JP2017109928A - Composite particles - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide composite particles comprising at least one core particle coated with at least one solid UV filter, the composite particles not losing UV protection ability which is improved in the presence of a particular anionic surfactant, and to provide cosmetic compositions comprising the composite particles, the compositions not losing the improved UV protectivity even when washed with water.SOLUTION: The present invention relates to composite particles comprising at least one (a) core particle, at least one portion of the core particle (a) being covered with at least one first coating layer comprising at least one solid UV filter (b), at least a portion of the first coating layer (c) being covered with at least one second coating layer comprising at least one hydrophobic block copolymer; and to a cosmetic composition comprising the composite particles. The composite particles according to the invention can maintain UV protection ability improved in the presence of a particular anionic surfactant, and the composition according to the invention can maintain UV protectivity improved even when washed with water.SELECTED DRAWING: None

Description

  The present invention relates to composite particles comprising core particles having at least one first coating layer comprising at least one solid UV filter and at least one second coating layer comprising at least one hydrophobic block copolymer. And a composition comprising the composite particles, preferably a cosmetic composition, a method for preparing the composite particles, and the like.

Many cosmetic products include one or more UV filters to shield ultraviolet radiation. In particular, skin cosmetics generally include a solid inorganic UV filter, such as TiO ₂ particulates, to protect the skin from ultraviolet radiation.

  WO2012 / 105060 and WO2012 / 105723 disclose composite pigments comprising small core particles coated with solid inorganic UV filters and / or colored pigments.

  WO 2014/010101 discloses a composite pigment comprising small hollow core particles that are coated with a solid inorganic UV filter.

The above composite pigments can provide improved UV protection performance compared to simple powders of solid inorganic UV filters such as TiO ₂ particulates. Thus, cosmetic compositions comprising the above composite pigments can provide improved UV protection compared to compositions comprising simple powders of solid inorganic UV filters.

WO2012 / 105060 WO2012 / 105723 WO2014 / 010101 U.S. Pat.No. 4,617,390 U.S. Patent No. 6,225,467 WO2004 / 085412 WO06 / 035000 WO06 / 034982 WO06 / 034991 WO06 / 035007 WO2006 / 034992 WO2006 / 034985 USP5240975 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-19,726,184 EP-893,119 WO93 / 04665 DE-19855649 US-A-2002 / 005562 USP5221534 European Patent No. 0293795 JP-A-2-295912 U.S. Pat.No. 3,709,437 U.S. Pat.No. 3,937,364 U.S. Pat.No. 4,022,351 U.S. Pat.No. 4,1147,306 U.S. Pat.No. 4,184,615 U.S. Pat.No. 4,598,862 U.S. Pat.No. 4,615,467 U.S. Pat.No. 5,364,031

Cosmetics & Toiletries, February 1990, 105, 53-64 `` Symmetrical Triazine Derivatives '', IP.COM Journal, IP.COM INC, WEST HENRIETTA, NY, USA (September 20, 2004)

  However, the composite pigments described above may lose improved UV protection performance in the presence of several specific anionic surfactants, and cosmetic compositions containing the composite pigments may be washed with water. It has been observed that even if you do, you may lose your improved UV protection.

  The object of the present invention is a composite particle comprising at least one core particle coated with at least one solid UV filter and does not lose enhanced UV protection performance in the presence of certain anionic surfactants It is to provide a composite particle, as well as a cosmetic composition comprising the composite particle, which does not lose enhanced UV protection when washed with water.

The above purpose is
(a) a composite particle comprising at least one core particle,
The (a) core particles are at least partially covered with (b) at least one first coating layer comprising at least one solid UV filter;
Said first coating layer can be achieved by composite particles, which are at least partially covered by (c) at least one second coating layer comprising at least one hydrophobic block copolymer.

  (a) The average particle diameter of the core particles may be 100 nm or more, preferably 200 nm or more, more preferably 300 nm or more, and / or 50 μm or less, preferably 20 μm or less, more preferably 10 μm or less.

  (a) The core particles may comprise at least one inorganic material and / or at least one organic material, preferably at least one organic material.

  (b) The solid UV filter can be selected from solid inorganic UV filters, preferably selected from the group consisting of silicon carbide, metal oxides, and mixtures thereof, more preferably titanium oxide.

  (b) The solid UV filter may have an average particle size of 1 nm to 200 nm, preferably 5 nm to 100 nm, more preferably 10 nm to 50 nm.

  The mass ratio of (a) core particles to (b) solid UV filter may be 10:90 to 90:10, preferably 20:80 to 80:20, more preferably 30:70 to 70:30.

  (c) The hydrophobic block copolymer may have a recovery rate of 50% or more, preferably 60% or more, more preferably 70% or more.

  (c) the hydrophobic block copolymer is optionally hydrogenated with at least one styrene block and at least one block comprising units selected from butadiene, ethylene, propylene, butylene and isoprene or mixtures thereof; It may be a hydrocarbon-based block copolymer which preferably contains

  (c) Hydrophobic block copolymers are optionally hydrogenated, styrene-ethylene / propylene, styrene-ethylene / butadiene, styrene-ethylene / butylene, styrene-ethylene / isoprene block copolymers, and optionally hydrogen. Added from styrene-ethylene / propylene-styrene, styrene-ethylene / butadiene-styrene, styrene-ethylene / butylene-styrene, styrene-isoprene-styrene, and styrene-butadiene-styrene triblock copolymers, and mixtures thereof You can choose.

  The mass ratio of (a) core particles to (c) hydrophobic block copolymer may be 50:50 to 99: 1, preferably 60:40 to 95: 5, more preferably 70:30 to 90:10. .

  The amount of the second coating layer may be 0.01 to 30% by mass, preferably 0.1 to 20% by mass, more preferably 0.3 to 15% by mass, based on the total mass of the composite particles.

  The above objectives can also be achieved by a composition, preferably a cosmetic composition, comprising the composite particles according to the invention.

  The invention also relates to the cosmetic use of the composite particles according to the invention.

The present invention also provides
The present invention relates to a method, preferably a cosmetic method, comprising the step of applying a composite particle according to the invention or a cosmetic composition according to the invention to a keratin substance.

The present invention also provides
(a) at least one core particle,
(b) at least one solid UV filter, and
(c) relates to a method for producing composite particles comprising the step of subjecting at least one hydrophobic block copolymer to a mechanochemical fusion process.

  As a result of intensive studies, the present inventors have found that composite particles comprising at least one core particle coated with at least one solid UV filter are improved in the presence of a specific anionic surfactant. It has been discovered that it is possible to provide composite particles that do not lose their protective performance, as well as cosmetic compositions containing the composite particles that do not lose enhanced UV protection when washed with water.

Accordingly, the composite particle according to the present invention comprises (a) at least one core particle,
(a) the core particles are (b) at least partially covered with at least one first coating layer comprising at least one solid UV filter;
The first coating layer is at least partially covered with (c) at least one second coating layer comprising at least one hydrophobic block copolymer.

  The composition according to the present invention comprises the above composite particles.

  The composite particles according to the present invention can maintain improved UV protection performance even in the presence of certain anionic surfactants, and the cosmetic composition according to the present invention provides improved UV protection even when washed with water. Can be maintained.

  Hereinafter, the composite particles and the composition according to the present invention will be described in detail.

[Composite particles]
The composite particles according to the present invention comprise (b) at least one core particle that is at least partially covered with at least one first coating layer comprising at least one solid UV filter, The layer is at least partially covered with (c) at least one second coating layer comprising at least one hydrophobic block copolymer. (a) Core particles, (b) solid UV filter, and (c) hydrophobic block copolymer are described below.

{Core particle}
The composite particles according to the present invention comprise at least one (a) core particle. When two or more kinds of (a) core particles are used, these may be the same or different.

  The (a) core particle used in the composite particle according to the present invention is not limited as long as it can be at least partially covered with the first and second coating layers.

  (a) The average particle diameter of the core particles is preferably 100 nm or more, preferably 200 nm or more, more preferably 300 nm or more, and / or 50 μm or less, preferably 20 μm or less, more preferably 10 μm or less.

  Unless otherwise defined, the average particle size or average particle diameter is the arithmetic average diameter, for example, calculating the average of the dimensions of 100 particles selected on an image obtained with a scanning electron microscope. Can be obtained.

  (a) The core particles may have any shape.

  For example, (a) the core particle may be a concave particle having at least one concave surface, preferably generally concave. The concave surface is not a small depression or hole, but a large cavity or depression, preferably containing the geometric center or centroid of the particle. Preferably, (a) the core particle defines a concave inner surface and a convex outer surface opposite the concave inner surface. In particular, (a) the core particles are preferably part of hollow spheres or in the form of ridges. (a) The core particles may have a horseshoe or arch-shaped cross section.

  On the other hand, it is possible to use core particles in the form of plates having an aspect ratio of at least 5, preferably more than 10, more preferably more than 20, more preferably more than 50. The aspect ratio can be determined according to the formula of aspect ratio = length / thickness according to the average thickness and the average length.

  When plate-like particles are used in the present invention, the plate-like particles are 100 nm or more, preferably 200 nm or more, more preferably 300 nm or more, and / or 30 μm or less, preferably 20 μm or less, more preferably 10 μm or less (longest ) Preferably having a length.

  In a preferred embodiment, (a) the core particles are spherical.

  (a) The core particles may be solid or hollow.

  (a) The material of the core particle is not limited. (a) The core particle material may include at least one inorganic material and / or at least one organic material. (a) The core particles may preferably include at least one organic material.

The inorganic material and / or the organic material may be hollow or porous. The porosity of the material, by the BET method, 0.05 m ² / g from 1,500 m ² / g, more preferably ^{0.1m 2 / g 1,000m 2 / g} , more preferably 500 meters ² / g from 0.2 m ² / g It can be characterized by the specific surface area of However, it is preferred to use solid inorganic materials and / or solid organic materials, preferably “non-hollow” materials.

  Preferably, the organic material is (co) poly (meth) acrylate, (co) polyamide, silicone (especially silicone resin), (co) polyurethane, (co) polyethylene, (co) polypropylene, (co) polystyrene, ( (Co) polyhydroxyalkanoate, (co) polycaprolactam, (co) poly (butylene) succinate, (co) polysaccharide, (co) polypeptide, (co) polyvinyl alcohol, (co) polyvinyl resin, fluoro (co) It can be selected from the group consisting of polymers, (co) polyesters, (co) polylactic acid, waxes, amidosulfonic acid polyvalent metal salts, acylated amino acids, and mixtures thereof.

