Water-in-oil emulsion cosmetic

Abstract

The present invention addresses the problem of providing a water-in-oil type emulsion cosmetic having excellent ultraviolet protection ability and durability. [Solution] A water-in-oil type emulsion cosmetic containing the following components (A)-(D): (A) an oil-soluble ultraviolet absorber and / or a metal oxide that is solid at 25 DEG C; (B) a siloxane-based coating film forming agent; (C) a water-soluble or water-dispersible ultraviolet absorber; and (D) at least one selected from the group consisting of polyvinyl acetate and acrylic acid (ester) / C1-18 alkanol acrylate / C1-8 alkyl acrylamide copolymer AMP salts.

Description

Technical Field

[0001] This invention relates to water-in-oil emulsion cosmetics. Background Technology

[0002] Sunburn caused by ultraviolet (UV) radiation can promote skin browning, reduce skin elasticity, and cause wrinkles. Therefore, sunscreens containing UV absorbers and UV scatterers are used to prevent these problems. Sunscreens are generally classified into oil-in-water (O / W) and water-in-oil (W / O) types, with users expecting both to provide consistently excellent UV protection.

[0003] For example, Patent Document 1 discloses an emulsified cosmetic product characterized by containing: (a) optionally surface-treated particulate metal oxide; (b) hexyl ethylamino hydroxybenzoyl benzoate and / or tert-butyl methoxy dibenzoyl methane; (c) optionally surface-treated particulate metal oxide; and (d) powder selected from spherical silica, spherical polymethyl methacrylate and flake glass, wherein (a) and (b) are contained in an oil phase and (c) is contained in an aqueous phase.

[0004] In addition, Patent Document 2 discloses an oil-in-water emulsion composition containing (a) an aqueous dispersion of an oil-soluble ultraviolet absorber, (b) an ultraviolet scattering agent of 6% by mass and 20% by mass and (c) a phenyl-modified polysiloxane.

[0005] However, the emulsified cosmetic described in Patent Document 1 and the water-in-oil emulsified composition described in Patent Document 2 contain ultraviolet absorbers and ultraviolet scatterers in both the oil and aqueous phases, and have excellent ultraviolet defense capabilities, but they have the following problems: the film-forming agent is only contained in the oil phase. Therefore, when the ultraviolet absorbers and ultraviolet scatterers contained in the aqueous phase come into contact with water, they are easy to fall off from the skin surface, making it difficult to continuously obtain sufficient ultraviolet defense capabilities.

[0006] Existing technical documents Patent documents Patent Document 1: Japanese Patent Application Publication No. 2017-114900 Patent Document 2: Japanese Patent Application Publication No. 2019-34916. Summary of the Invention

[0007] The problem that the invention aims to solve This invention provides an oil-in-water emulsion cosmetic with excellent UV protection and durability.

[0008] In order to solve the above-mentioned problems, the inventors have repeatedly conducted in-depth research and found that by making the oil phase and the water phase contain ultraviolet absorbers and / or metal oxides, and by making each phase contain a specific film-forming agent, it is possible to obtain an oil-in-water emulsion cosmetic with excellent ultraviolet protection and durability, thereby completing the present invention.

[0009] means for solving problems The present invention includes the following methods.

[0010] [1] Water-in-oil emulsion cosmetics containing the following ingredients (A) to (D): (A) Oil-soluble ultraviolet absorbers and / or metal oxides that are solid at 25°C; (B) Siloxane-based coating forming agents; (C) Water-soluble or water-dispersible ultraviolet absorbers; (D) is selected from at least one of polyvinyl acetate and acrylate (ester) / C1-18 alkanol acrylate / C1-8 alkyl acrylamide copolymer AMP salt.

[0011] [2] According to the water-in-oil emulsion cosmetic described in [1], the content of (C) water-soluble or water-dispersible ultraviolet absorber is 0.05 to 5% by mass.

[0012] [3] The water-in-oil emulsion cosmetic according to [1] or [2], wherein (D) is selected from at least one of polyvinyl acetate and acrylate / C1-18 alkanol acrylate / C1-8 alkyl acrylamide copolymer AMP salt in an amount of 0.1 to 5 by mass.

[0013] [4] According to the water-in-oil emulsion cosmetic described in [1] or [2], the total amount of ingredient (A) and ingredient (C) {(A) + (C)} is 0.1 to 100% of the total amount of ingredient (B) and ingredient (D) {(B) + (D)}.

[0014] [5] The water-in-oil emulsion cosmetic according to [1] or [2] further comprises (E) siloxane surfactants.

[0015] [6] According to the water-in-oil emulsion cosmetic described in [5], the content of (E) siloxane surfactant is 0.1 to 3% by mass.

[0016] [7] The oil-in-water emulsified cosmetic described in [1] or [2] is a sunscreen cosmetic.

[0017] Invention Effects The water-in-oil emulsion cosmetic of the present invention has excellent UV protection and durability, as well as excellent stability over time. Detailed Implementation

[0018] The present invention will now be described in detail. The following description of the present invention is sometimes based on suitable embodiments of the invention, and the invention is not limited to such embodiments.

[0019] In this specification, the "~" symbol, which indicates a range of values, means that the values ​​listed before and after it are used as the lower and upper limits.

[0020] The water-in-oil emulsion cosmetic of the present invention (hereinafter referred to as "the cosmetic of the present invention") contains component (A), which is an oil-soluble ultraviolet absorber and / or metal oxide that is solid at 25°C. Component (A) is contained in the oil phase of the cosmetic of the present invention, and absorbs and / or scatters ultraviolet light in the oil phase formed when applied to the skin.

[0021] In the cosmetic of the present invention, as ingredient (A), it is sufficient to include either an oil-soluble ultraviolet absorber or a metal oxide that is solid at 25°C. From the viewpoint of further improving the ability to defend against ultraviolet rays, it is preferable to use both in combination.

[0022] As an oil-soluble ultraviolet absorber that is solid at 25°C, there are no particular limitations as long as it is a substance commonly used in cosmetics. Examples include diethylaminohydroxybenzoylhexyl benzoate, bisethylhexyloxyphenol methoxyphenyl triazine, tert-butylmethoxydibenzoylmethane, and ethylhexyl triazine ketone, etc., and one or more of these can be used. In this specification, oil solubility means that it dissolves at least 1% by mass in a common oil-based formulation that can be used in cosmetics at room temperature or under heating conditions.

