 100 T, MT 100 TX, MT 100 Z or MT-01", Uniqema's products "Solaveil CT-10 W" and "Solaveil CT 100", Merck's products "Eusolex T-AVO", etc. , Titanium oxide coated with alumina and aluminum stearate,
Titanic products such as "Microtitanium Dioxide MT 100 S", titanium oxide coated with alumina and aluminum laurate;
Takeda products such as "Microtitanium Dioxide MT 100 F", titanium oxide coated with iron oxide and iron stearate;
Titanium products coated with zinc oxide and zinc stearate, such as Takeka's product "BR351";
Taketa's products `` Microtitanium Dioxide MT 600 SAS '', `` Microtitanium Dioxide MT 500 SAS '', `` Microtitanium Dioxide MT 100 SAS '', etc., titanium oxide coated with silica and alumina and treated with silicone,
Titanium oxide coated with silica, alumina and aluminum stearate and treated with silicone, such as "STT-30-DS" product of Titanium Industry Co., Ltd .;
Titanium oxide coated with silica and treated with silicone, such as Kemira's "UV-Titan X 195"product;
Titanium oxide coated with alumina and treated with silicone, such as "Tipaque TTO-55 (S)" from Ishihara Sangyo Co., Ltd. or "UV Titan M 262" from Kemira;
Titanium oxide coated with triethanolamine, such as "STT-65-S" from Titanium Industry Co., Ltd .;
Titanium oxide coated with stearic acid such as “Tipaque TTO-55 (C)” manufactured by Ishihara Sangyo Co., Ltd .; or titanium oxide coated with sodium hexametaphosphate such as “Microtitanium Dioxide MT 150 W” manufactured by Teika There may be.

Other titanium oxide pigments treated with silicone, is treated with octyltrimethylsilane, TiO ₂ average size of the individual particles is 25 to 40 nm, for example, is sold under the trademark "T 805" by Degussa Silices TiO ₂ which has been treated with polydimethylsiloxane and whose average particle size is 21 nm, for example, sold under the trademark “70250 Cardre UF TiO ₂ SI ₃ ” by Cardre, polydimethylhydrosiloxane Preferably, the anatase / rutile TiO ₂ is processed under the trade name of, and sold under the trademark “Microtitanium Dioxide USP Grade Hydrophobic” by Color Techniques.

Preferably, the following coated TiO ₂ can be used as a coated inorganic UV screening agent:
Stearic acid (and) aluminum hydroxide (and) TiO ₂ , e.g. the product `` MT-100 TV '' from Teika with an average primary particle size of 15 nm;
Dimethicone (and) stearic acid (and) aluminum hydroxide (and) TiO <sub>2</sub> , for example the product `` SA-TTO-S4 '' from Miyoshi Kasei with an average primary particle size of 15 nm;
Silica (and) TiO ₂ , for example, the product `` MT-100 WP '' from Taker with an average primary particle size of 15 nm;
Dimethicone (and) silica (and) aluminum hydroxide (and) TiO <sub>2</sub> , e.g., the products `` MT-Y02 '' and `` MT-Y-110 M3S '' from Tayka with an average primary particle size of 10 nm;
Dimethicone (and) aluminum hydroxide (and) TiO <sub>2</sub> , for example the product `` SA-TTO-S3 '' from Miyoshi Kasei with an average primary particle size of 15 nm;
Dimethicone (and) alumina (and) TiO ₂ , for example the product `` UV TITAN M170 '' from Sachtleben, with an average primary particle size of 15 nm; and silica (and) aluminum hydroxide (and) alginate (and) TiO ₂ , such as MT-100 AQ, a product from Teika, with an average primary particle size of 15 nm.

From the viewpoint of ultraviolet shielding ability, TiO ₂ coated with at least one organic ultraviolet shielding agent is more preferable. For example, avobenzone (and) stearic acid (and) aluminum hydroxide (and) TiO ₂ , for example the product “HXMT-100ZA” from Tayka with an average primary particle size of 15 nm can be used.