  In particular, copolystyrene may be preferred as the organic material, and styrene / acrylate copolymers and cross-linked styrene / methyl methacrylate copolymers may be more preferred. Thus, (a) core particles include, for example, Sunspheres (small hollow particles made from styrene / acrylate copolymers) marketed by Rohm and Haas, as well as SX859 (A ) And SX866 (B) (small hollow particles made from crosslinked styrene / methyl methacrylate copolymer) may be preferred. Polymethyl methacrylate particles such as MP-2200, MP-2701 and MP-1451 and methyl methacrylate crosspolymers such as MR-7GC (commercially available from Soken Chemical Co., Japan) may also be preferred as organic materials. is there.

  (Co) polyamides such as Nylon®, polyhydroxyalkanoates such as polylactic acid, (co) polyurethanes, silicones and mixtures thereof may also be preferred. As the (co) polyamide particles, SP-500 marketed by Toray Industries, Inc. and Orgasol marketed by Arkema may be more preferred. As the (co) polyurethane particles, D-400 marketed by Toyo Pigment Co., Ltd. may be more preferable. As the silicone, a silicone resin (particularly polymethylsilsesquioxane), for example Tospearl marketed by Momentive Performance Materials, may be more preferred as the organic material.

  As the fluoro (co) polymer, for example, PTFE can be used. As an amidosulfonic acid polyvalent metal salt, for example, N-lauroyl taurine calcium can be used. Lauroyl lysine can be used as the acylated amino acid.

  Polysaccharides can include starch, cellulose and derivatives thereof, and mixtures thereof. Cellulose and its derivatives are preferred. Cellulose and its derivatives may be porous or non-porous. However, it is preferred that cellulose and its derivatives are porous. According to one embodiment, the cellulose derivative can be selected from cellulose esters and ethers.

  The term “cellulose ester” means, in the text above and below, a polymer consisting of an α (1-4) sequence of a partly or fully esterified anhydroglucose ring, All or only part of the free hydroxyl function of the anhydroglucose ring, and a linear or branched carboxylic acid or carboxylic acid derivative (acid chloride or acid anhydride) containing 1 to 4 carbon atoms; It is obtained by the reaction of Preferably, the cellulose ester is obtained by reaction of a portion of the free hydroxyl function of the ring with a carboxylic acid containing 1 to 4 carbon atoms. Advantageously, the cellulose ester is selected from cellulose acetate, propionate, butyrate, isobutyrate, acetobutyrate and acetopropionate, and mixtures thereof.

  The term “cellulose ether” refers to a polymer consisting of an α (1-4) sequence of a partially etherified anhydroglucose ring, wherein a portion of the free hydroxyl function of the ring is replaced by an —OR group R is preferably a linear or branched alkyl group containing from 1 to 4 carbon atoms. Accordingly, the cellulose ether is preferably selected from cellulose alkyl ethers having an alkyl group containing 1 to 4 carbon atoms, such as cellulose methyl, propyl, isopropyl, butyl and isobutyl ether.

Examples of the core particles containing cellulose and derivatives thereof include the following cellulose particles:
Cellulobeads USF (porous cellulose), Cellulobeads D-5, Cellulobeads D-10, MOISCELL PW D-5 XP (potassium succinate), and MOISCELL PW D-50 XP (succinic acid) sold by Daito Kasei Kogyo Co., Ltd. Acid potassium cellulose),
CELFLOW C-25 (cellulose), CELFLOW T-25 (cellulose acetate), CELFLOW TA-25 cellulose acetate marketed by Chisso Corporation
MICROPEARL CB-10 (cellulose) marketed by Matsumoto Yushi Seiyaku Co., Ltd.
Avicel PH105 (microcrystalline cellulose) marketed by FMC corporation,
Celus PH-101 (microcrystalline cellulose), Celus PH-F20JP (microcrystalline cellulose), CEOLUS RC-A591NF (microcrystalline cellulose / cellulose gum) marketed by Asahi Kasei Corporation,
ETHOCEL standard 100 premium (ethyl cellulose) marketed by DOW Chemical.

  As polylactic acid, for example, Ecosoft 608XF and Ecosoft 611 (commercially available from Micro Powder) can be used.

  Preferably, the inorganic material is mica, synthetic mica, talc, sericite, boron nitride, glass flake, calcium carbonate, barium sulfate, titanium oxide, hydroxyapatite, silica, silicate, zinc oxide, magnesium sulfate, magnesium carbonate, trisilicate. May be selected from the group consisting of magnesium oxide, aluminum oxide, aluminum silicate, calcium silicate, calcium phosphate, magnesium oxide, bismuth oxychloride, kaolin, hydrotalcite, mineral clay, synthetic clay, iron oxide, and mixtures thereof it can. In particular, natural mica, synthetic mica, sericite, kaolin, talc, silica, and mixtures thereof are preferable.

  In particular, silica particles such as Cosmo 30, Satinier M16 and BA-1 marketed by JGC Catalysts & Chemicals, Inc. and Sunsphere H33 marketed by AGC S-Tech Co., Ltd. may be preferred.

  (a) The core particles may or may not be coated in advance.

  In certain embodiments, (a) the core particles may be originally coated. (a) The original coating material of the core particles is not limited, but organic materials such as amino acids, N-acylamino acids, amides, silicones, and modified silicones may be preferred. Organic materials include lauroyl lysine and acrylic modified silicone.

  It may be preferred to use a combination of at least one small core particle and at least one large core particle.

  The average particle size or average particle diameter of the small core particles may be greater than 100 nm and less than 1 μm, preferably less than 800 nm, more preferably less than 600 nm.

  The average particle diameter or average particle diameter of the large core particles may be 2 μm or more, preferably 3 μm or more, more preferably 4 μm or more, and even more preferably 5 μm or more. The average particle size of the large core particles can be limited to 30 μm or less, preferably 20 μm or less, more preferably 10 μm or less.

  The material for the small and large core particles can be selected independently. As the material, the organic and inorganic materials described above can be used.

  In the composite particles according to the present invention, the mass ratio of small core particles to large core particles is 10:90 to 90:10, preferably 20:80 to 80:20, more preferably 30:70 to 70:30. It's okay.

In a preferred embodiment, the composite particles according to the invention can meet the following requirements:
The small core particles comprise at least one copolystyrene, preferably a styrene / acrylate copolymer, and / or silica,
The large core particles comprise at least one poly (meth) acrylate, preferably a methyl methacrylate polymer, and / or a silicone resin.

  (a) The core particles in the composite particles have a content of 45 to 90% by mass, preferably 40 to 80% by mass, more preferably 35 to 70% by mass, based on the total mass of the composite particles. May exist.

{Solid UV filter}
The first coating layer of the composite particles according to the present invention comprises at least one (b) solid UV filter. When two or more (b) solid UV filters are used, these may be the same or different.

  (b) The solid UV filter has a content of 1 to 50% by weight, preferably 4 to 40% by weight, more preferably 8 to 35% by weight, based on the total weight of the composite particles in the composite particles. May be present.

(Solid inorganic UV filter)
(a) The solid UV filter (b) in the first coating layer on the core particles may be a solid inorganic UV filter. If two or more solid inorganic UV filters are used, these may be the same or different, preferably the same. The solid inorganic UV filter may be hydrophilic and / or lipophilic. Solid inorganic UV filters are suitably insoluble in solvents such as water and ethanol commonly used in cosmetics. The term “solid” means a solid at 25 ° C. under 1 atm.

  The solid inorganic UV filter is preferably in the form of medium-sized fine particles whose average (primary) particle diameter is in the range of 1 nm to 200 nm, preferably 5 nm to 100 nm, more preferably 10 nm to 50 nm. The average (primary) particle size or average (primary) particle diameter herein is the arithmetic average diameter.

  The solid inorganic UV filter may comprise at least one inorganic compound selected from the group consisting of silicon carbide, metal oxides that may or may not be coated, and mixtures thereof.

  Preferably, the solid inorganic UV filter is a pigment formed of a metal oxide (average primary particle size: generally 1 nm to 200 nm, preferably 5 nm to 100 nm, more preferably 10 nm to 50 nm), e.g. all itself Is a well-known UV photoprotective agent, such as a pigment formed of titanium oxide (amorphous or rutile and / or anatase type crystalline), iron oxide, zinc oxide, zirconium oxide or cerium oxide.

  The solid inorganic UV filter may or may not be coated. The solid inorganic UV filter may have at least one coating. The coating can be alumina, silica, aluminum hydroxide, silicone, silane, fatty acid or salt thereof (e.g. sodium, potassium, zinc, iron or aluminum salt), fatty alcohol, lecithin, amino acid, polysaccharide, protein, alkanolamine, wax, For example, it may contain at least one compound selected from the group consisting of bead wax, (meth) acrylic polymer, organic UV filter, and (per) fluoro compound.

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

Other titanium oxide pigments treated with silicone are preferably treated with octyltrimethylsilane and TiO ₂ with individual particles having an average diameter of 25 to 40 nm, for example marketed under the trademark `` T 805 '' by Degussa Silices. TiO ₂ treated with polydimethylsiloxane and having an average particle size of 21 nm, such as that marketed by Cardre under the trademark “70250 Cardre UF TiO ₂ Si ₃ ”, with polydimethylhydrosiloxane Anatase / rutile TiO ₂ that has been processed and has an average particle size of 25 nm, such as that marketed by Color Techniques under the trademark “Microtitanium Dioxide USP Grade Hydrophobic”.

Preferably, the following coated TiO ₂ can be used as a coated inorganic UV filter:
Stearic acid (and) aluminum hydroxide (and) TiO ₂ , for example, product manufactured by Teika Co., Ltd. `` MT-100 TV '', average primary particle diameter 15 nm,
Dimethicone (and) stearic acid (and) aluminum hydroxide (and) TiO <sub>2</sub> , for example, product `` SA-TTO-S4 '' manufactured by Miyoshi Kasei Co., Ltd., average primary particle diameter 15 nm,
Silica (and) TiO ₂ , for example, product `` MT-100 WP '' manufactured by Teika, average primary particle diameter 15 nm,
Dimethicone (and) silica (and) aluminum hydroxide (and) TiO <sub>2</sub> , for example, products manufactured by Teika Co., Ltd. `` MT-Y02 '' and `` MT-Y-110 M3S '', average primary particle diameter 10 nm,
Dimethicone (and) aluminum hydroxide (and) TiO <sub>2</sub> , for example, product `` SA-TTO-S3 '' manufactured by Miyoshi Kasei Co., Ltd., average primary particle diameter 15 nm,
Dimethicone (and) alumina (and) TiO ₂ , such as the product “UV TITAN M170” from Sachtleben, average primary particle diameter of 15 nm, and silica (and) aluminum hydroxide (and) alginate (and) TiO ₂ , such as Teica stock Company-made product “MT-100 AQ”, average primary particle diameter of 15 nm.