[0023] Examples of commercially available oil-soluble UV absorbers that are solid at 25°C include Uvinul (registered trademark) A Plus Granular (diethylaminohydroxybenzoylhexyl benzoate, manufactured by BASF JAPAN), Tinosorb (registered trademark) S (bisethylhexyloxyphenol methoxyphenyl triazine, manufactured by BASF JAPAN), PARSOL (registered trademark) 1789 (tert-butylmethoxydibenzoylmethane, manufactured by DSM), and Uvinul (registered trademark) T150 (ethylhexyl triazine, manufactured by BASF JAPAN).

[0024] As for metal oxides, there are no particular limitations on any substance commonly used in cosmetics. Examples include titanium dioxide, zinc oxide, zirconium oxide, cerium oxide, and iron oxide, and one or more of these can be used. Among these, titanium dioxide and zinc oxide, which have excellent UV protection capabilities, are preferred, and zinc oxide is more preferred. In this specification, metal oxides refer to metal oxides that have UV absorption and / or UV scattering capabilities.

[0025] The shape, particle size, and particle structure of the aforementioned metal oxides are not particularly limited. For example, spherical, elliptical, plate-like, granular, needle-like, spindle-shaped, radial, and other shapes are acceptable; non-porous and porous particle structures are also acceptable.

[0026] From the viewpoint of ultraviolet defense capability, the average particle size of the metal oxide is preferably 100 nm or less, more preferably 50 nm or less, as an upper limit. As a lower limit, it is preferably 1 nm or more, more preferably 3 nm or more, and even more preferably 5 nm or more. As a range, it is preferably 1 to 100 nm, more preferably 3 to 100 nm, and even more preferably 5 to 50 nm. The average particle size of the metal oxide is determined by image analysis of transmission electron microscopy images.

[0027] Furthermore, the metal oxide can be surface-treated using known methods as needed. There are no particular limitations on the surface treatment, but hydrophobic treatment is preferred from the viewpoint of UV protection capability and its durability.

[0028] As for the hydrophobic treatment agent used, there are no particular limitations as long as it can impart hydrophobicity to the metal oxide. Examples include siloxane treatment agents, fluorine treatment agents, organotitanate treatment agents, fatty acid treatment agents, lecithin treatment agents, amino acid treatment agents, acyl amino acid treatment agents, and coupling agents (such as silane-based, aluminum-based, and titanium-based agents treated with alkylalkoxysilanes). Among these, from the viewpoint of UV protection capability and its persistence, siloxane treatment agents and coupling agents are preferred.

[0029] Examples of commercially available metal oxides include STR-40-OTS (titanium oxide with an average particle size of 15 nm surface-treated with triethoxyoctylsilane, manufactured by Sakai Chemical Industry Co., Ltd.), MZX-304OTS (zinc oxide with an average particle size of 35 nm surface-treated with triethoxyoctylsilane, manufactured by Tayca Corporation), and MZY-505M (zinc oxide with an average particle size of 25 nm surface-treated with polydimethylsiloxane, manufactured by Tayca Corporation).

[0030] The content of ingredient (A) is not particularly limited. From the viewpoint of UV protection capability and stability over time, relative to the total amount of the cosmetic of the present invention, in the case of a solid oil-soluble UV absorber at 25°C, for example, as a lower limit, it is preferably 0.1% by mass (hereinafter referred to as "%)" or more, more preferably 0.5% or more, and even more preferably 1% or more. As an upper limit, it is preferably 10% or less, more preferably 8% or less, and even more preferably 6% or less. In addition, the content of solid oil-soluble UV absorber is preferably, for example, 0.1 to 10%, more preferably 0.5 to 8%, and even more preferably 1 to 6%. In the case of metal oxides, for example, as a lower limit, it is preferably 1% or more, more preferably 5% or more, and even more preferably 10% or more. As an upper limit, it is preferably 30% or less, more preferably 25% or less, and even more preferably 20% or less. In addition, the content of metal oxides is preferably, for example, 1 to 30%, more preferably 5 to 25%, and even more preferably 10 to 20%. When using oil-soluble UV absorbers and metal oxides that are solid at 25°C in combination, the content ranges should be set to the same ranges as described above.

[0031] The cosmetic of the present invention contains ingredient (B), a siloxane-based film-forming agent. In the cosmetic of the present invention, ingredient (B) is contained in the oil phase and forms a film in the oil phase formed when applied to the skin.

[0032] Ingredient (B) is not particularly limited to any substance commonly used in cosmetics, and examples include trimethylsilyloxysilicone, polymethylsilsesquioxane, polypropylsilsesquioxane, trifluoroalkyl dimethyltrimethylsilyloxysilicone, (trimethylsilyloxysilicone / polydimethylsiloxane alcohol) crosspolymer, (polydimethylsiloxane / vinyltrimethylsilyloxysilicone) crosspolymer, (polydimethylsiloxane / vinylpolydimethylsiloxane) crosspolymer, (vinyldimethyl / trimethylsilyloxysilicone / polydimethylsiloxane) crosspolymer, (vinyldimethyl / trimethylsilyloxysilicone stearyl polydimethylsiloxane) crosspolymer, etc., and one or more of these can be used. Among these, from the viewpoint of durability, trimethylsilyloxysilicone and (polydimethylsiloxane / vinyltrimethylsilyloxysilicone) crosspolymers are preferred.

[0033] Examples of commercially available products that constitute ingredient (B) include KF-9021 (trimethylsiloxane, manufactured by Shin-Etsu Chemical Co., Ltd.), BELSIL (registered trademark) TMS 803 (trimethylsiloxane, manufactured by Wacker AsahikaseiSilicone Co., Ltd.), and BELSIL (registered trademark) REG 102 ((polydimethylsiloxane / vinyltrimethylsiloxane) crosspolymer, manufactured by Wacker Asahikasei Silicone Co., Ltd.).

[0034] The content of ingredient (B) is not particularly limited. From the viewpoint of stability and durability over time, relative to the total amount of the cosmetic of the present invention, for example, in terms of pure amount, the lower limit is preferably 0.1% or more, more preferably 0.5% or more, and even more preferably 1% or more. The upper limit is preferably 10% or less, more preferably 5% or less, and even more preferably 4% or less. In addition, the content of ingredient (B) in terms of pure amount is preferably 0.1 to 10%, more preferably 0.5 to 5%, and even more preferably 1 to 4%.

[0035] The cosmetic of the present invention contains ingredient (C), a water-soluble or water-dispersible ultraviolet absorber. In the cosmetic of the present invention, ingredient (C) is contained in an aqueous phase and absorbs ultraviolet rays in the aqueous phase formed when applied to the skin.

