TWI909990B - Water-based oil-based emulsified cosmetics - Google Patents

Abstract

The water-based oil-based emulsified cosmetic of this invention contains the following components (A1), (A2), (B), and (C): Component (A1): A non-water-soluble organic ultraviolet absorber that is solid at 25°C Component (A2): A liquid oil Component (B): An acrylamide polymer Component (C): A hydrophobically treated microparticle metal oxide The mass ratio of component (C) to the total mass of components (A1) and (A2) [(C)/(A1+A2)] is 0.25 or more and 1.8 or less; The total mass content of 2-ethylhexyl p-methoxycinnamate and octocrylene in component (A2) is less than 2% by mass of the total mass of the water-based oil-based emulsified cosmetic.

Description

Water-based oil-based emulsified cosmetics

This invention relates to an oil-based emulsified cosmetic with excellent UV protection.

In recent years, the importance of protecting against ultraviolet rays in daily life has been increasing, and the demand for sunscreen cosmetics is also expanding. In response to this market demand, a water-based oil-emulsion sunscreen cosmetic has been developed that can easily provide a refreshing feel even with continuous use.

In these water-based oil-based emulsion cosmetics, UV absorbers and UV scattering agents are used to enhance UV protection. In particular, 2-ethylhexyl p-methoxycinnamate and octocrylene (2-cyano-3,3-diphenyl-2-acrylate-2-ethylhexyl ester), which are UV absorbers, are widely used in most sunscreen cosmetics due to their extremely high absorption wavelength in the UVB region and their high affinity for oil-based agents. However, these UV absorbers can irritate the skin of users with sensitive skin. Therefore, there are proposals to reduce the content of these UV absorbers in sunscreen cosmetics. For example, Japanese Patent Application Publication No. 2017-078054 (Patent Document 1) aims to provide a sunscreen cosmetic that, even with a specific blend of ethylhexyl methoxycinnamate and octocrylene (both liquid UV absorbers), still achieves high UV protection and excellent stability. It describes a sunscreen cosmetic containing, in a specific blend amount, a specific solid UV absorber, a specific ester oil, and a UV scattering agent with a refractive index within a specific range. The described sunscreen cosmetic has a total blend amount of ethylhexyl methoxycinnamate and octocrylene of less than 3% by mass.

The water-based oil-based emulsified cosmetic of this invention contains the following components (A1), (A2), (B), and (C): Component (A1): A non-water-soluble organic ultraviolet absorber that is solid at 25°C Component (A2): A liquid oil Component (B): An acrylamide polymer Component (C): A hydrophobically treated microparticle metal oxide The mass ratio of component (C) to the total mass of components (A1) and (A2) [(C)/(A1+A2)] is 0.25 or more and 1.8 or less; The total mass content of 2-ethylhexyl p-methoxycinnamate and octocrylene in component (A2) is less than 2% by mass of the total mass of the water-based oil-based emulsified cosmetic.

The sunscreen cosmetic described in Patent 1 is known to be insufficient in terms of UV protection and emulsification stability, and it tends to cause stickiness when applied to the skin. Furthermore, it leads to poor makeup adhesion when applying foundation or base makeup on top, and causes shine due to sebum. This invention relates to a water-oil emulsified cosmetic that, even with lower concentrations of 2-ethylhexyl methoxycinnamate and octocrylene, still exhibits excellent UV protection, excellent emulsification stability, minimal stickiness upon application, good makeup adhesion, and suppressed shine caused by sebum.

The inventors have discovered an oil-in-water emulsified cosmetic containing: a non-water-soluble organic ultraviolet absorber that is solid at 25°C, a liquid oil, an acrylamide polymer, and hydrophobically treated microparticle metal oxides; by ensuring that the mass ratio of the microparticle metal oxide content to the total content of the non-water-soluble organic ultraviolet absorber and the liquid oil is within a specific range, and that the total content of 2-ethylhexyl methoxycinnamate and octocrylene used as the liquid oil is below a specific value in the total amount of the oil-in-water emulsified cosmetic, a water-in-water emulsified cosmetic with high emulsification stability, excellent ultraviolet protection, less stickiness during application, good makeup adherence, and suppressed shine caused by sebum can be obtained.

That is, the water-based oil-based emulsified cosmetic of this invention contains the following components (A1), (A2), (B), and (C): Component (A1): A non-water-soluble organic ultraviolet absorber that is solid at 25°C Component (A2): A liquid oil Component (B): An acrylamide polymer Component (C): A hydrophobically treated microparticle metal oxide Wherein, the mass ratio of component (C) to the total content of components (A1) and (A2) [(C)/(A1+A2)] is 0.25 or more and 1.8 or less; The total content of 2-ethylhexyl p-methoxycinnamate and octocrylene in component (A2) accounts for less than 2% by mass of the total amount of the water-based oil-based emulsified cosmetic.

This invention provides an oil-based emulsified cosmetic that, even with reduced content of 2-ethylhexyl methoxycinnamate and octocrylene, still offers excellent UV protection, superior emulsification stability, minimal stickiness during application, good makeup adherence, and suppressed shine caused by sebum.

[Water-Based Oil-Based Emulsified Cosmetics] The water-based oil-based emulsified cosmetics of this invention (hereinafter also referred to as "emulsified cosmetics") are water-based oil-based emulsified cosmetics containing the following components (A1), (A2), (B), and (C): Component (A1): A non-water-soluble organic ultraviolet absorber that is solid at 25°C Component (A2): A liquid oil Component (B): An acrylamide polymer Component (C): A hydrophobically treated microparticle metal oxide Wherein, the mass ratio of the content of component (C) to the total content of components (A1) and (A2) [(C)/(A1+A2)] is 0.25 or more and 1.8 or less. The combined content of 2-ethylhexyl p-methoxycinnamate and octocrylene in ingredient (A2) is less than 2% by mass in the total amount of the water-based oil-based emulsion cosmetic. Furthermore, in this invention, the phrase "containing ingredients (A1), (A2), (B), and (C)" refers to "admixtures of ingredients (A1), (A2), (B), and (C)".