From the viewpoint of UV filter capability, TiO ₂ coated with at least one organic UV filter may be more preferable. Organic UV filters include dibenzoylmethane derivatives, such as butylmethoxydibenzoylmethane (Avobenzone) and 2,2′-methylenebis [6- (2H-benzotriazole-2-) marketed as “TINOSORB” M by the company BASF. Yl) -4- (1,1,3,3-tetramethyl-butyl) phenol] (methylenebis-benzotriazolyl tetramethylbutylphenol) may be preferred. Therefore, for example, avobenzone (and) stearic acid (and) aluminum hydroxide (and) TiO ₂ , for example, product “HXMT-100ZA” manufactured by Teika Co., Ltd., average primary particle diameter of 15 nm can be preferably used.

  The uncoated titanium oxide pigment is, for example, the trademark `` Microtitanium Dioxide MT500B '' or `` Microtitanium Dioxide MT600B '' by Teika Co., Ltd. It is marketed under the trademark “UFTR” by Miyoshi Kasei Co., Ltd., under the trademark “ITS” by Tomen, and under the trademark “Tioveil AQ” by Tioxide.

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

Coated zinc oxide pigments are, for example:
Those marketed by Toshiba under the trademark "Oxide Zinc CS-5" (ZnO coated with polymethylhydrosiloxane),
Marketed by Nanophase Technologies under the trademark “Nanogard Zinc Oxide FN” [Finsolv TN, as 40% dispersion in alkyl benzoate (C ₁₂ -C ₁₅ )],
Those marketed by Daito Kasei Kogyo Co., Ltd. under the trademarks “Daitopersion Zn-30” and “Daitopersion Zn-50” (oxyethylene containing 30% or 50% nano zinc oxide coated with silica and polymethylhydrosiloxane) Polydimethylsiloxane / cyclopolymethylsiloxane dispersion),
Those marketed by Daikin Industries Ltd. under the trademark "NFD Ultrafine ZnO" (ZnO coated with perfluoroalkyl phosphate and perfluoroalkylethyl-based copolymer as a cyclopentasiloxane dispersion),
Those marketed by Shin-Etsu Chemical Co., Ltd. under the trademark `` SPD-Z1 '' (ZnO coated with a silicone grafted acrylic polymer dispersed in cyclodimethylsiloxane),
Commercially available under the trademark `` Escalol Z100 '' by ISP (alumina-treated ZnO dispersed in ethylhexyl methoxycinnamate / PVP-hexadecene copolymer / methicone mixture), trademark `` Fuji ZnO-SMS- 10 '' (ZnO coated with silica and polymethylsilsesquioxane), and
What is marketed by Elementis under the trademark “Nanox Gel TN” [ZnO dispersed at 55% in alkyl benzoate (C ₁₂ -C ₁₅ ) with hydroxystearic acid polycondensate].

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

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

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

  A mixture of metal oxides, in particular a mixture of titanium dioxide and cerium dioxide, such as silica-coated titanium dioxide and silica-coated cerium dioxide marketed under the trademark “Sunveil A” by Ikeda Bussan Co., Ltd. Equal-mass mixture, or a mixture of titanium dioxide and alumina, silica, and zinc dioxide coated with silicone, for example the product “M 261” marketed by Kemira, or coated with titanium dioxide and alumina, silica and glycerol Mention may also be made of admixed zinc dioxide, for example the product “M 211” marketed by the company Kemira.

  It may be preferred that the coating of the solid inorganic UV filter comprises stearic acid and / or isostearic acid. As solid inorganic UV filters, titanium dioxide (and) aluminum hydroxide (and) stearic acid marketed as “MT-100V” by Teika Co., Ltd. and dioxide dioxide marketed as “MT-10EX” by Teika Co., Ltd. Titanium (and) aluminum hydroxide (and) isostearic acid and titanium dioxide (and) dimethicone (and) stearic acid (and) aluminum hydroxide marketed as "SA-TTO-S-4" by Miyoshi Kasei Co., Ltd. Can be mentioned.

  As is known, the silicone in the coating of the solid inorganic UV filter may be an organosilicon polymer or oligomer containing linear or cyclic and branched or cross-linked structures of various molecular weights, which are suitable functionalities. Obtained by polymerization and / or polycondensation of a functional silane, wherein silicon atoms are bonded to one another via an oxygen atom (siloxane bond), and optionally substituted hydrocarbon groups directly to the silicon atom via a carbon atom It consists essentially of repeating main units that are joined together.

  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. More preferably, the silicone is selected from the group consisting of octyltrimethylsilane, polydimethylsiloxane, and polymethylhydrosiloxane.

  Of course, inorganic UV filters made of metal oxides may have other surface treatment agents, in particular cerium oxide, alumina, silica, aluminum compounds, silicon compounds or their compounds, prior to their treatment with silicone. It may be treated with a mixture.

  Coated solid inorganic UV filters, solid inorganic UV filters, any of the above compounds, as well as polyethylene, metal alkoxides (titanium or aluminum alkoxides), metal oxides, sodium hexametaphosphate, and for example Cosmetics & Toiletries, February 1990. 105, pages 53-64, and may be prepared by subjecting one or more surface treatments of chemical, electronic, mechanochemical, and / or mechanical properties.

  A coated solid inorganic UV filter is preferable because the UV filter effect of the solid inorganic UV filter can be improved. In addition, the coating can function as a binder to immobilize the UV filter on the core particles.

  On the other hand, uncoated solid inorganic UV filters such as uncoated titanium oxide pigments such as JA-1, JP-3, and JA-C marketed by Teika Co. can be used as the solid inorganic UV filter.

  The composite particles according to the invention can have an effect in that they can give a transparent or clear appearance rather than a white appearance, because (b) the solid UV filter does not agglomerate, (a) This is because it spreads on the core particles. (b) Note that the free particles of the solid UV filter aggregate easily and give the skin a white appearance.

  The solid inorganic UV filter is a composite particle according to the present invention, wherein (a) the mass ratio of the core particles to the solid inorganic UV filter is 90:10 to 10:90, preferably 80:20 to 20:80, more preferably 70. Can be used at a ratio of: 30 to 30:70.

(Solid organic UV filter)
(a) The solid UV filter in the first coating layer on the core particle may be a solid organic UV filter. If two or more solid organic UV filters are used, these may be the same or different, preferably the same. The solid organic UV filter may be hydrophilic and / or lipophilic. Solid organic UV filters are suitably insoluble in solvents such as water and ethanol commonly used in cosmetics. The term “solid” means a solid at 25 ° C. under 1 atm.

  The solid organic UV filter is preferably in the form of medium-sized particles whose average (primary) particle diameter is in the range of 100 nm to less than 300 nm, preferably 100 nm to less than 250 nm, more preferably 100 nm to less than 200 nm. The average (primary) particle size or average (primary) particle diameter herein is the arithmetic average diameter.

  The material of the solid organic UV filter is not limited as long as it is organic. When two or more kinds of solid organic UV filters are used, the materials of the solid organic UV filters may be the same or different from each other.

  The solid organic UV filter may include at least one organic compound selected from the group consisting of benzotriazole derivatives, oxanilide derivatives, triazine derivatives, triazole derivatives, vinyl group-containing amides, cinnamic acid amides, and sulfonated benzimidazoles. Good.

  A preferred class of solid oxanilide UV absorbers has the formula:

[Wherein R ₁ and R ₂ are independently C ₁ -C ₁₈ alkyl or C ₁ -C ₁₈ alkoxy]
It is what has. A preferred compound of formula (1) is N- (2-ethoxyphenyl) -N ′-(2-ethylphenyl) -ethanediamide.

  A preferred class of solid triazine UV absorbers has the formula:

[Wherein R ₃ , R ₄ and R ₅ are independently H, OH, C ₁ -C ₁₈ alkoxy, NH ₂ , NH—R ₆ or N (R ₆ ) ₂ (where R ₆ is , C ₁ -C ₁₈ alkyl), OR ₆ (wherein R ₆ is C ₁ -C ₁₈ alkyl), phenyl, phenoxy or anilino, or pyrrole (wherein each phenyl, phenoxy or anilino) Or the pyrrolo moiety is optionally substituted with 1, 2 or 3 substituents selected from OH, carboxy, CO-NH ₂ , C ₁ -C ₁₈ alkyl or alkoxy), C ₁ -C ₁₈ carboxyalkyl, C ₅ -C ₈ cycloalkyl, methylidene camphor group,-(CH = CH) _m C (= O) -OR ₆ group (wherein m is 0 or 1, R ₆ Have the same meaning as above), or

Or the corresponding alkali metal, ammonium, mono-, - di - or tri -C ₁ -C ₄ alkylammonium, mono-, - di - or tri -C ₂ -C ₄ salts alkanolammonium, or a C ₁ -C ₁₈ alkyl Is an ester]
It is what has.

  A preferred compound of formula (2) is:

As well as 2,4,6-tris (diisobutyl-4'-aminobenzalmalonate) -s-triazine and 2,4-bis (diisobutyl-4-aminobenzalmalonate) -6- (4'-aminobenzylidene camphor) -s-triazine. Particularly preferred is bis-ethylhexyloxyphenol methoxyphenyl triazine marketed by Ciba-Geigy under the trademark “Tinosorb S”.

  Particularly preferred compounds of formula (2) are:

Wherein the individual R ₇ groups are the same or different and are each hydrogen; alkali metal; ammonium group N (R ₈ ) _{4 where} R ₈ is hydrogen or an organic group; C _{1 to} C ₂₀ alkyl; or a polyoxyethylene group containing 1 to 10 ethylene oxide units, the terminal OH group of which may be etherified with a C _{1 to} C ₃ alcohol]
It is what has.

For the compound of formula (30), when R ₇ is an alkali metal, this is preferably potassium or especially sodium; R ₇ is a N (R ₈ ) ₄ group, wherein R ₈ is If it is with the meaning of), this is preferably mono -, di - or tri -C ₁ -C ₄ alkyl ammonium salts, mono -, di - or tri -C ₂ -C ₄ alkanolammonium salts, or There at its C ₁ -C ₂₀ alkyl esters; when R ₈ is C ₁ -C ₂₀ alkyl group, this is preferably, C ₆ -C ₁₂ alkyl groups, more preferably C ₈ -C ₉ alkyl group, It is preferably a 3,5,5-trimethylpentyl group, or most particularly a 2-ethylhexyl group; when R ₈ is a polyoxyethylene group, it preferably contains 2 to 6 ethylene oxide units.