[0036] Ingredient (C) is not particularly limited to any substance commonly used in cosmetics. Examples of water-soluble UV absorbers include phenylbenzimidazole sulfonic acid and its salts, hydroxymethoxybenzophenone sulfonic acid and its salts, dihydroxydimethoxybenzophenone sulfonic acid and its salts, terephthalimide dicamphor sulfonic acid, tetrahydroxybenzophenone, 4-(2-β-glucanylsiloxy)propoxy-2-hydroxybenzophenone, etc., and one or more of these may be used. In this specification, water solubility means: dissolving in water at room temperature or under heating conditions, with or without a neutralizing agent.

[0037] Examples of commercially available water-soluble UV absorbers include Eusolex 232 (phenylbenzimidazole sulfonic acid, manufactured by Merck Performance Materials), Uvinul MS 40 (hydroxymethoxybenzophenone sulfonic acid, manufactured by BASF JAPAN), and Uvinul TS Hydro (approximately 30% aqueous solution of terephthalic dicamphor sulfonic acid, manufactured by BASF JAPAN).

[0038] Examples of water-dispersible ultraviolet absorbers include bis(ethylhexyloxyphenol) methoxyphenyl triazine and methylenebisbenzotriazolyltetramethylbutylphenol, and one or more of them can be used.

[0039] In the cosmetics of this invention, the water-dispersible ultraviolet absorber refers to a substance formed by pre-dispersing a water-insoluble ultraviolet absorber in an aqueous solution containing a surfactant or other dispersant.

[0040] Examples of commercially available water-dispersible UV absorbers include Tinosorb (registered trademark) S Aqua (20% water dispersion of bis(ethylhexyloxyphenol) methoxyphenyl triazine, manufactured by BASF JAPAN), Tinosorb (registered trademark) M (50% water dispersion of methylene bisbenzotriazolyl tetramethylbutylphenol, manufactured by BASF JAPAN), and K22-M40 (40% water dispersion of methylene bisbenzotriazolyl tetramethylbutylphenol, manufactured by Dai Nippon Chemical Co., Ltd.).

[0041] From the viewpoint of UV protection capabilities, the preferred ingredient (C) used in the cosmetic of this invention is phenylbenzimidazole sulfonic acid or methylenebisbenzotriazolyltetramethylbutylphenol, and more preferably methylenebisbenzotriazolyltetramethylbutylphenol.

[0042] The content of ingredient (C) is not particularly limited. From the viewpoint of stability over time, UV protection capability, and durability, the lower limit relative to the total amount of the cosmetic of the present invention, for example, in terms of pure amount, is preferably 0.05% or more, more preferably 0.1% or more, and even more preferably 0.5% or more. As an upper limit, it is preferably 5% or less, more preferably 2.5% or less, and even more preferably 1.5% or less. In addition, the content of ingredient (C) relative to the total amount of the cosmetic of the present invention, for example, in terms of pure amount, is preferably 0.05 to 5%, more preferably 0.1 to 2.5%, and even more preferably 0.5 to 1.5%.

[0043] The cosmetic of the present invention contains ingredient (D) selected from at least one of polyvinyl acetate and AMP salts of acrylates / C1-18 alkanol acrylates / C1-8 alkyl acrylamide copolymers. In the cosmetic of the present invention, ingredient (D) is contained in an aqueous phase and forms a film in the aqueous phase formed when applied to the skin.

[0044] As for polyvinyl acetate, any substance that meets the requirements of the 2006 Standard for Raw Materials for External Pharmaceutical Products—specifically, polyvinyl acetate liquid or polyvinyl acetate emulsion—is not subject to any particular limitation and can be used. Its INCI name is polyvinyl acetate.

[0045] The aforementioned polyvinyl acetate emulsion is a polymer emulsion obtained by emulsion polymerization of polyvinyl acetate in an aqueous solvent. Commercially available examples include VINYBLAN GV-5651 (manufactured by Nissin Chemical Industry Co., Ltd.). As the polyvinyl acetate polymer emulsion used in this invention, an emulsion with a solids content of 30-60% using water as a medium is suitable.

[0046] Acrylic (ester) / C1-18 alkanol acrylate / C1-8 alkyl acrylamide copolymer AMP salt is a copolymer of 2-amino-2-methyl-1-propanol (AMP) salt containing a monomer of one of acrylic acid, methacrylic acid or their monoesters with C1-18 alkanol acrylate or C1-18 alkanol methacrylate with C1-8 alkyl acrylamide.

[0047] Examples of commercially available AMP salts of acrylates / C1-18 alkanol acrylates / C1-8 alkyl acrylamide copolymers include Plascize L-9716U (manufactured by Mutsuyo Chemical Industry Co., Ltd.).

[0048] From the viewpoint of stability over time, polyvinyl acetate is preferred as ingredient (D) used in the cosmetic of the present invention.

[0049] The content of ingredient (D) is not particularly limited. From the viewpoint of stability and durability over time, the lower limit relative to the total amount of the cosmetic of the present invention, for example, in terms of pure amount, is preferably 0.1% or more, more preferably 0.2% or more, and even more preferably 0.3% or more. As an upper limit, it is preferably 5% or less, more preferably 4% or less, and even more preferably 3% or less. In addition, the content of ingredient (D), for example, in terms of pure amount, is preferably 0.1 to 5%, more preferably 0.2 to 4%, and even more preferably 0.3 to 3%.

[0050] In the cosmetic of the present invention, the mass ratio ({(A)+(C)} / {(B)+(D)}) of the total amount of ingredient (A) and ingredient (C) {(A)+(C)} relative to the total amount of ingredient (B) and ingredient (D) {(B)+(D)}) is not particularly limited. From the viewpoint of long-term stability, UV protection capability, and durability, for example, the lower limit is preferably 0.01 or more, more preferably 0.1 or more, and even more preferably 1 or more. As the upper limit, it is preferably 100 or less, more preferably 75 or less, and even more preferably 15 or less. In addition, the mass ratio ({(A)+(C)} / {(B)+(D)}) is preferably 0.01 to 100, more preferably 0.1 to 75, and even more preferably 1 to 15.

[0051] The cosmetic of the present invention preferably also contains ingredient (E) a siloxane-based surfactant. Ingredient (E) is not particularly limited to any substance commonly used in cosmetics, and examples include, for instance, polyoxyalkylene-modified organopolysiloxanes, polyoxyalkylene-modified organopolysiloxanes containing long-chain hydrocarbon groups, polyglycerol-modified organopolysiloxanes, and polyglycerol-modified organopolysiloxanes containing long-chain hydrocarbon groups; one or more of these may be used.