  The uncoated titanium oxide pigments are, for example, Miyoshi, the trademark of “Microtitanium Dioxide MT500B” or “Microtitanium Dioxide MT600B” by Teika, the trademark “P 25” by Degussa, and the trademark “Oxyde de titane transparent PW” by Wacker. It is marketed under the “UFTR” trademark by Kasei, under the “ITS” trademark by Tomen, and under the “Tioveil AQ” trademark by Tioxide.

Uncoated zinc oxide pigments are, for example,
Those sold under the trademark "Z-cote" by Sunsmart,
Sold under the trademark "Nanox" by Elementis, and
It is sold under the trademark “Nanogard WCD 2025” by Nanophase Technologies.

The coated zinc oxide pigment is, for example,
Those sold under the trademark "Oxide Zinc CS-5" by Toshiba (ZnO coated with polymethylhydrosiloxane),
The Nanophase Technologies (as C ₁₂ ~C ₁₅ Finsolv 40% dispersion TN alkyl benzoate) "Nanogard Zinc Oxide FN" trademark those sold,
Those sold under the trademarks `` Daitopersion Zn-30 '' and `` Daitopersion Zn-50 '' by Daito Kasei (containing 30% or 50% zinc nanooxide coated with silica and polymethylhydrosiloxane, Dimethylsiloxane / cyclopolymethylsiloxane dispersion),
Sold under the trademark "NFD Ultrafine ZnO" by Daikin Industries (ZnO as cyclopentasiloxane dispersion coated with a copolymer based on perfluoroalkyl phosphate ester and perfluoroalkylethyl),
Products sold by Shin-Etsu Chemical Co., Ltd. under the trademark `` SPD-Z1 '' (ZnO coated with silicone graft acrylic polymer dispersed in cyclodimethylsiloxane),
What is sold under the trademark "Escalol Z100" by ISP (ethyl hexyl methoxycinnamate / PVP-hexadecene copolymer / alumina-treated ZnO dispersed in a methicone mixture), and Fuji ZnO-SMS-10 Sold under the trademark (ZnO coated with silica and polymethylsilsesquioxane), sold under the trademark `` Nanox Gel TN '' by Elementis (C containing hydroxystearic acid polycondensate) ₁₂ is a -C ₁₅ ZnO dispersed at 55% in alkyl benzoate).

  Uncoated cerium oxide pigments are sold, for example, by Rhone-Poulenc under the trademark “Colloidal Cerium Oxide”.

  Non-coated iron oxide pigments are, for example, trademarks of “Nanogard WCD 2002 (FE 45B)”, “Nanogard Iron FE 45 BL AQ”, “Nanogard FE 45R AQ” and “Nanogard WCD 2006 (FE 45R)” by Arnaud, Or sold under the trademark “TY-220” by Mitsubishi.

  Coated iron oxide pigments are, for example, trademarks of “Nanogard WCD 2008 (FE 45B FN)”, “Nanogard WCD 2009 (FE 45B 556)”, “Nanogard FE 45 BL 345” and “Nanogard FE 45 BL” by Arnaud, Or sold under the trademark “Oxyde de fer transparent” by BASF.

  Mixtures of metal oxides, especially titanium dioxide, including the same mass mixture of silica-coated titanium dioxide and silica-coated cerium dioxide sold under the trademark “Sunveil A” by Ikeda A mixture of titanium dioxide and zinc dioxide coated with alumina, silica and silicone, for example the product “M 261” sold by Kemira, or titanium dioxide and alumina, silica and Mention may also be made of mixtures with zinc dioxide coated with glycerol, for example the product “M 211” sold by Kemira.

  The coated inorganic ultraviolet shielding agent is preferable because it can enhance the ultraviolet shielding effect of the inorganic ultraviolet shielding agent. In addition, the coating may help to uniformly or uniformly disperse the UV screening agent in the composition according to the present invention.