  A preferred class of solid triazole UV absorbers has the formula:

Wherein T ₁ is C ₁ -C ₁₈ alkyl or preferably hydrogen and T ₂ is C ₁ -C ₁₈ alkyl optionally substituted with hydrogen, hydroxyl, or phenyl, preferably α, α-dimethylbenzyl]
It is what has.

  A further preferred class of solid triazole UV absorbers has the formula:

[Wherein T ₂ has the above-mentioned meaning]
It is what has.

  A still further preferred class of solid triazole UV absorbers has the formula:

[Wherein T ₂ has the above-mentioned meaning, preferably t-butyl]
It is what has.

A preferred class of solid vinyl group-containing amide UV absorbers has the formula:
_{R 9 - (Y) m -CO} -C (R 10) = C (R 11) -N (R 12) (R 13) (34)
[Wherein R ₉ is C ₁ -C ₁₈ alkyl, preferably C ₁ -C ₅ alkyl, or OH, C ₁ -C ₁₈ alkyl, C ₁ -C ₁₈ alkoxy or CO-OR ₆ (where R ₆ is phenyl optionally substituted with one, two or three substituents selected from those having the aforementioned meanings; R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ are Are the same or different and are each C ₁ -C ₁₈ alkyl, preferably C ₁ -C ₅ alkyl, or hydrogen; Y is N or O; m has its aforementioned meaning]
It is what has.

  Preferred compounds of formula (34) are 4-octyl-3-penten-2-one, ethyl-3-octylamino-2-butenoate, 3-octylamino-1-phenyl-2-buten-1-one, and 3-dodecylamino-1-phenyl-2-buten-1-one.

  A preferred class of solid cinnamide amide UV absorbers has the formula:

Wherein R ₁₄ is hydroxy or C ₁ -C ₄ alkoxy, preferably methoxy or ethoxy; R ₁₅ is hydrogen or C ₁ -C ₄ alkyl, preferably methyl or ethyl; R ₁₆ is -(CONH) _m -phenyl, wherein m has the meaning as previously described, and the phenyl group is OH, C ₁ -C ₁₈ alkyl, C ₁ -C ₁₈ alkoxy, or CO-OR ₆ (wherein , R ₆ is optionally substituted with 1, 2 or 3 substituents selected from:
It is what has. Preferably R ₁₆ is a phenyl, 4-methoxyphenyl or phenylaminocarbonyl group.

  A preferred class of solid sulfonated benzimidazole UV absorbers has the formula:

[Wherein M is hydrogen or an alkali metal, preferably sodium, an alkaline earth metal such as magnesium or calcium, or zinc]
It is what has.

In the compounds of formulas (1) (35), C 1 ~C 18 alkyl groups are methyl, ethyl, n- propyl, isopropyl, n- butyl, isobutyl, tert- butyl, n- amyl, n- hexyl, n It may be -heptyl, n-octyl, isooctyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, tetradecyl, hexdecyl, or octadecyl, where C ₁ -C ₁₈ alkoxy groups include methoxy, ethoxy, Propoxy, butoxy, n-hexoxy, n-heptoxy, n-octoxy, isooctoxy, n-nonoxy, n-decoxy, n-undecoxy, n-dodecoxy, tetradecoxy, hexadecoxy or octadecoxy are preferred, and methoxy and ethoxy are preferred.

The C ₁ -C ₁₈ carboxyalkyl, carboxymethyl, carboxyethyl, carboxypropyl, carboxy isopropyl, carboxybutyl, carboxyalkyl isobutyl, carboxybutyl, carboxyalkyl amyl, carboxymethyl hexyl, carboxymethyl heptyl, carboxymethyl octyl, carboxymethyl isooctyl, Karubokishinoniru, Carboxydecyl, carboxyundecyl, carboxydodecyl, carboxytetradecyl, carboxyhexadecyl, and carboxyoctadecyl are included, with carboxymethyl being preferred.

The C ₅ -C ₈ cycloalkyl includes cyclopentyl, cyclohexyl, and cyclooctyl.

  Compounds of formulas (1) to (35) are known. The compound of formula (30), along with its production, is described in US Pat. No. 4,617,390.

  Solid organic UV filters are benzotriazole derivatives, in particular phenylbenzotriazole derivatives, such as those sold under the trademark "Silatrizole" by Rhodia Chimie or under the trademark "Mexoryl XL" by L'Oreal. Metrizol trisiloxane is preferred.

  The composite particles according to the present invention can have an effect in that they can give a transparent or clear appearance because the solid organic UV filter does not agglomerate and spreads over the core particles (a). is there. Note that the free particles of the solid organic UV filter can easily aggregate.

  Furthermore, when the solid organic UV filter is used with a solid inorganic UV filter, the composite particles according to the present invention sufficiently disperse the particles of the solid inorganic UV filter in the first coating layer due to the presence of the solid organic UV filter. Can thus have an additional effect in that the solid inorganic UV filter can be present in the form of primary particles in the first coating layer. On the other hand, in the above case, the particles of the solid organic UV filter can also be well dispersed in the first coating layer due to the presence of the solid inorganic UV filter, so the solid organic UV filter is In the form of primary particles. Therefore, both the UV filter effect of the solid inorganic UV filter and the solid organic UV filter can be improved.

  The solid organic UV filter has a mass ratio of 90:10 to 10:90, preferably 80:20 to 20:80, more preferably 70, in the composite particles according to the present invention, in the composite particles according to the invention. Can be used at a ratio of: 30 to 30:70.

{First layer}
(a) The core particles are at least partially covered with at least one first coating layer comprising at least one (b) solid UV filter. Preferably, (a) 10% or more of the surface of the core particle can be covered with the first coating layer. More preferably, (a) 50% or more of the surface of the core particle can be covered with the first coating layer. More preferably, (a) 80% or more of the surface of the core particle can be covered with the first coating layer. Most preferably, (a) the entire surface of the core particles can be covered by the first coating layer.

  The (b) solid UV filter in the first coating layer on the core particles may have an average particle size of 1 nm to 200 nm, preferably 5 nm to 100 nm, more preferably 10 nm to 50 nm.

  (b) By using a solid UV filter, the composite particles according to the present invention can have a UV shielding effect.

  The thickness of the first coating layer may vary depending on several factors such as (b) the size of the solid UV filter. Typically, (b) depending on the average particle size of the solid UV filter, the thickness of the first coating layer ranges from 1 nm to 200 nm, preferably from 5 nm to 100 nm, more preferably from 10 nm to less than 50 nm. It's okay.

  (a) When two or more first coating layers are present on the core particle, the thickness and composition of the first coating layer may be the same or different from each other.

  The first coating layer may include any additional material such as (b) at least one additional liquid UV filter in addition to the solid UV filter. The additional material may be present in an amount ranging from 1 to 50% by weight relative to the total weight of the first coating layer.

  The amount of the first coating layer may be 0.1 to 30% by mass, preferably 1 to 20% by mass, more preferably 5 to 15% by mass, based on the total mass of the composite particles.

(Additional UV filter)
As described above, (a) the first coating layer on the core particles may further comprise at least one additional liquid UV filter. If two or more additional liquid UV filters are used, these may be the same or different and are preferably the same. The additional liquid UV filter may be hydrophilic and / or lipophilic.

  The term “liquid” means a liquid at 25 ° C. under 1 atm. The additional liquid UV filter may be made of at least one organic or inorganic material, preferably at least one inorganic material.

  Additional liquid UV filters include anthranilic acid derivatives; dibenzoylmethane derivatives; liquid cinnamic acid derivatives; salicylic acid derivatives; camphor derivatives; benzophenone derivatives; β, β-diphenyl acrylate derivatives; liquid triazine derivatives; liquid benzotriazole derivatives; Malonate derivatives; benzimidazole derivatives; imidazoline derivatives; bis-benzoazolyl derivatives; p-aminobenzoic acid (PABA) and its derivatives; methylene bis (hydroxyphenylbenzotriazole) derivatives; benzoxazole derivatives; shielding polymers and shielding silicones; α -Dimers derived from alkyl styrene; 4,4-diarylbutadiene; octocrylene and its derivatives, guaiazulene and its derivatives, rutin and its derivatives, flavonoids, biflavonoids, oryzanol and its derivatives , Quinic acid and its derivatives, phenols, retinol, cysteine, aromatic amino acids, peptides having an aromatic amino acid residues, and may be a liquid organic UV filter selected from the group consisting of mixtures thereof.

  Examples of liquid organic UV filters include those indicated by their INCI names below and mixtures thereof.

  Anthranilic acid derivative: Menthyl anthranilate marketed under the trademark “Neo Heliopan MA” by Haarmann and Reimer.

  Dibenzoylmethane derivatives: in particular butylmethoxydibenzoylmethane and isopropyldibenzoylmethane marketed under the trademark “Parsol 1789” by the company Hoffmann-La Roche.

  Liquid cinnamic acid derivatives: ethyl hexyl methoxycinnamate; isopropyl methoxycinnamate; isopropoxy methoxycinnamate; marketed under the trademark “Neo”, in particular by Hoffmann-La Roche under the trademark “Parsol MCX” Isoamyl methoxycinnamate commercially available from Heliopan E 1000; synoxate (2-ethoxyethyl-4-methoxycinnamate); DEA methoxycinnamate; diisopropyl methylcinnamate; and glyceryl ethyl hexacinnamate dimethoxycinnamate.

  Salicylic acid derivatives: 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; salicylate glycol; butyloctyl salicylate Phenyl salicylate; dipropylene salicylate marketed under the trademark “Dipsal” by Scher; and TEA salicylic acid marketed under the trademark “Neo Heliopan TS” by Haarmann and Reimer.

  Camphor derivatives, in particular benzylidene camphor derivatives: 3-benzylidene camphor manufactured under the trademark `` Mexoryl SD '' by Chimex; 4-methylbenzylidene camphor sold under the trademark `` Eusolex 6300 '' by Merck; trademark `` Chimex Benzylidene camphorsulfonic acid manufactured by Mexoryl SL; camphorbenzalkonium methosulfate manufactured by Chimex under the trademark “Mexoryl SO”; terephthalylli manufactured by Chimex under the trademark “Mexoryl SX” Dendican full sulfonic acid; and polyacrylamidomethylbenzylidene camphor manufactured by the company Chimex under the trademark “Mexoryl SW”.