[0052] Examples of polyoxyalkylene-modified organopolysiloxanes include linear polyoxyalkylene-modified organopolysiloxanes such as PEG-3 polydimethylsiloxane, PEG-8 polydimethylsiloxane, PEG-9 polydimethylsiloxane, PEG-10 polydimethylsiloxane, PEG-9 methyl ether polydimethylsiloxane, PEG-10 methyl ether polydimethylsiloxane, and PEG-11 methyl ether polydimethylsiloxane; branched polyoxyalkylene-modified organopolysiloxanes such as PEG-9 polydimethylsiloxyethyl polydimethylsiloxane; and cross-linked polyoxyalkylene-modified organopolysiloxanes such as (polydimethylsiloxane / (PEG-10 / 15)) cross-linked polymer. One or more of these types can be used.

[0053] Examples of linear polyoxyalkylene-modified organopolysiloxanes containing long-chain hydrocarbon groups include cetyl PEG / PPG-10 / 1 polydimethylsiloxane, PEG / PPG-10 / 3 oleyl ether polydimethylsiloxane, and PEG / PPG-20 / 22 butyl ether polydimethylsiloxane; and branched polyoxyalkylene-modified organopolysiloxanes containing long-chain hydrocarbon groups, such as lauryl PEG-9 polydimethylsiloxyethyl polydimethylsiloxane. Oxyalkylene modified organopolysiloxanes; cross-linked polymers containing long-chain hydrocarbon groups such as (PEG-15 / lauryl polydimethylsiloxane) cross-linked polymers, (PEG-10 / lauryl polydimethylsiloxane) cross-linked polymers, (PEG-15 / lauryl polydimethylsiloxane) cross-linked polymers, and (PEG-15 / lauryl polydimethylsiloxyethyl polydimethylsiloxane) cross-linked polymers, can use one or more of these types of cross-linked organopolysiloxanes containing long-chain hydrocarbon groups.

[0054] Examples of polyglycerol-modified organopolysiloxanes include branched polyglycerol-modified organopolysiloxanes such as polyglycerol-3 disiloxane polydimethylsiloxane and polyglycerol-3 polydimethylsilylhydroxyethyl polydimethylsiloxane; and cross-linked polyglycerol-modified organopolysiloxanes such as (polydimethylsiloxane / polyglycerol-3) cross-linked polymers. One or more of these can be used.

[0055] Examples of polyglycerol-modified organopolysiloxanes containing long-chain hydrocarbon groups include branched polyglycerol-modified organopolysiloxanes containing long-chain hydrocarbon groups such as lauryl polyglycerol-3 polydimethylsiloxyethyl polydimethylsiloxane; and cross-linked polyglycerol-modified organopolysiloxanes containing long-chain hydrocarbon groups such as (lauryl polydimethylsiloxane / polyglycerol-3) cross-linked polymers and (polyglycerol-3 / lauryl polydimethylsiloxyethyl polydimethylsiloxane) cross-linked polymers. One or more of these can be used.

[0056] Among these siloxane-based surfactants, from the viewpoint of stability over time, polyoxyalkylene-modified organopolysiloxanes and polyoxyalkylene-modified organopolysiloxanes containing long-chain hydrocarbon groups are preferred, and linear and branched polyoxyalkylene-modified organopolysiloxanes and branched polyoxyalkylene-modified organopolysiloxanes containing long-chain hydrocarbon groups are more preferred.

[0057] Among them, PEG-9 polydimethylsiloxane is particularly preferred as a linear polyoxyalkylene modified organopolysiloxane, PEG-9 polydimethylsiloxane is particularly preferred as a branched polyoxyalkylene modified organopolysiloxane, and lauryl PEG-9 polydimethylsiloxane is particularly preferred as a branched polyoxyalkylene modified organopolysiloxane containing long-chain hydrocarbon groups.

[0058] The aforementioned siloxane-based surfactants can be commercially available products, such as KF-6011, KF-6011P, KF-6012, KF-6015, KF-6017, KF-6017P, KF-6028, KF-6043 (polyoxyalkylene modified organopolysiloxane, manufactured by Shin-Etsu Chemical Industry Co., Ltd.); KF-6038, KF-6048 (polyoxyalkylene modified organopolysiloxane containing long-chain hydrocarbon groups, manufactured by Shin-Etsu Chemical Industry Co., Ltd.); KF-6104, KF-6106 (polyglycerol modified organopolysiloxane, manufactured by Shin-Etsu Chemical Industry Co., Ltd.); KF-6105, KF-6115 (polyoxyalkylene modified organopolysiloxane containing long-chain hydrocarbon groups, manufactured by Shin-Etsu Chemical Industry Co., Ltd.), etc.

[0059] The content of ingredient (E) is not particularly limited. From the viewpoint of stability over time, it is preferably 0.1% or more, more preferably 0.25% or more, and even more preferably 0.5% or more in the total amount of the cosmetic of the present invention, for example, as a lower limit. Furthermore, it is preferably 3% or less, more preferably 2.5% or less, and even more preferably 2% or less, as an upper limit. Additionally, the content of (E) relative to the total amount of the cosmetic of the present invention is preferably 0.1 to 3%, more preferably 0.25 to 2.5%, and even more preferably 0.5 to 2%.

[0060] The cosmetic products of this invention may contain other ingredients without compromising the effectiveness of this invention. Examples of other ingredients include, for instance, oily ingredients, powders other than the metal oxide of ingredient (A), surfactants other than ingredient (E), UV absorbers other than ingredients (A) and (C), aqueous ingredients such as moisturizers, antioxidants, and cosmetic ingredients.

[0061] Oily components can include, for example, hydrocarbon oils such as isodecane, isododecane, hydrogenated polyisobutylene, light liquid paraffin, liquid paraffin, and squalane; isopropyl myristate, isopropyl palmitate, octyl dodecyl myristate, glyceryl tricaprylate, diisostearate, diglyceryl triisostearate, diisostearate malate, propylene glycol didecanoate, cetyl 2-ethylhexanoate, 2-ethylhexyl hydroxystearate, pentaerythritol tetraisostearate, octyl dodecyl stearate, 2-ethylhexyl p-methoxycinnamate, and alkyl benzoate (C12-15) esters. PG ester oils, etc.; silicone oils such as dimethylpolysiloxane, decamethylcyclopentasiloxane, octamethylcyclotetrasiloxane, and fluorinated siloxane; higher alcohols such as cetearyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, arachidyl alcohol, behenyl alcohol, 2-hexyldecyl alcohol, isostearyl alcohol, and 2-octyldodecyl alcohol; higher fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, isostearic acid, hydroxystearic acid, 12-hydroxystearic acid, oleic acid, undecenoic acid, linoleic acid, ricinoleic acid, and lanolin fatty acids. One or more of these can be used.