  The composition according to the present invention comprises an inorganic ultraviolet screening agent in an amount of 0.1 to 40% by mass, preferably 1 to 30% by mass, more preferably 5 to 20% by mass, based on the total mass of the composition. it can.

  The composition according to the invention can comprise an aqueous phase.

  The aqueous phase contains water. Water suitable for use in the present invention may be floral water, such as cornflower water, and / or mineral water, such as Vittel water, Lucas water or La Roche Posay water, and / or spring water.

The aqueous phase is a water-miscible organic solvent (at room temperature: 25 ° C.), for example a monoalcohol containing 2 to 6 carbon atoms, such as ethanol or isopropanol; in particular glycerol, propylene glycol, butylene glycol, pentylene glycol, Polyols containing 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms, preferentially 2 to 6 carbon atoms, such as xylene glycol, dipropylene glycol or diethylene glycol; mono, di or tripropylene glycol (C ₁ -C ₄₎ alkyl ethers, mono-, di- or triethylene glycol (C ₁ -C ₄₎ alkyl ethers such as (in particular including 3 to 16 carbon atoms) glycol ether, as well as mixtures thereof You can also.

  The aqueous phase can also contain stabilizers such as sodium chloride, magnesium dichloride or magnesium sulfate.

  The aqueous phase can also include any water-soluble or water-dispersible compound that is compatible with the aqueous phase, such as gelling agents, film-forming polymers, thickeners or surfactants, and mixtures thereof.

  In particular, the composition according to the invention has an aqueous phase content of 1 to 95% by weight, in particular 5 to 85% by weight, more particularly 10 to 75% by weight, based on the total weight of the composition. Can be included.

  The composition according to the invention can comprise at least one liquid and / or solid fatty phase.

  In particular, the composition according to the invention can comprise at least one liquid fatty phase, in particular at least one oil as described below.

  The term “oil” means any fatty substance in liquid form at room temperature (20-25 ° C.) and atmospheric pressure.

  The composition of the present invention comprises the liquid fatty phase, based on the total weight of the composition, 1 to 90% by weight, in particular 5 to 80% by weight, in particular 10 to 70% by weight, more particularly 20 to 50% by weight. It can be included with a content in the range of.

  Suitable oil phases for the preparation of the composition according to the invention can comprise hydrocarbon-based oils, silicone oils, fluoro oils or non-fluoro oils, or mixtures thereof.

  The oil may be volatile or non-volatile.

  The oil may be of animal, vegetable, mineral or synthetic origin.

The term “non-volatile oil” means an oil that remains on the skin or keratin fibers at room temperature and atmospheric pressure. More specifically, the non-volatile oil has an evaporation rate of strictly less than 0.01 mg / cm ² / min.

To measure this evaporation rate, 15 g of the oil or oily mixture to be tested is placed in a 7 cm diameter crystal dish, placed in a large chamber of about 0.3 m ³ and placed in a chamber at 25 ° C. Temperature control and relative humidity measurement control at 50%. The liquid is allowed to evaporate freely without agitation, while ventilating with a blower (Papst-Motoren, reference 8550N, rotating at 2700 rpm) placed vertically on the crystal dish containing the oil or mixture. The blades of the blower are placed 20 cm away from the bottom of the crystal dish, facing the crystal dish. The mass of oil remaining in the crystallization dish is measured periodically. The evaporation rate is expressed in mg of oil evaporated per unit area (cm ² ) and unit time (minutes).

The term “volatile oil” means any non-aqueous medium that can evaporate in less than an hour when it contacts the skin or lips at room temperature and atmospheric pressure. Volatile oil is a cosmetic volatile oil that is liquid at room temperature. More particularly, the volatile oil has an evaporation rate of 0.01 to 200 mg / cm ² / min (including upper and lower limits).

  For the purposes of the present invention, the term “silicone oil” means an oil comprising at least one silicon atom, in particular at least one Si—O group.

  The term “fluoro oil” means an oil containing at least one fluorine atom.