  Benzophenone derivatives: benzophenone-1 (2,4-dihydroxybenzophenone) marketed by BASF under the trademark `` Uvinul 400 ''; benzophenone-2 (tetrahydroxybenzophenone) marketed by BASF under the trademark `` Uvinul D50 ''; Benzophenone-3 (2-hydroxy-4-methoxybenzophenone) or oxybenzone marketed by BASF under the trademark `` Uvinul M40 ''; Benzophenone-4 (hydroxymethoxybenzophenone sulfone marketed by BASF under the trademark `` Uvinul MS40 '' Acid); benzophenone-5 (sodium hydroxymethoxybenzophenone sulfonate); benzophenone-6 (dihydroxydimethoxybenzophenone) marketed under the trademark `` Helisorb 11 '' by Norquay; trademark `` Spectra-Sorb UV-24 '' by American Cyanamid Benzophenone-8 available on the market at BASF Thus, benzophenone-9 (disodium dihydroxydimethoxybenzophenone disulfonate) marketed under the trademark “Uvinul DS-49”; benzophenone-12, and n-hexyl 2- (4-diethylamino-2-hydroxybenzoyl) benzoate.

  β, β-diphenyl acrylate derivatives: Octocrylene sold in particular under the trademark “Uvinul N539” by the company BASF and in particular ethocrylene marketed under the trademark “Uvinul N35” by the company BASF.

  Liquid triazine derivatives: diethylhexylbutamide triazone marketed by Sigma 3V under the trademark "Uvasorb HEB"; 2,4,6-tris (dineopentyl 4'-aminobenzalmalonate) -s-triazine; and the United States Patent No. 6,225,467, WO2004 / 085412 (see compounds 6 and 9) or literature `` Symmetrical Triazine Derivatives '', IP.COM Journal, IP.COM INC, WEST HENRIETTA, NY, USA (September 20, 2004) The described symmetrical triazine screening agents, in particular 2,4,6-tris (biphenyl) -1,3,5-triazine [especially 2,4,6-tris (biphenyl-4-yl) -1,3 , 5-triazine] and 2,4,6-tris (terphenyl) -1,3,5-triazine, which are WO06 / 035000, WO06 / 034982, WO06 / 034991, WO06 / 035007, WO2006 / 034992 and It is taken up again in WO2006 / 034985.

  Liquid benzotriazole derivatives, especially phenylbenzotriazole derivatives: branched and linear 2- (2H-benzotriazol-2-yl) -6-dodecyl-4-methylpheno, and those described in USP 5240975.

  Benzalmalonate derivatives: dineopentyl 4'-methoxybenzalmalonate and polyorganosiloxanes containing benzalmalonate functional groups, such as Polysilicone-15 marketed under the trademark "Parsol SLX" by the company Hoffmann-LaRoche.

  Benzimidazole derivatives, in particular phenylbenzimidazole derivatives: phenyldibenzimidazole sulfonic acid marketed in particular under the trademark “Eusolex 232” by Merck and phenyldibenzimidazole marketed under the trademark “Neo Heliopan AP” by Haarmann and Reimer Disodium tetrasulfonate.

  Imidazoline derivative: ethylhexyl dimethoxybenzylidene dioxoimidazoline propionate.

  Bis-benzoazolyl derivatives: Derivatives described in EP-669,323 and US Pat. No. 2,463,264.

  Para-aminobenzoic acid and its derivatives: PABA (p-aminobenzoic acid), ethyl PABA, ethyldihydroxypropyl PABA, dimethyl PABA pentyl, especially dimethyl PABA ethylhexyl, glyceryl PABA marketed by ISP under the trademark `` Escalol 507 '' PEG-25 PABA marketed by BASF under the trademark “Uvinul P25”.

  Methylene bis (hydroxyphenylbenzotriazole) derivative: marketed in solid form by Fairmount Chemical under the trademark "Mixxim BB / 100" or in micronized form in an aqueous dispersion under the trademark "Tinosorb M" by Ciba Specialty Chemicals Methylenebis-benzotriazolyltetramethylbutylphenol and derivatives described in US Pat. Nos. 5,237,071, 5,166,355, GB-2,303,549, DE-19,726,184 and EP-893,119.

  Benzoxazole derivatives: 2,4-bis [5-1 (dimethylpropyl) benzoxazol-2-yl- (4-phenyl) imino] -6- (2-) marketed by Sigma 3V under the trademark Uvasorb K2A Ethylhexyl) imino-1,3,5-triazine.

  Shielding polymer and shielding silicone: Silicone described in WO93 / 04665.

  Dimer derived from α-alkylstyrene: a dimer described in DE-19855649.

  4,4-Diarylbutadiene derivative: 1,1-dicarboxy (2,2′-dimethylpropyl) -4,4-diphenylbutadiene.

  Octocrylene and its derivatives: Octocrylene.

  Guaiazulene and its derivatives: Guaiazulene and sodium guaiazulene sulfonate.

  Rutin and its derivatives: rutin and glucosyl rutin.

  Flavonoids: Lobustin (isoflavonoid), genistein (flavonoid), tectocricin (flavonoid) and hispidone (flavonoid).

  Biflavonoids: Lanseoratin A, Lanseoratin B and Hypnane biflavonoid A.

  Oryzanol and its derivatives: γ-oryzanol.

  Quinic acid and its derivatives: quinic acid.

  Phenols: Phenol.

  Retinols: Retinol.

  Cysteine: L-cysteine.

  Peptides having aromatic amino acid residues: Peptides having tryptophan, tyrosine, or phenylalanine.

Preferred liquid organic UV filters can be selected from:
Butylmethoxydibenzoylmethane, ethylhexyl methoxycinnamate, homosalate, ethylhexyl salicylate, octocrylene, phenylbenzimidazolesulfonic acid, benzophenone-3, benzophenone-4, benzophenone-5, n-hexyl 2- (4-diethylamino-2-hydroxy Benzoyl) benzoate, 4-methylbenzylidene camphor, terephthalylidene dican full sulfonic acid, disodium phenyldibenzimidazole tetrasulfonate, ethylhexyltriazone, bis-ethylhexyloxyphenol methoxyphenyltriazine, diethylhexylbutamide triazone, 2,4 , 6-Tris (dineopentyl 4'-aminobenzalmalonate) -s-triazine, 2,4,6-tris (diisobutyl 4'-aminobenzalmalonate) -s-triazine, 2,4,6-tris (Bi Phenyl-4-yl) -1,3,5-triazine, 2,4,6-tris (terphenyl) -1,3,5-triazine, methylenebis-benzotriazolyltetramethylbutylphenol, polysilicone-15, Dineopentyl 4'-methoxybenzalmalonate, 1,1-dicarboxy (2,2'-dimethylpropyl) -4,4-diphenylbutadiene, 2,4-bis [5-1 (dimethylpropyl) benzoxazole-2 -Yl- (4-phenyl) imino] -6- (2-ethylhexyl) imino-1,3,5-triazine, and mixtures thereof. A more preferred liquid organic UV filter is butylmethoxydibenzoylmethane (Avobenzone).

  The additional liquid UV filter has a mass ratio of 50:50 to 90:10, preferably 50:50 to 80:20, more preferably in the composite particles according to the present invention (a) core particles to the additional UV filter. It can be used at a ratio of 50:50 to 70:30.

{Hydrophobic block copolymer}
The second coating layer of the composite particles according to the present invention comprises at least one (c) hydrophobic block copolymer. When two or more (c) hydrophobic block copolymers are used, they may be the same or different.

  (c) The hydrophobic block copolymer preferably has elasticity. Specifically, the (c) hydrophobic block copolymer preferably has a recovery rate of 50% or more, preferably 60% or more, more preferably 70% or more.

The recovery rate can be determined by the following process:
(1) (c) a step of placing a hydrophobic block copolymer on a substrate;
(2) (c) Hydrophobic block copolymer is compressed at a compression rate of 0.1 mm / sec with a probe equipped with a pressure sensor, for example 35 mm in diameter, until a force of 1 kgf is detected by the pressure sensor Process,
(3) a step of obtaining a curve of the force value detected by the pressure sensor according to the distance between the substrate and the probe,
(4) calculating the integral value (1) of the curve (Y axis = force value, X axis = distance),
(5) when the detected force reaches 1 kgf, stop the compression, move the probe in the opposite direction at a speed of 0.1 mm / sec, and (c) release the hydrophobic block copolymer;
(6) a step of re-determining the curve of the force value detected by the pressure sensor according to the distance between the substrate and the probe,
(7) calculating the integral value (2) of the curve,
(8) A step of obtaining a ratio of (2) / (1) as a recovery rate, and
(9) A step of repeating the above steps (1) to (8) three times and calculating an average recovery rate.

  (c) The hydrophobic block copolymer is preferably thermoplastic.

  (c) The blocks of the hydrophobic block copolymer preferably have different glass transition temperatures (Tg).

  One of the blocks may have a Tg of 50 ° C. or higher, preferably 70 ° C. or higher, more preferably 90 ° C. or higher.

  Another one of the blocks may have a Tg of less than 50 ° C, preferably 0 ° C or less, more preferably -50 ° C or less.

  (c) The hydrophobic block copolymer may be a block copolymer of at least one (meth) acrylate block and at least one fluorinated block and / or at least one silicone block.

  Examples of block copolymers of (meth) acrylate blocks and fluorinated blocks and / or silicone blocks include fluorinate / acrylate copolymers marketed as “Modiper F606” by NOF Corporation in Japan and “Modiper FS700”. Mention may be made of the dimethicone / acrylate copolymers that have been prepared.

  (c) The hydrophobic block copolymer is preferably a hydrocarbon block copolymer.

  The hydrocarbon block copolymer is preferably an amorphous polymer. The term “amorphous polymer” means a polymer that does not have a crystalline form. The hydrocarbon-based block copolymer is also preferably film-forming, that is, it can form a film when applied to the skin or the like.

  The hydrocarbon-based block copolymer may be a diblock, triblock, multiblock, radical or star copolymer, or a mixture thereof, among others.

  Such hydrocarbon-based block copolymers are described in patent application US-A-2002 / 005562 and patent USP5221534.

  The hydrocarbon-based block copolymer preferably comprises at least one styrene monomer (ie derived from at least one styrene monomer).

  The hydrocarbon-based block copolymer may contain at least one block whose glass transition temperature is less than 20 ° C, preferably 0 ° C or less, more preferably -20 ° C or less, and further preferably -40 ° C or less. . The glass transition temperature of the block may be between −150 ° C. and 20 ° C., in particular between −100 ° C. and 0 ° C.

  The hydrocarbon block copolymer used in the present invention is preferably an amorphous copolymer formed by polymerization of olefin. The olefin may be an elastomeric ethylenically unsaturated monomer, among others.

  Examples of olefins that may be mentioned are ethylenic carbide monomers, such as ethylene, propylene, butadiene, isoprene or pentadiene, which contain, inter alia, 1 or 2 ethylenic unsaturations and contain 2 to 5 carbon atoms. Is included.

  Advantageously, the hydrocarbon-based block copolymer may be an amorphous block copolymer of styrene and olefin.