[0062] Powders are powders other than component (A) metal oxides. As a powder component, as long as it is commonly used in cosmetics, it is not particularly limited by shape (spherical, plate-like, needle-like, etc.), particle size (smoke-like, microparticle, pigment-grade, etc.), or particle structure (porous, non-porous, etc.). Examples include inorganic powders, glossy powders, organic powders, and composite powders. Examples include white inorganic pigments such as barium sulfate and calcium carbonate; colored inorganic pigments such as carbon black, chromium hydroxide, Prussian blue, and ultramarine; white body powders such as talc, mica, sericite, synthetic sericite, silicon dioxide, anhydrous silicate, synthetic phlogopite, kaolin, silicon carbide, saponin, lithium montmorillonite, montmorillonite, diatomaceous earth, aluminum silicate, magnesium aluminum metasilicate, calcium silicate, barium silicate, magnesium silicate, calcium carbonate, magnesium carbonate, hydroxyapatite, and boron nitride; and chlorine oxides. Bright powders such as bismuth suboxide, calcite, polyethylene terephthalate-aluminum-epoxy laminated powder, polyethylene terephthalate-polyolefin laminated film powder, and polyethylene terephthalate-polymethyl methacrylate laminated film powder; polyamide resins, polyethylene resins, polyacrylic resins, polyester resins, fluorine resins, cellulose resins, polystyrene resins, styrene-acrylic copolymer resins, and siloxane elastic system resins. Synthetic resins; polypropylene resins, urethane resins and other organic polymer resin powders; organic pigment powders such as Red 201, Red 202, Red 205, Red 226, Red 228, Orange 203, Orange 204, Blue 404, Yellow 401 and other organic pigment powders; zirconium, barium or aluminum lake and other organic pigment powders such as Red 3, Red 104, Red 106, Orange 205, Yellow 4, Yellow 5, Green 3, Blue 1 and other organic pigment powders; metal soap powders, N-acyl lysine and other organic low molecular weight powders, etc., may use one or more of these powders, and may use fluorine compounds, siloxane compounds, metal soaps, collagen, hydrocarbons, higher fatty acids, higher alcohols, esters, waxes, surfactants and other substances as needed, and subject them to surface treatment or further compounding using known methods.

[0063] Surfactants are surfactants other than component (E), and examples include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, etc. One or more of them can be used.

[0064] Ultraviolet absorbers are ultraviolet absorbers other than components (A) and (C), and examples include ethylhexyl methoxycinnamate, homosalate, polysiloxane-15, etc., and one or more of them can be used.

[0065] Aqueous components can include, for example, purified water, ion-exchanged water, seawater, deep ocean water, water vapor distillation from plants, alcohols such as ethanol, glycols such as propylene glycol, 1,2-pentanediol, 1,3-butanediol, dipropylene glycol, tripropylene glycol, polyethylene glycol, etc.; glycerin such as glycerin, diglycerin, polyglycerin, etc.; sugar alcohols such as sorbitol and maltitol; plant extracts, etc., and one or more of them can be used.

[0066] Antioxidants can be listed as tocopherol, ascorbic acid, etc.; cosmetic ingredients can be listed as vitamins, anti-inflammatory agents, medicinal herbs, etc.; preservatives can be listed as parabens, phenoxyethanol, etc., and one or more of them can be used.

[0067] The cosmetic of the present invention can be manufactured using conventional methods. Specifically, for example, an oil phase is prepared by mixing components (A) and (B) with component (E) as needed. On the other hand, an aqueous phase is prepared by mixing components (C) and (D). Furthermore, the cosmetic of the present invention can be obtained by adding the aqueous phase containing components (C) and (D) to the oil phase containing components (A) and (B) and mixing and dispersing it. The cosmetic of the present invention obtained in this manner contains ultraviolet absorbers and / or metal oxides in both the oil phase and the aqueous phase, and contains specific film-forming agents in each of the two phases.

[0068] The average particle size of the emulsion droplets in the cosmetic of the present invention is not particularly limited, but is preferably 0.1 to 100 μm, more preferably 1 to 100 μm, and even more preferably 5 to 50 μm. By adjusting the average particle size of the emulsion droplets to the above range, the deterioration of skin texture and the formation of aggregates are less likely to occur, and the cosmetic of the present invention with excellent long-term stability can be obtained. The average particle size of the emulsion droplets is defined as the value obtained by observing 100 emulsion droplets in a single field of view using an optical microscope (200x magnification).

[0069] The physical properties of the cosmetics of this invention are not particularly limited, and examples include liquid, two-layer type, emulsion, cream, semi-solid, and solid forms. Two-layer type cosmetics are cosmetics that achieve a uniform emulsification state through oscillation. In the case of two-layer type cosmetics, the average particle size of the emulsion droplets mentioned above refers to the average particle size of the emulsion droplets after oscillation.

[0070] The specific uses of the cosmetics of this invention are not particularly limited, but can be listed as, for example, color cosmetics such as foundation, makeup base, eyeshadow, blush, lipstick, and lip balm; skin care cosmetics such as lotion, cream, and sunscreen; and hair care cosmetics such as hair mask, hair cream, and conditioner. From the viewpoint of easily obtaining the effects of the cosmetics of this invention, they are preferably used in skin care cosmetics, and more preferably in sunscreens. The method of use is not particularly limited, but can be listed as, for example, mixing the product thoroughly before use and then applying it to the skin with the palm or fingers.

[0071] Alternatively, the present invention can also adopt the following technical solutions.

[0072] [1] Water-in-oil emulsion cosmetics containing the following ingredients (A) to (D): (A) Oil-soluble ultraviolet absorbers and / or metal oxides that are solid at 25°C; (B) Siloxane-based coating forming agents; (C) Water-soluble or water-dispersible ultraviolet absorbers; (D) is selected from at least one of polyvinyl acetate and acrylate (ester) / C1-18 alkanol acrylate / C1-8 alkyl acrylamide copolymer AMP salt.

[0073] [2] According to the water-in-oil emulsion cosmetic described in [1], the content of (C) water-soluble or water-dispersible ultraviolet absorber is 0.05 to 5% by mass.

[0074] [3] The water-in-oil emulsion cosmetic according to [1] or [2], wherein (D) is selected from at least one of polyvinyl acetate and acrylate / C1-18 alkanol acrylate / C1-8 alkyl acrylamide copolymer AMP salt in an amount of 0.1 to 5 by mass.