  The term “hydrocarbon-based oil” means an oil mainly containing hydrogen atoms and carbon atoms.

  The oil can optionally contain oxygen, nitrogen, sulfur and / or phosphorus atoms, for example in the form of hydroxyl groups or acid groups.

  The composition according to the invention can be used, for example, for gums, anionic, cationic, amphoteric or nonionic surfactants, silicone surfactants, resins, thickeners, structuring agents such as waxes, dispersants, antioxidants. , Essential oils, preservatives, fragrances, neutralizers, bactericides, UV blockers, vitamins, moisturizers, emollients or cosmetic protective agents such as collagen protectants, and mixtures thereof Any additive commonly used in can also be included.

  The composition according to the invention can be used in various formulation forms conventionally used for topical application, in particular the serum type, by dispersing (O / W) the fatty phase in the aqueous phase or vice versa (W / O). Emulsions containing a liquid or semi-liquid conforming to an emulsion type, or suspensions or emulsions containing a soft semi-solid or solid conforming to a cream or gel type, or multiple of ionic and / or non-ionic types It can be provided in the form of a dispersion of an emulsion (W / O / W or O / W / O), a microemulsion or a cell dispersion. These compositions can be prepared according to conventional methods.

  In addition, the compositions used according to the invention may be fluid to varying degrees and may have the appearance of gels, white or colored creams, ointments, emulsions, serums, pastes or foams.

[Makeup method or process]
The present invention also relates to cosmetic methods, and in particular, non-therapeutic cosmetic methods for caring for and / or making up the skin, reducing skin darkening, improving facial color and unevenness, and / or treating skin aging. It preferably relates to non-therapeutic cosmetic methods for caring for and / or making up the skin and / or treating skin aging. Each possible non-therapeutic cosmetic method includes the step of applying the composition according to the invention onto the skin.

  The cosmetic method according to the present invention can give a cosmetic effect to skin such as facial skin by the ultraviolet shielding effect imparted by the organic ultraviolet shielding agent in the composition used in the present invention of (A). The UV shielding effect can be based on skin care and / or makeup, limiting skin darkening and improving facial color and unevenness, and / or treating skin aging.

  Furthermore, due to the combination of the components (B) to (F), the composition according to the present invention changes the appearance of the skin even though it contains the organic ultraviolet shielding agent (A). For example, visible pores on the skin can be reduced. Therefore, the present invention also relates to a cosmetic skin care process for reducing visible pores on the skin surface, particularly comprising the step of applying a composition according to the present invention on the skin.

  The composition according to the present invention can instantly change or modify the appearance of the skin, such as by changing the light reflection on the skin. Therefore, the composition according to the present invention can conceal skin defects such as pores or wrinkles, and can particularly reduce visible pores.

  Accordingly, the composition according to the present invention can effectively protect the skin from ultraviolet rays, while effectively hiding skin defects such as wrinkles and pores.

  The present invention will be described in more detail through examples. However, these should not be construed as limiting the scope of the invention.

(Example 1 and Comparative Examples 1 to 5)

[Preparation]
The following cosmetic compositions according to Example 1 and Comparative Examples 1 to 5 shown in Table 1 were prepared by mixing the components shown in Table 1. All numerical values for the amounts of ingredients shown in the table are based on “mass%” of the active ingredient.

[Evaluation]
(Pore concealment effect)
Apply each composition of Example 1 and Comparative Examples 1-5 to the face of each of the 5 expert panelists, score the composition according to the following evaluation criteria, and calculate the average score for each composition By doing so, the pore concealing effect of each composition was evaluated.

Evaluation criteria: Visibility of cheek pores
4: greatly reduced
3: decreased
2: Slightly decreased
1: Increased

  The results of evaluation of the pore concealment effect are shown in Table 2 below. The results shown in the column of “pore concealment effect” in Table 2 are based on the following criteria.