  The hydrocarbon-based block copolymer comprises at least one styrene block, optionally hydrogenated, and at least one block comprising units selected from butadiene, ethylene, propylene, butylene and isoprene or mixtures thereof. It is preferable.

  According to one preferred embodiment, the hydrocarbon-based block copolymer is hydrogenated to reduce residual ethylenic unsaturation after polymerization of the monomer.

In particular, the hydrocarbon-based block copolymer is an optionally hydrogenated copolymer containing styrene blocks and ethylene / C ₃ -C ₄ alkylene blocks.

  According to one preferred embodiment, the hydrocarbon-based block copolymer used in the present invention is preferably hydrogenated, preferably styrene-ethylene / propylene copolymer, styrene-ethylene / butadiene copolymer, styrene-ethylene / butylene. It may be a diblock copolymer selected from copolymers and styrene-ethylene / isoprene copolymers.

  According to one embodiment of the present invention, styrene and ethylene / propylene, or styrene and ethylene / butylene based linear diblock copolymers or hydrogenated styrene / isoprene copolymers are preferred as hydrocarbon-based block copolymers. Such diblock copolymers are sold, inter alia, under the names Kraton® G1701EU, Kraton® G1701H and Kraton® G1730M by the company Kraton Polymers.

  According to another preferred embodiment, the hydrocarbon-based block copolymers used in the present invention are preferably hydrogenated, preferably styrene-ethylene / propylene-styrene copolymers, styrene-ethylene / butadiene-styrene copolymers, It may be a triblock copolymer selected from styrene-ethylene / butylene-styrene copolymers, styrene-ethylene / isoprene-styrene copolymers, styrene-isoprene-styrene copolymers, and styrene-butadiene-styrene copolymers. Triblock copolymers are notably named by Kraton Polymers under the names Kraton® G1650, Kraton® G1651, Kraton® G1652, Kraton® G1654, Kraton® G1657M, Kraton® Trademark) D1101, Kraton® D1102, and Kraton® D1160.

  According to one embodiment of the present invention, the hydrocarbon-based block copolymer may be a hydrogenated styrene-ethylene / butylene-styrene triblock copolymer or a hydrogenated styrene / butadiene copolymer. Such triblock copolymers are sold by the company Kraton Polymers under the names Kraton (R) G1651, Kraton (R) G1654, and Kraton (R) G1657M, among others.

  According to one preferred embodiment of the present invention, it is possible to use, among other things, a mixture of styrene-ethylene / butylene-styrene triblock copolymer and styrene-ethylene / butylene block copolymer as the hydrocarbon-based block copolymer. .

  According to another preferred embodiment, the composition according to the invention comprises a mixture of a styrene-butylene / ethylene-styrene hydrogenated triblock copolymer and an ethylene-propylene-styrene hydrogenated star polymer as a hydrocarbon-based block copolymer. Such a mixture may optionally be present in isododecane or another oil, among others. Such mixtures are sold, for example, by the company Penreco under the trade names Versagel® M5960 and Versagel® M5670.

  Advantageously, diblock copolymers such as those described above are used as polymer gelling agents, in particular styrene-ethylene / propylene diblock copolymers or mixtures of diblock and triblock copolymers as described above. .

  Hydrocarbon block copolymers include styrene-ethylene / butylene-styrene triblock copolymer, styrene-ethylene / butylene diblock copolymer, styrene-ethylene / isoprene-styrene triblock copolymer, styrene / ethylene-propylene diblock copolymer, styrene-ethylene Preferably, it is selected from the group consisting of / isoprene diblock copolymers and mixtures thereof.

  The mass ratio of (a) core particles to (c) hydrophobic block copolymer may be 50:50 to 99: 1, preferably 60:40 to 95: 5, more preferably 70:30 to 90:10. .

  (c) The hydrophobic block copolymer is contained in the composite particles in the range of 1 to 35% by weight, preferably in the range of 4 to 30% by weight, more preferably 8 to 25% by weight, based on the total weight of the composite particles. May exist at a rate.

{Second layer}
The first layer is at least partially covered with at least one second coating layer comprising at least one (c) hydrophobic block copolymer. Preferably, 10% or more of the surface of the outermost first coating layer can be covered by the second coating layer. More preferably, 50% or more of the surface of the outermost first coating layer can be covered by the second coating layer. More preferably, 80% or more of the surface of the outermost first coating layer can be covered by the second coating layer. Most preferably, the entire surface of the outermost first coating layer can be covered by the second coating layer.

  (c) By using the hydrophobic block copolymer, the composite particles according to the present invention can maintain an improved UV shielding effect.

  The thickness of the second coating layer may vary depending on several factors such as (c) the type of hydrophobic block copolymer. The thickness of the second coating layer may range from 1 nm to 200 nm, preferably from 5 nm to 100 nm, more preferably from 10 nm to less than 50 nm.

  When two or more second coating layers are present on the first coating layer, the thickness and composition of the second coating layer may be the same or different from each other.

  The second coating layer may include any additional material in addition to (c) the hydrophobic block copolymer. The additional material may be present in an amount ranging from 1 to 50% by weight relative to the total weight of the second coating layer. However, the second coating layer is preferably made of (c) a hydrophobic block copolymer.

  The amount of the second coating layer may be 0.01 to 30% by mass, preferably 0.1 to 20% by mass, more preferably 0.3 to 15% by mass, based on the total mass of the composite particles.

[Production method of composite particles]
The composite particles according to the present invention are obtained by subjecting (a) at least one core particle, (b) at least one solid UV filter, and (c) at least one hydrophobic block copolymer to a mechanochemical fusion process. Can be manufactured.

  The (a) core particle, (b) solid UV filter, and (c) hydrophobic block copolymer are as described above.

  The mechanochemical fusion process means a process in which mechanical force such as impact force, friction force or shear force is applied to a plurality of objects to cause fusion between the objects.

  The mechanochemical fusion process may be performed, for example, by an apparatus comprising a rotating chamber and a fixed internal part having a scraper, such as a mechanofusion system marketed by Hosokawa Micron Corporation of Japan.

  It is preferable to use a hybridizer process as the mechanochemical fusion process.

  The hybridizer process was developed in the 1980s. The hybridizer process is a class of mechanochemical fusion process that applies a strong mechanical force to a plurality of particles to cause a mechanochemical reaction to form composite particles.

  According to the hybridizer process, the mechanical force is imparted by a high speed rotor that can have a diameter of 10 cm to 1 m and can rotate at a speed of 1,000 rpm to 100,000 rpm. Thus, the hybridizer process can be defined as a mechanochemical fusion process using such a high speed rotor. The hybridizer process is performed in air or under dry conditions. Therefore, a high-speed air flow can be generated near the rotor by the high-speed rotation of the rotor. However, some liquid materials can be subjected to a hybridizer process with solid materials. The term “hybridizer process” is used as a technical term.

  The hybridizer process can be performed, for example, by using a hybridization system marketed by Nara Machinery Co., Ltd. in Japan, in which at least two types of particles, typically core particles and Fine particles are fed into a hybridizer equipped with a high speed rotor having a plurality of blades in a chamber under dry conditions to disperse the particles in the chamber and provide mechanical and thermal energy (e.g. compression, friction and shear stress). For a relatively short period of time, for example 1 to 10 minutes, preferably 1 to 5 minutes. As a result, one type of particle (eg, a microparticle) is embedded or immobilized on the other type of particle (eg, a core particle) to form a composite particle. It is preferred to subject the particles to electrostatic treatment such as shaking to form an “ordered mixture” in which one type of particle spreads and covers the other type of particle. The hybridizer process can also be carried out by using a theta composer marketed by Tokuju Corporation in Japan.

  A hybridizer process can also be implemented by using Composi Hybrid or Mechano Hybrid marketed by Nippon Coke Kogyo Co., Ltd.

  According to one embodiment of the present invention, for example, additional components such as (a) core particles, (b) solid UV filters and (c) hydrophobic block copolymers, and optionally additional liquid UV filters if necessary. The material can be fed into such a hybridizer to form composite particles. The hybridizer process can be carried out by using a rotor rotating at about 8,000 rpm (100 m / sec) for about 3 minutes.

  When using small and large core particles as (a) core particles, the small core particles and large core particles have a mass ratio of small core particles to large core particles of 10:90 to 90:10, preferably from 20:80. The ratio can be 80:20, more preferably 30:70 to 70:30.

  In certain embodiments, the mass ratio of small core particles / large core particles / (b) solid UV filter is from 20:80:30 to 80:20:30, preferably 30:70:30 to 70:30:30. More preferably, it may be 40:60:30 to 60:40:30.

  In a preferred embodiment, the mass ratio of [(a) core particles + (b) solid UV filter] :( c) hydrophobic block copolymer is 100: 1 to 100: 50, preferably 100: 5 to 100: 40, More preferably, it may be 100: 10 to 100: 30.

  The mechanochemical fusion process, in particular the hybridizer process, comprises at least one first (a) core particles comprising at least one (b) a solid UV filter and optionally at least one additional liquid UV filter. Providing composite particles at least partially covered by a coating layer, wherein the first coating layer is at least partially covered by at least one second coating layer comprising at least one (c) hydrophobic block copolymer Make it possible to do.

  Further, the mechanochemical fusion process, particularly the hybridizer process, can provide (a) an ordered arrangement (e.g., uniform covering) of solid UV filters on the core particles (a) the surface of the core particles. And (b) providing a strong bond in the first coating layer comprising a solid UV filter and optionally an additional liquid UV filter.

  When a combination of small and large core particles is used, (b) the solid UV filter must (a) bind effectively to the surface of the core particles due to the anchor effect caused by the collision of the large core particles against the small core particles. Can do. Therefore, the UV filter effect can be further improved.

  Since (b) the first layer containing a solid UV filter is further coated with a second coating layer containing (c) a hydrophobic block copolymer, (b) the solid UV filter is (a) a core particle. It adheres firmly and (a) is difficult to peel off from the core particles. Thus, the composite particles according to the present invention can maintain the improved UV shielding effect provided by (b) a solid UV filter even when in contact with an anionic surfactant and / or water.

  It should be noted that the mechanochemical fusion process, in particular the hybridizer process, is quite different from other processes using, for example, bead mills and jet mills. Indeed, bead mills cause pulverization or agglomeration of the core particles, and jet mills cause pulverization of the core particles, making it difficult to form a uniform coating of the core particles with fine particles.

  If necessary, additional processes may be performed to further coat the composite particles with, for example, UV filters and / or coloring materials. As a result of this additional process, the composite particles according to the invention may be coated with at least one further layer, for example comprising UV filters and / or colored materials, preferably consisting of UV filters and / or colored materials. Good.