[0075] [4] According to the water-in-oil emulsion cosmetics described in [1]~[3], the total amount of ingredient (A) and ingredient (C) {(A) + (C)} relative to the total amount of ingredient (B) and ingredient (D) {(B) + (D)} is 0.1~100 by mass.

[0076] [5] The water-in-oil emulsion cosmetics described in [1] to [4] further contain (E) siloxane surfactants.

[0077] [6] According to the water-in-oil emulsion cosmetic described in [5], the content of (E) siloxane surfactant is 0.1 to 3% by mass.

[0078] [7] The oil-in-water emulsified cosmetics described in [1] to [6] are sunscreen cosmetics. Example

[0079] The present invention will now be described in detail through embodiments. It should be noted that the present invention is not limited to these embodiments.

[0080] Water-in-oil emulsion cosmetics as shown in Tables 1 and 2 below were prepared using the following methods. The resulting water-in-oil emulsion cosmetics were evaluated using the following methods for (i) stability over time, (ii) UV protection capability, and (iii) durability. The results are also shown in Tables 1 and 2. It should be noted that the content of each component in Tables 1 and 2 is expressed in "mass %".

[0081] [Table 1] .

[0082] [Table 2] *1 KF-6038 (manufactured by Shin-Etsu Chemical Industry Co., Ltd.) *2 MZX-304OTS (average particle size 25nm, manufactured by Tayca) *3 Uvinul (registered trademark) A Plus Granular (manufactured by BASF JAPAN) *4 Tinosorb (registered trademark) S (manufactured by BASF JAPAN) *5 Uvinul (registered trademark) T150 (made by BASF JAPAN) *6 K22-M40 (40% purity, manufactured by Dai Nippon Chemical Co., Ltd.) *7 Eusolex (registered trademark) 232 (Made by Merck Performance Materials) *8 VINYBLAN GV-5651 (40% purity, manufactured by Nissin Chemical Industry Co., Ltd.)

[0083] [Preparation methods of water-in-oil emulsion cosmetics in Examples 1-13 and Comparative Examples 1-4] A: Mix and disperse a portion of components (1) and (2) with components (3) and (5).

[0084] B: Heat and dissolve components (4) and (6) to (8) evenly.

[0085] C: Mix A and the remainder of component (2) and (9) to (14) into B and disperse evenly.

[0086] D: Mix components (15) to (22) and disperse them evenly.

[0087] E: Add D to C and disperse evenly to obtain a water-in-oil sunscreen.

[0088] <Evaluation Method: (I) Stability over Time> Place the samples recorded in Tables 1 and 2 into glass standard bottles, and store them in a constant temperature bath at 50°C for one month. After shaking the glass bottle up and down 20 times, take out 1g of sample, spread it on a 7cm×12cm glass plate with your finger and observe its state. Make a judgment according to the following judgment criteria.

[0089] <Judgment Criteria> (Evaluation): (Judgment) No signs of skin texture deterioration or aggregation were observed: A Almost no deterioration or accumulation of skin texture can be observed: B (No roughness or agglomeration when stretched) Poor skin texture, aggregates observed: C.

[0090] (The aggregate felt rough when it was stretched) <Evaluation Method: (II) Ultraviolet Defense Capability> The samples listed in Tables 1 and 2 were placed into glass standard vials, shaken up and down 20 times, and then coated onto PMMA plates (Labsphere, HELIOPLATED HD6) at a concentration of 2 mg / cm³. 2 After standing for 20 minutes, SPF was measured using an SPF analyzer (Labsphere UV-2000S). Ten points were measured on the aforementioned plate, and the average value was determined according to the following criteria.

[0091] <Judgment Criteria> (Average score of evaluation): (Judgment) 35 and above: A 25 and above but less than 35: B Less than 25: C.

[0092] <Evaluation Method: (III) Durability> The samples listed in Tables 1 and 2 were placed into glass standard vials, shaken up and down 20 times, and then coated onto PMMA plates (Labsphere, HELIOPLATED HD6) at a concentration of 2 mg / cm³. 2After standing for 20 minutes, the SPF value was measured using an SPF analyzer (Labsphere UV-2000S). Ten points were measured on the aforementioned plate, and the average value was taken as the pre-water bath SPF value. Next, the sample was subjected to a water bath. The water bath was conducted by attaching the sample to the side of a container filled with 2L of water at 35°C, and stirring the water in the container at 300rpm for 5 minutes using a paddle mixer. After the water bath, the sample was allowed to stand and dry for 20 minutes. The value obtained using the aforementioned measurement and calculation methods was taken as the post-water bath SPF value. The ratio of the pre-water bath SPF value to the post-water bath SPF value was calculated as (post-water bath SPF value) / (pre-water bath SPF value), and the following criteria were used for determination.

[0093] <Judgment Criteria> Ratio [(SPF measurement after water bath) / (SPF measurement before water bath)] : (Judgment) 0.7 or above: A 0.5 or higher and less than 0.7: B 0.3 or higher and less than 0.5: C Less than 0.3: D.

[0094] As shown in Table 1, the water-in-oil emulsion cosmetics of Examples 1-13 exhibit excellent long-term stability, UV protection capability, and durability.

[0095] On the other hand, as shown in Table 2, the water-in-oil emulsion cosmetic of Comparative Example 1, which contains a film-forming agent other than component (B), has poor long-term stability and durability.

[0096] In addition, the water-in-oil emulsion cosmetic of Comparative Example 2, which does not contain ingredient (D), has poor UV protection and durability.

[0097] Furthermore, the water-in-oil emulsion cosmetics of Comparative Examples 3 and 4, which contain film-forming agents other than component (D), exhibit poor long-term stability and durability.

[0098] Example 14: Water-in-oil sunscreen (shake-free) (Element) (%) 1. Microparticle zinc oxide (average particle size: 25 nm) treated with 3% triethoxyoctylsilane and 10% dimethylpolysiloxane 15 2. Polyhydroxystearic acid 0.2 3. Laureth PEG-9 polydimethylsiloxyethyl polydimethylsiloxane*1 4. Dimethylpolysiloxane 15 5. Diisopropyl sebacate 5 6. Diethylaminohydroxybenzoyl benzoate hexyl ester *3 1 7. Diethylhexyloxyphenol methoxyphenyl triazine*4 1 8. Ethylhexyltriazinone*5 1 9. 2-Ethylhexyl salicylate 3 10. Alkyl benzoate (C12-C15) 5 11. Diethylhexyl succinate 5 12. Di(Caprylic / Capric Acid) PG 5 13. Polysiloxane-15 2 14. Trimethylsilyloxysilicic acid 2.5 15. Isododecane 2.5 16. Silicon dioxide 5 17. Remaining purified water 18. Phenylenolbenzimidazole sulfonic acid*7 2 19. Triethanolamine 1.12 20. Ethanol 10 21. Polyvinyl acetate emulsion *8 2.5 22. Sodium chloride 0.1.