Excellent: Average score over 3.5: Average score 2.5-3.5
Inferior: Average score is less than 1.5 to 2.5 Poor: Average score is less than 1.5

(SPF value)
Each composition of Example 1 and Comparative Examples 1 to 5 was placed on a PMMA plate in an amount of 0.75 ml / cm ² , and the SPF value was measured by SPF analyzer UV2000. The SPF values of the compositions are shown in Table 2 below.

  The cosmetic composition of Example 1 has an excellent pore concealing effect, while the cosmetic compositions of Comparative Examples 1 to 5 have inferior pore concealing effects, whereas Example 1 and Comparative Examples 1 to 5 For the other cosmetic compositions, the SPF values of the compositions were found to be comparable.

Claims (17)

In a physiologically acceptable medium,
(A) at least one organic ultraviolet screening agent,
(B) at least one hydrophobic silica airgel particle,
(C) at least one elastic silicone particle,
(D) at least one sebum-absorbing particle different from (B) or (C),
(E) solid at ambient temperature and having a melting point of less than 70 ° C., a) a polymer backbone, b) at least one crystalline organic side chain and / or at least one crystallizable organic in said polymer backbone At least one semicrystalline polymer comprising a block and having a number average molecular weight of 2000 or more, and
(F) A composition comprising at least one kind of particles having a refractive index of 1.5 or more, preferably a refractive index of 1.6 or more. Hydrophobic airgel particles (B) is, per unit mass 200~1500m ² / g, preferably 600~1200m ² / g, more preferably from 600~800m ² / g specific surface,
1-30 μm in terms of volume average diameter, preferably 5-25 μm, more preferably 5-20 μm, even more preferably 5-15 μm in size and / or 5 to 15 μg per gram measured by wet point Having an oil absorption capacity in the range of 18 ml, preferably 6-15 ml, more preferably 8-12 ml,
The composition according to claim 1.   3. The composition according to claim 1, wherein the hydrophobic silica airgel particles of (B) are surface-modified with trimethylsilyl groups.   4. The composition according to any one of claims 1 to 3, wherein the organic ultraviolet shielding agent (A) is lipophilic.   The composition according to any one of claims 1 to 4, wherein the amount of the organic ultraviolet shielding agent (A) is 3 to 50 mass% with respect to the total mass of the composition.   6. The composition according to claim 1, wherein the amount of the hydrophobic silica airgel particles of (B) is 0.01 to 10% by mass with respect to the total mass of the composition.   The composition according to any one of claims 1 to 6, wherein the amount of the elastic silicone particles (C) is 0.01 to 20% by mass relative to the total mass of the composition.   8. The composition according to claim 1, wherein the sebum-absorbing particles of (D) different from (B) or (C) are porous spherical particles.   The composition according to any one of claims 1 to 8, wherein the amount of sebum-absorbing particles (D) is 0.01 to 20% by mass relative to the total mass of the composition.   10. The composition according to any one of claims 1 to 9, wherein the particles having a refractive index of (F) of 1.5 or more are white.   11. The composition according to any one of claims 1 to 10, wherein the particles having a refractive index of (F) of 1.5 or more are titanium dioxide, boron nitride or zinc oxide.   The particles having a refractive index of (F) of 1.5 or more are titanium dioxide having an average particle size of more than 70um, preferably 100um to 500um, more preferably 120um to 300um. The composition as described.   The composition according to any one of claims 1 to 12, wherein the amount of the particles (F) having a refractive index of 1.5 or more is 0.01 to 20% by mass relative to the total mass of the composition.   14. The composition according to any one of claims 1 to 13, which is a cosmetic composition containing a cosmetically acceptable medium.   15. A non-therapeutic cosmetic method for caring for and / or making up the skin, comprising applying the composition according to any one of claims 1 to 14 onto the skin.   15. A cosmetic skin care method for reducing visible pores on the surface of the skin comprising the step of applying the composition according to any one of claims 1 to 14 on the skin.   15. A non-therapeutic cosmetic method for treating skin aging comprising the step of applying the composition according to any one of claims 1 to 14 onto the skin.