[Composition]
The composition according to the invention, preferably a cosmetic composition, comprises the composite particles according to the invention.

  In the composition according to the present invention, the above composite particles according to the present invention are 0.01% to 99% by weight, preferably 0.1% to 50% by weight, more preferably 1% by weight, based on the total weight of the composition. It can be present in an amount in the range of 30% by weight.

  Preferably, the composite particles according to the present invention or the composition according to the present invention can provide an excellent UV shielding effect when applied to keratin materials such as skin, hair and nails, because the composite particles This is because a good UV filter effect can be exhibited together with a transparent or clear appearance without risk of affecting the keratin substance.

  The composite particles according to the present invention have reduced friction because the composite particles according to the present invention can reduce free particles that do not spread easily on the skin due to having a high coefficient of friction and cause an unpleasant feeling of use. Therefore, it is possible to bring about an effect of a better feeling of use.

  The composition according to the invention may further comprise at least one filler and / or at least one oil.

  As used herein, the term “filler” should be understood to mean any form of colorless natural or synthetic particles that are insoluble in the medium of the composition regardless of the temperature at which the composition is produced. It is.

  The filler may be inorganic or organic and has any crystallographic form (e.g., sheet, cubic, hexagonal, orthorhombic, etc.) , Spherical, and oval). Examples of suitable additional fillers include talc; mica; silica; kaolin; polyamide, eg Nylon® powder; poly-β-3-alanine powder; polyethylene powder; polyurethane powder, eg Toyo Pigment Co., Ltd. Powder formed with hexamethylene diisocyanate and trimethylol hexyl lactone copolymer sold under the name Plastic Powder D-400 by; powder formed with tetrafluoroethylene polymer [Teflon®]; lauroyl lysine; starch; nitriding Boron; polymer hollow microspheres such as poly (vinylidene chloride) / acrylonitrile microspheres such as Expancel® (Nobel Industrie), and acrylic acid copolymer microspheres; silicone resin powder such as silsesquioxane powder [ Examples include the silicone resin powder disclosed in European Patent No. 0293795 and Toshiba Corporation. Tospearls®]; poly (methyl methacrylate) particles; precipitated calcium carbonate; magnesium carbonate; basic magnesium carbonate; hydroxyapatite; hollow silica microspheres; glass microcapsules; ceramic microcapsules; 8 to 22 carbons Metal soaps derived from organic carboxylic acids containing atoms, such as 12 to 18 carbon atoms, such as zinc stearate, magnesium stearate, lithium stearate, zinc laurate, and magnesium myristate; barium sulfate; and mixtures thereof Is included, but is not limited to these.

  The filler is present in the composition according to the invention in an amount ranging from 0.1% to 80% by weight, for example from 1% to 25% by weight, or from 3% to 15% by weight relative to the total weight of the composition. May exist.

  The term “oil” is understood to mean a fatty substance that is liquid at room temperature (25 ° C.).

Oils that can be used in the compositions of the present invention include, for example, hydrocarbon oils of animal origin, such as perhydrosqualene (or squalane); hydrocarbon oils of plant origin, such as caprylic / capric triglycerides, For example, those marketed by Sterineries Dubois or marketed by Dynamite Nobel under the trademarks Miglyol 810, 812 and 818, or oils of plant origin such as sunflower, corn, soybean, cucumber, grape seed, sesame, hazelnut , Apricot, macadamia, alara, coriander, castor, avocado or jojoba oil, or shea oil; synthetic oil; silicone oil, eg volatile or non-volatile, containing linear or cyclic silicone chains that are liquid or paste at room temperature Polymethylsiloxane (PDMS); fluorinated oils such as partially hydrocarbon and / Or those which are silicones such as those described in JP-A-2-295912; ethers, for example dicaprylyl ether (CTFA name); esters such as benzoates C ₁₂ -C ₁₅ fatty alcohol (manufactured by Finetex Inc. Finsolv TN); arylalkyl benzoate derivatives such as 2-phenylethyl benzoate (X-Tend 226 from ISP); amidated oils such as N-lauroyl sarcosine isopropyl (Eldew SL-205 from Ajinomoto Co.); and Mixtures of them can be used.

  The oily phase can also be selected from, for example, fatty alcohols (cetyl alcohol, stearyl alcohol, cetearyl alcohol), fatty acids (stearic acid) or waxes (paraffin wax, polyethylene wax, carnauba wax, beeswax), Multiple fatty substances can be included. The oily phase can contain lipophilic gelling agents, surfactants or even organic or inorganic particles.

  The oily phase can preferably account for 1 to 70% by weight, for example 1% to 25% by weight, or 3% to 15% by weight, based on the total weight of the composition according to the invention.

  The composition according to the invention can be used, for example, for coloring pigments, hydrophilic or lipophilic gelling agents and / or thickeners, anionic, cationic, nonionic, amphoteric or zwitterionic surfactants, antioxidants. Agents, fragrances, preservatives, neutralizers, sunscreens, vitamins, moisturizers, self-tanning compounds, anti-wrinkle active agents, emollients, hydrophilic or lipophilic active agents, anti-staining and / or anti-free radical agents Sequestering agent, film-forming agent, dermo-decontracting active agent, soothing agent, agent that stimulates synthesis of dermis or epidermis and / or prevents its degradation, anti-glycation agent Anti-inflammatory agent, exfoliating agent, depigmenting agent, antipigmenting agent, coloring agent, NO synthase inhibitor, fibroblast and / or keratinocyte proliferation and / or keratinocyte Further comprising at least one additional conventional cosmetic ingredient, which can be selected from drugs that stimulate differentiation, drugs that act on the microcirculation, drugs that affect cellular energy metabolism, healing agents, and mixtures thereof Good.

  Compositions according to the present invention can be in various forms, such as suspensions, dispersions, solutions, gels, oil-in-water (O / W), water-in-oil (W / O), and multiple (e.g., W / (O / W, polyol / O / W, and O / W / O) emulsions, such as emulsions, creams, foams, sticks, dispersions of vesicles, eg of ionic and / or nonionic lipids, two phases And multiphase lotions, sprays, powders, and pastes. The composition according to the invention may be anhydrous, for example an anhydrous paste or stick. The composition according to the invention may be a leave-in composition.

  According to one embodiment, the composition according to the invention may be in the form of a powdered composition or a liquid or solid composition, for example an oily solid composition or an anhydrous composition.

  In particular, the powdered composition according to the present invention can have a reduced friction resulting in a smooth usability by incorporating the composite particles according to the present invention, and a good compactness resulting in a high stability against physical impact. Can have.

  Furthermore, the powdery composition according to the present invention, by incorporating the composite particles according to the present invention, has good skin compatibility, a homogeneous appearance, skin color hiding, pores and wrinkles hiding on the skin, on the skin It is possible to show a favorable cosmetic effect such as making the pores and wrinkles inconspicuous and improving the matte appearance.

  On the other hand, the liquid composition according to the present invention can show good visual optical effects such as a matte and haze effect by incorporating the composite particles according to the present invention.

  In any case, the powdered and liquid composition according to the present invention has a better UV filter effect in addition to reducing the risk of solid UV filter particulates penetrating into the skin through pores on the skin. Have.

  According to another embodiment, the composition according to the invention comprises, for example, a compact powder, lotion, serum, emulsion, cream, base foundation, undercoat, makeup base coat, foundation, face powder, blusher, lipstick, lip balm , Eye shadow, eyeliner, loose powder, concealer, nail coat, mascara, sunscreen and the like.

  According to another embodiment, the composition according to the invention may be in the form of a foam.

  According to this embodiment, the composition according to the invention can be packed into a foam dispenser. This is dispensed from the pressurized container by the propellant gas and thus from the container by a product called an “aerosol” that forms a foam upon its dispensing, or by a mechanical pump connected to the dispensing head. Any product that is to be dispensed can be required to pass into the foam at the latest in the region of the outlet opening of such head by passing the composition through the dispensing head.

  According to a first variant, the dispenser may be an aerosol further containing the composition according to the invention and a propellant gas. For the purposes of the present invention, the term “propellant” means any compound that is gaseous at a temperature of 20 ° C. and atmospheric pressure and can be stored under pressure in a liquid or gaseous form in an aerosol container. To do. The propellant may be selected from optionally halogenated volatile hydrocarbons such as n-butane, propane, isobutane, pentane or halogenated hydrocarbons, and mixtures thereof. Carbon dioxide, nitrous oxide, dimethyl ether (DME), nitrogen or compressed air may be used as a propellant. A mixture of propellants may be used. Dimethyl ether and / or non-halogenated volatile hydrocarbons are preferably used.

  Propellant gases that can be used are, among others, carbon dioxide, nitrogen, nitrogen oxides, dimethyl ether, volatile hydrocarbons such as butane, isobutane, propane and pentane, and mixtures thereof. You can choose from.

  According to another variant, the composition according to the invention may be a “pump bottle” type foam dispenser. These dispensers include a dispensing head for delivering the composition, a pump, and a plunger tube for transferring the composition from the container into the head for dispensing the product. The foam is formed by passing the composition through a material containing a porous material, such as a sintered material, a plastic or metal filter grid, or similar structure.

  Such dispensers are known to those skilled in the art and are described in the following patents: U.S. Patent 3,709,437 (Wright), U.S. Patent 3,937,364 (Wright), U.S. Patent 4,022,351 (Wright), U.S. Pat. Patent No. 4,1147,306 (Bennett), U.S. Pat.No. 4,184,615 (Wright), U.S. Pat.No. 4,598,862 (Rice), U.S. Pat.No. 4,615,467 (Grogan et al.), And U.S. Pat.No. 5,364,031 (Taniguchi et al.) .

  Those skilled in the art will select the appropriate delivery form and method of preparation based on their general knowledge, taking into account the nature of the components used, e.g. its solubility in the vehicle and the intended use of the composition. Please understand that you can.

[Usage and method]
The invention also relates to the cosmetic use of the composite particles according to the invention. In one embodiment, the composite particles according to the invention can be applied to keratin materials such as skin, scalp and / or lips, preferably to the skin. Thus, the composite particles and compositions according to the invention can be used in methods for the skin, preferably cosmetic methods. The use according to the invention may be intended to absorb ultraviolet light and / or to protect especially human keratin materials from ultraviolet radiation. It is well known in the art that protecting keratin materials from ultraviolet radiation provides anti-aging, anti-wrinkle, and moisturizing effects. Thus, the composition of the present invention can further constitute a composition intended for anti-aging, anti-wrinkle and / or moisturizing effects.