[0099] (Preparation method) A: Mix and disperse a portion of components (1), (2) and (3) to (5).

[0100] B: Heat and dissolve the remaining amount of component (5) and components (6) to (12) evenly.

[0101] C: Mix A and the remainder of components (3) and (4) and (13) to (15) into B and disperse them evenly.

[0102] D: Mix and disperse components (17) to (22) evenly.

[0103] E: Add (16) and D to C, and disperse and emulsify evenly to obtain water-in-oil sunscreen (shaking type).

[0104] (result) The water-in-oil sunscreen material (shaking type) of Example 14 exhibits excellent long-term stability, UV protection capability, and durability.

[0105] Example 15: Water-in-oil sunscreen (cream form) (Element) (%) 1. Diethylaminohydroxybenzoyl benzoate hexyl ester *3 1 2. Diethylhexyloxyphenol methoxyphenyl triazine*4 1 3. Ethylhexyltriazinone*5 1 4. Ethylhexyl methoxycinnamate 7 5. Polysiloxane-15 2 6. (Polydimethylsiloxane / (PEG-10 / 15) crosslinked polymer mixture *9 10) 7. Tris(2-ethylhexanoate) glyceryl ester 2 8. Microparticle zinc oxide (average particle size: 25 nm) treated with 3% triethoxyoctylsilane and 10% dimethylpolysiloxane. 9. Polyhydroxystearic acid 0.2 10. Dimethylsilylated silica (average particle size: 7 nm) 11. Dimethylpolysiloxane 1.5 12. Polymethylsilsesquioxane (average particle size: 6 μm) 3 13. Fragrance composition 0.1 14. Trimethylsilyloxysilicic acid 2.5 15. Isododecane 2.5 16. PEG-9 Polydimethylsiloxyethyl polydimethylsiloxane * 10 1 17. Laureth PEG-9 polydimethylsiloxyethyl polydimethylsiloxane*1 0.5 18. Quaternary ammonium salt - 18-lithium montmorillonite * 11 0.9 19. Cyclopentasiloxane 4 20. Remaining purified water 21. Ethanol 5 22. Methylenebisbenzotriazolyltetramethylbutylphenol dispersion*6 2.5 23. Acrylic (ester) / C1-18 alkanol acrylate / C1-8 alkyl acrylamide copolymer AMP salt 2.5 24. Sodium chloride 0.1 *9 KSG-210 (25% purity, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) *10 KF-6028P (manufactured by Shin-Etsu Chemical Industry Co., Ltd.) *11 SUMECTON-SAN-P (Made by KUNIMINE INDUSTRIES).

[0106] (Preparation method) A: Heat and dissolve components (1) to (11) evenly.

[0107] B: Add A and ingredients (12) and (13), and mix and disperse.

[0108] C: Add components (14) to (19) to B and mix and disperse.

[0109] D: Add (20)~(24) to C and emulsify to obtain a water-in-oil sunscreen cosmetic (cream).

[0110] (result) The water-in-oil sunscreen (cream) of Example 15 exhibits excellent long-term stability, UV protection capability, and durability.

[0111] Example 16: Water-in-oil sunscreen (spray type) (Element) (%) 1. Ethylhexyl methoxycinnamate 9 2. Diethylaminohydroxybenzoyl benzoate hexyl ester *3 2 3. Diethylhexyloxyphenol methoxyphenyl triazine*4 2 4. Ethylhexyltriazinone*5 2 5. 2-Ethylhexyl salicylate 3 6. Alkyl benzoate (C12-15) 5 7. Diethylhexyl succinate 10 8. Di(caprylic / capric acid) PG 10 9. Polysiloxane-15 1.5 10. Dimethylpolysiloxane 5 11. PEG-9 Polydimethylsiloxyethyl polydimethylsiloxane *10 1.5 12. Trimethylsilyloxysilicic acid 2.5 13. Isododecane 2.5 14. Silicon dioxide 5 15. Ethanol 30 16. Purified water balance 17. Methylenebisbenzotriazolyltetramethylbutylphenol dispersion*6 2.5 18. Polyvinyl acetate emulsion *8 2.5 19. 0.1% of the spice composition.

[0112] (Manufacturing method) A: Heat and dissolve components (1) to (8) evenly.

[0113] B: Mix ingredients (9) to (14).

[0114] C: Mix A and B and disperse them evenly.

[0115] D: Mix components (15) to (19).

[0116] E: Add D to C and disperse to obtain a water-in-oil emulsion type cosmetic stock solution.

[0117] F: After filling 30g of the cosmetic stock solution obtained through E into a pressure-resistant container, fix the valve, and fill the pressure-resistant container with 50g of LPG 0.15 and 20g of dimethyl ether through the valve to obtain a water-in-oil sunscreen (spray type).

[0118] (result) The water-in-oil sunscreen material (spray type) of Example 16 exhibits excellent long-term stability, UV protection capability, and durability.

[0119] Example 17: Water-in-oil foundation (Element) (%) 1. Siloxane-treated titanium dioxide (average particle size: 15nm) * 12 5 2. Siloxane-treated titanium dioxide (average particle size: 270nm) *13 5 3. Siloxane-treated zinc oxide (average particle size: 25nm) *14 10 4. 0.2g of red iron oxide 5. Yellow iron oxide 0.6 6. Black iron oxide 0.2 7. Siloxane-treated sericite 3 8. Isotridecyl isononanoate 6 9. PEG-9 Polydimethylsiloxyethyl polydimethylsiloxane *10 1.5 10. Laureth PEG-9 polydimethylsiloxyethyl polydimethylsiloxane*1 0.5 11. (Acrylic ester / ethylhexyl acrylate / polydimethylsiloxane copolymer*15 0.5) 12. Cyclopentasiloxane 15 13. Distearate dimethylammonium lithium montmorillonite 0.5 14. Silachlorite 0.5 15. Ethanol 0.5 16. Ethylhexyl methoxycinnamate 7 17. Diethylaminohydroxybenzoyl benzoate hexyl ester *3 2 18. Methyl polytrimethylsiloxane 5 19. Trimethylsilyloxysilicic acid solution * 16 5 20. Isododecane 2.5 21. Methylparaben 0.3 22. Ethanol 5 23. Glycerin 1 24. Purified water balance 25. Diethylhexyloxyphenol methoxyphenyl triazine dispersion*17 5.0 26. Polyvinyl acetate emulsion *8 2.5 *12 MTY-100SAS (Made by Tayca) *13 SA-TR-8 (Made by Miyoshi Chemical Co., Ltd.) *14 MZY-505M (manufactured by Tayca) *15 KF-578P (manufactured by Shin-Etsu Chemical Industry Co., Ltd.) *16 Cyclopentasiloxane solution (purity 50%) *17 Tinosorb (registered trademark) S Aqua (20% purity, manufactured by BASF JAPAN).