  The method or cosmetic use for keratin materials such as skin according to the present invention comprises at least the step of applying the composite particles or compositions according to the present invention to the keratin materials. The present invention also includes a method of protecting a keratin material from ultraviolet radiation, comprising the step of applying the composite particle or composition according to the present invention to a keratin material, and a step of applying the composite particle or composition according to the present invention to a keratin material; And a method of absorbing ultraviolet light, comprising exposing the keratin material to ultraviolet light. These methods can be defined as non-therapeutic methods.

  The invention is explained in more detail by means of examples. However, these examples should not be construed to limit the scope of the invention. The following examples are presented as non-limiting illustrations in the field of the invention.

(Examples 1-5 and Comparative Examples 1-2)
The components shown in Table 1 were subjected to a hybridizer process using a hybridizer device to obtain composite particles according to Examples 1 to 5 and Comparative Examples 1 and 2. The numerical values of the amounts of components shown in Table 1 are all based on “mass%” as an active raw material.

  The detailed conditions of the hybridizer process are summarized in Table 2. After the hybridizer process, to remove the hydrogenated styrene / butadiene copolymer (1) and (2) that did not react with or coat the particles, it was sieved with an opening diameter of 212 μm and / or 106 μm. Carried out.

(Coating amount)
Each of the composite particles according to Examples 1 and 2 was packed in a column and eluted with hexane to extract each of the hydrogenated styrene / butadiene copolymers (1) and (2), respectively. Thus, the coating amount of the extracted hydrogenated styrene / butadiene copolymer (1) or (2) was determined as the amount of hydrocarbon using a continuous solid phase extraction column. The coating amount of each of the hydrogenated styrene / butadiene copolymers (1) and (2) with respect to the total mass of the composite particles in each of the composite particles according to Examples 1 and 2 is as follows.

[Evaluation]
The composite particles obtained in Examples 1 to 5 and Comparative Examples 1 to 2 were evaluated as follows.

{SEM observation}
The composite particles obtained by Examples 1 to 5 and Comparative Examples 1 to 2 were observed by using SEM (scanning electron microscope) by Hitachi S-4800. The initial shape of the core particles was spherical. Therefore, it was observed whether the composite particles obtained in Examples 1-5 and Comparative Examples 1-2 were spherical. The results are shown in Table 3. The shape of the particles obtained in Comparative Example 2 was not spherical but plate-like.

{UV absorption}
The absorbance of each of the composite particles obtained in Examples 1 to 5 and Comparative Examples 1 and 2 is as follows by using a V-550 type UV-visible spectrophotometer (JASCO Corporation, Japan). Was measured as follows.

  A solvent was prepared by mixing isododecane and polyhydroxystearic acid so that the concentration of polyhydroxystearic acid was 3% by mass.

  Each of the composite particles obtained by Examples 1 to 5 and Comparative Examples 1 to 2 was dispersed in the above solvent by using ultrasonic waves at room temperature for 1 minute, so that the concentration of the composite particles in the sample was 0.1. A sample was obtained so as to be mass%. If aggregates were still present, sonication was repeated.

  The obtained sample was placed in a quartz cell having a 2 mm optical path. The UV absorbance of the samples at wavelengths from 280 to 400 nm was measured by using a V-550 type UV-visible spectrophotometer (JASCO Corporation, Japan). The integrated value of UV absorbance in the wavelength range of 280 to 400 nm was calculated as “UV absorption”.

  The results are shown in the “UV absorption” column of Table 3. High value of “UV absorption” indicates high UV protection performance.

{Stability}
(Filtration test)
The stability of each of the composite particles obtained in Examples 1 to 5 and Comparative Examples 1 to 2 was tested as follows.

  A solvent was prepared by mixing water and sodium lauryl sulfate so that the concentration of sodium lauryl sulfate was 1% by mass.

  Each of the composite particles obtained by Examples 1 to 5 and Comparative Examples 1 to 2 was dispersed in the above solvent by using ultrasonic waves at 30 to 40 ° C. for 30 minutes, and the composite particles in the sample were dispersed. A sample was obtained so that the concentration was 0.5% by mass. If aggregates were still present, sonication was repeated.

  The obtained sample was centrifuged at 5250 rpm (approximately 2900 G) for 5 minutes to separate the supernatant.

  The supernatant was filtered through a conical filter (Millipore SLGP033NB) having a bottom circle with a diameter of 33 mm and a top circle with a diameter of 0.22 μm.

  The filtered supernatant was placed in a quartz cell having a 2 mm optical path. The UV absorbance of the sample in the wavelength range of 280 to 400 nm was measured by using a V-550 type UV-visible spectrophotometer (JASCO Corporation, Japan).

  The results are shown in the column “Filtration test” in Table 3. A high value for the “filtration test” indicates that more UV filters were detached (unstable) from the composite particles.

(Form test)
The stability of each of the composite particles obtained in Examples 1 to 5 and Comparative Examples 1 to 2 was tested as follows.

  The solvent was prepared by mixing water and disodium stearoyl glutamate so that the concentration of disodium stearoyl glutamate was 1% by mass.

  Each of the composite particles obtained by Examples 1 to 5 and Comparative Examples 1 to 2 was dispersed in the above solvent by using ultrasonic waves at 30 to 40 ° C. for 30 minutes, and the composite particles in the sample were dispersed. A sample was obtained so that the concentration was 1% by mass. If aggregates were still present, sonication was repeated.

  The obtained sample was diluted with ethanol so that the concentration of the composite particles became 0.1% by volume. The composition of the diluted sample was 0.1 volume% particles / 0.1 volume% disodium stearoyl glutamate / about 10 volume% water / about 90 volume% ethanol.

  The diluted sample was placed on a silicon wafer and observed by using SEM (scanning electron microscope) with Hitachi S-4800.

The results are shown in the “morphological test” column of Table 3. “Good” means that the TiO ₂ particles are firmly attached to the composite particles (stable), whereas “Poor” means that the TiO ₂ particles are detached (unstable) from the composite particles. Means.

  From Tables 1 to 3, the composite particles according to Examples 1 to 5 coated with a hydrophobic block copolymer are more complex than the composite particles according to Comparative Example 1 (uncoated) or Comparative Example 2 (polyethylene: coated with a hydrophobic homopolymer). Is also stable.

  Thus, the UV filters on the composite particles according to Examples 1 to 5 adhered firmly to the surface of the composite particles and did not peel from the surface of the composite particles even in the presence of an anionic surfactant.

  On the other hand, the UV filter on the composite particles according to Comparative Examples 1 and 2 did not adhere firmly to the surface of the composite particles, and peeled off from the surface of the composite particles in the presence of an anionic surfactant.

(Example 6 and Comparative Examples 3 to 4)
A sun care formulation in the form of an O / W emulsion was prepared by mixing the ingredients shown in Table 4. The numerical values of the amounts of components shown in Table 4 are all based on “mass%” as the active raw material.

[In vitro SPF evaluation]
(initial)
Each of the sun care formulations according to Example 6 and Comparative Examples 3-4 was applied to a PMMA plate in an amount of 0.75 mg / cm ² and the SPF value of the sample was measured by SPF analyzer UV-2000S. The results are shown in Table 4.

(After washing)
The sample prepared above was washed with running tap water for 1 minute. The SPF value of the washed sample was measured by SPF analyzer UV-2000S. The results are shown in Table 4.

  From Table 4, the composite particles according to Example 1 and Comparative Example 1 can improve the UV filter properties of the formulation, and the UV filter properties provided by the composite particles according to Example 1 are more than those according to Comparative Example 1. Is also stable. This is because the UV filter on the composite particle according to Example 1 adhered firmly to the surface of the composite particle after washing, and the composite particle retained its UV filter function even after washing, whereas Comparative Example 1 This is because the UV filter on the composite particles according to the above was peeled off from the surface of the composite particles after washing, and the composite particles could not retain their UV filter function after washing.

Claims (14)

(a) a composite particle comprising at least one core particle,
The (a) core particles are at least partially covered with (b) at least one first coating layer comprising at least one solid UV filter;
Composite particles, wherein the first coating layer is at least partially covered by (c) at least one second coating layer comprising at least one hydrophobic block copolymer.   (a) The average particle diameter of the core particles is 100 nm or more, preferably 200 nm or more, more preferably 300 nm or more, and / or 50 μm or less, preferably 20 μm or less, more preferably 10 μm or less. Composite particles.   3. Composite particles according to claim 1 or 2, wherein (a) the core particles comprise at least one inorganic material and / or at least one organic material, preferably at least one organic material.   (b) The solid UV filter is selected from solid inorganic UV filters, preferably selected from the group consisting of silicon carbide, metal oxides, and mixtures thereof, more preferably titanium oxide. The composite particle according to any one of the above.   The composite particles according to any one of claims 1 to 4, wherein the (b) solid UV filter has an average particle size of 1 nm to 200 nm, preferably 5 nm to 100 nm, more preferably 10 nm to 50 nm.   The mass ratio of (a) core particles to (b) solid UV filter is 10:90 to 90:10, preferably 20:80 to 80:20, more preferably 30:70 to 70:30. The composite particle according to any one of 1 to 5.   The composite particle according to any one of claims 1 to 6, wherein (c) the hydrophobic block copolymer has a recovery rate of 50% or more, preferably 60% or more, more preferably 70% or more.   (c) Hydrophobic block copolymer is an optionally hydrogenated hydrocarbon block copolymer, preferably units selected from at least one styrene block and butadiene, ethylene, propylene, butylene and isoprene or mixtures thereof. The composite particle according to any one of claims 1 to 7, which is a hydrocarbon-based block copolymer containing at least one block.   (c) styrene-ethylene / propylene, styrene-ethylene / butadiene, styrene-ethylene / butylene, styrene-ethylene / isoprene diblock copolymers, and optionally hydrogen, where the hydrophobic block copolymer is optionally hydrogenated. Added from styrene-ethylene / propylene-styrene, styrene-ethylene / butadiene-styrene, styrene-ethylene / butylene-styrene, styrene-isoprene-styrene, and styrene-butadiene-styrene triblock copolymers, and mixtures thereof 9. The composite particle according to any one of claims 1 to 8, which is selected.   The amount of the second coating layer is 0.01 to 30% by weight, preferably 0.1 to 20% by weight, more preferably 0.3 to 15% by weight, based on the total weight of the composite particles. The composite particle according to one item.   A composition, preferably a cosmetic composition, comprising the composite particles according to any one of claims 1 to 10.   Cosmetic use of the composite particles according to any one of claims 1 to 10. A method, preferably a cosmetic method, comprising a step of applying the composite particles according to any one of claims 1 to 10 or the cosmetic composition according to claim 11 to a keratin substance. (a) at least one core particle,
(b) at least one solid UV filter, and
(c) A method for producing composite particles comprising the step of subjecting at least one hydrophobic block copolymer to a mechanochemical fusion process.