[0120] (Manufacturing method) A: Mix and disperse components (1) to (15) evenly.

[0121] B: Heat and dissolve components (16) and (17) evenly.

[0122] C: Mix A, B, and components (18) to (20) and disperse them evenly.

[0123] D: Mix components (21) to (26).

[0124] E: Add D to C and emulsify to obtain a water-in-oil foundation.

[0125] (result) The water-in-oil foundation of Example 17 exhibits excellent long-term stability, UV protection, and durability.

[0126] Example 18: Water-in-oil foundation (Element) (%) 1. Siloxane-treated titanium dioxide (average particle size: 15nm) * 12 5 2. Siloxane-treated titanium dioxide (average particle size: 270nm) *13 5 3. Siloxane-treated zinc oxide (average particle size: 25nm) *14 10 4. 0.2g of red iron oxide 5. Yellow iron oxide 0.6 6. Black iron oxide 0.2 7. Siloxane-treated sericite 5 8. Isotridecyl isononanoate 9. PEG-9 Polydimethylsiloxyethyl polydimethylsiloxane *10 1.5 10. Laureth PEG-9 polydimethylsiloxyethyl polydimethylsiloxane*1 0.5 11. (Acrylic ester / ethylhexyl acrylate / polydimethylsiloxane copolymer*15 0.5) 12. Cyclopentasiloxane 12 13. Distearate dimethylammonium lithium montmorillonite 0.5 14. Silachlorite 0.5 15. Ethanol 0.5 16. 2-Ethylhexyl salicylate 5 17. Diethylaminohydroxybenzoyl benzoate hexyl ester *3 2 18. Methyl polytrimethylsiloxane 5 19. Trimethylsilyloxysilicic acid solution * 16 5 20. Isododecane 5 21. Methylparaben 0.3 22. Ethanol 5 23. Glycerin 1 24. Purified water balance 25. Diethylhexyloxyphenol methoxyphenyl triazine dispersion*16 5.0 26. Polyvinyl acetate emulsion *8 2.5.

[0127] (Manufacturing method) A: Mix and disperse components (1) to (15) evenly.

[0128] B: Heat and dissolve components (16) and (17) evenly.

[0129] C: Mix A, B, and components (18) to (20) and disperse them evenly.

[0130] D: Mix components (21) to (26).

[0131] E: Add D to C and emulsify to obtain a water-in-oil foundation.

[0132] (result) The water-in-oil foundation of Example 18 exhibits excellent long-term stability, UV protection, and durability.

[0133] Example 19: Water-in-oil sunscreen material (shaking type) (Element) (%) 1. Microparticle zinc oxide (average particle size: 25 nm) treated with 3% triethoxyoctylsilane and 10% dimethylpolysiloxane. 2. Polyhydroxystearic acid 0.3 3. Laureth PEG-9 polydimethylsiloxyethyl polydimethylsiloxane*1 0.5 4. Dimethylpolysiloxane 15 5. Diisopropyl sebacate 5 6. Diethylaminohydroxybenzoyl benzoate hexyl ester *3 2 7. Diethylhexyloxyphenol methoxyphenyl triazine*4 2 8. Ethylhexyltriazinone*5 1 9. 2-Ethylhexyl salicylate 5 10. Alkyl benzoate (C12-C15) 5 11. Diethylhexyl succinate 5 12. Di(Caprylic / Capric Acid) PG 5 13. Polysiloxane-15 2 14. Trimethylsilyloxysilicic acid 2.5 15. Isododecane 2.5 16. Silicon dioxide 5 17. Remaining purified water 18. Phenylenolbenzimidazole sulfonic acid*7 2 19. Triethanolamine 1.12 20. Ethanol 10 21. Polyvinyl acetate emulsion *8 2.5 22. Sodium chloride 0.1.

[0134] (Preparation method) A: Mix and disperse a portion of components (1), (2) and (3) to (5).

[0135] B: Heat and dissolve the remaining amount of component (5) and components (6) to (12) evenly.

[0136] C: Mix A and the remainder of components (3) and (4) and (13) to (15) into B and disperse them evenly.

[0137] D: Mix and disperse components (17) to (22) evenly.

[0138] E: Add (16) and D to C and disperse and emulsify evenly to obtain water-in-oil sunscreen (shaking type).

[0139] (result) The water-in-oil sunscreen material (shaking type) of Example 19 exhibits excellent long-term stability, UV protection capability, and durability.

[0140] The fragrance compositions used in Examples 15 and 16 of the present invention are shown in Table 3 below.

[0141] [Table 3] .

Claims

1. A water-in-oil emulsified cosmetic comprising the following components (A) to (D): (A) an oil-soluble ultraviolet absorber and / or a metal oxide which is solid at 25°C; (B) a silicone film-forming agent; (C) a water-soluble or water-dispersible ultraviolet absorber; (D) at least one selected from the group consisting of polyvinyl acetate and (meth)acrylic acid / Ci_i8 alkanol acrylate / Ci-8 alkyl acrylamide copolymer AMP salt.

2. The water-in-oil emulsified cosmetic according to claim 1, wherein The content of the component (C) water-soluble or water-dispersible ultraviolet absorber is 0.05 to 5 mass%.

3. The water-in-oil emulsified cosmetic according to claim 1 or 2, wherein The content of the component (D) at least one selected from the group consisting of polyvinyl acetate and (meth)acrylic acid / Ci_i8 alkanol acrylate / Ci-8 alkyl acrylamide copolymer AMP salt is 0.1 to 5 mass%.

4. The water-in-oil emulsified cosmetic according to claim 1 or 2, wherein The mass ratio of the total amount of the component (A) and the component (C) {(A) + (C)} to the total amount of the component (B) and the component (D) {(B) + (D)} is 0.1 to 100.

5. The water-in-oil emulsified cosmetic according to claim 1 or 2, further comprising (E) a silicone surfactant.

6. The water-in-oil emulsified cosmetic according to claim 5, wherein The content of the (E) silicone surfactant is 0.1 to 3 mass%.

7. The water-in-oil emulsified cosmetic according to claim 1 or 2, which is a sunscreen cosmetic.

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