In this invention, "liquid state" refers to a state of fluidity at 1 atmosphere and 25°C, that is, a state exhibiting properties above the melting point (amorphous substances without a melting point exhibit this state). Conversely, "solid state" refers to a state of non-fluidity at 1 atmosphere and 25°C, that is, a state exhibiting properties below the melting point (amorphous substances without a melting point exhibit this state). In this invention, "non-water-soluble" refers to a solubility in water of less than 1 w/w%.

The water-based oil-based emulsified cosmetic of this invention exhibits excellent UV protection even with low contents of 2-ethylhexyl methoxycinnamate and octocrylene, and also demonstrates excellent emulsification stability, minimal stickiness during application, good makeup adherence, and suppression of shine caused by sebum. While the exact reason is not yet clear, it can be attributed to the following: In this invention, the surface of the microparticle metal oxide is treated with hydrophobicity, and the thickener used to thicken the continuous aqueous phase is an acrylamide-based polymer. When used in water-based oil-based emulsified cosmetics containing microparticle metal oxides, it is determined that the microparticle metal oxides can be stably present in the oil phase. Furthermore, by setting a predetermined range for the mass ratio of the content of hydrophobically treated microparticle metal oxides to the total content of solid, water-insoluble organic UV absorbers in the oil phase and liquid oils, emulsion stability can be improved, and UV scattering or absorption can be effectively achieved. Therefore, it was determined that even with lower contents of 2-ethylhexyl methoxycinnamate and octocrylene, UV protection capability can still be enhanced, and stickiness during application can be suppressed. Moreover, when the water-oil emulsion cosmetic of this invention is applied to the skin, by forming a film containing the aforementioned oils and hydrophobically treated microparticle metal oxides, it was determined that makeup adheres well and shine caused by sebum can be suppressed. Here, the liquid oils used, 2-ethylhexyl p-methoxycinnamate and octocrylene, are ingredients that cause stickiness upon application. The oiliness of the skin is attributed to the miscibility of these ingredients with the high-refractive-index oils in sebum secreted by the skin. In this invention, by setting the combined content of 2-ethylhexyl p-methoxycinnamate and octocrylene below a specific value in the total amount of an oil-based emulsion cosmetic in water, it is determined that the stickiness during application and the effect of suppressing shine caused by sebum can be further improved.

<Ingredient (A1): Non-water-soluble organic UV absorber in solid state at 25°C> This invention's water-based oil-based emulsion cosmetic, from the viewpoint of enhancing UV protection, contains ingredient (A1), a non-water-soluble organic UV absorber in solid state at 25°C. Component (A1) may include, for example: 4-tert-butyl-4'-methoxydibenzoylmethane, 2-(4-diethylamino-2-hydroxybenzoyl)hexyl benzoate, 2,4,6-tris[4-(2-ethylhexyloxycarbonyl)aniline]-1,3,5-tris(2-ethylhexyl)phenyl, 2-hydroxy-4-methoxydiphenyl ketone, cresoltrazolium trisiloxane, 2,4-bis{[4-(2-ethylhexyloxy)-2-hydroxy]phenyl}-6-(4-methoxyphenyl)-1,3,5-tris(2-ethylhexyl)dimethoxybenzyldioxyimidazolium propionate, etc. These water-insoluble organic ultraviolet absorbers may be contained individually or in combination of two or more.

Of these, component (A1) is preferably derived from 4-tert-butyl-4'-methoxydibenzoylmethane, 2-(4-diethylamino-2-hydroxybenzoyl)hexyl benzoate, 2,4,6-tris[4-(2-ethylhexyloxycarbonyl)anilino]-1,3,5-tris(2-ethylhexyloxy)phenylene, 2-hydroxy-4-methoxydiphenyl ketone, cresoltrazolium trisiloxane, and 2,4-bis{[4-(2-ethylhexyloxy)-2-hydroxy]phenyl}-6-(4-methoxy) The active ingredient (A1) is selected from the group consisting of 2-(4-diethylamino-2-hydroxybenzoyl)hexyl benzoate, more preferably from the group consisting of 2,4,6-tris[4-(2-ethylhexyloxycarbonyl)aniline]-1,3,5-tris[A2], and 2,4-bis{[4-(2-ethylhexyloxy)-2-hydroxy]phenyl}-6-(4-methoxyphenyl)-1,3,5-tris[A2]. Furthermore, in the water-oil emulsion cosmetic of the present invention, component (A1) is preferably present in a state of being dissolved in component (A2).

Commercially available products containing ingredient (A1) include, for example: "PARSOL 1789" (4-tert-butyl-4'-methoxydibenzoylmethane) (manufactured by DSM); "UVINUL A PLUS" (2-(4-diethylamino-2-hydroxybenzoyl)hexyl benzoate), "UVINUL T-150" (2,4,6-tris[4-(2-ethylhexyloxycarbonyl)aniline]-1,3,5-tris ... "A440" (Cresoltrazol trisiloxane) (manufactured by UFC CORPORATION); "SOFT SHADE DH" (2-ethylhexyl dimethoxybenzyl dioxyimidazolidine propionate) (manufactured by Ajinomoto Co., Ltd.), etc.

The content of component (A1) in the total amount of the water-based oil-based emulsified cosmetic of this invention, from the viewpoint of enhancing the UV protection effect, is preferably 0.5% by mass or more, more preferably 0.7% by mass or more, particularly preferably 1% by mass or more, and most preferably 2% by mass or more; and from the viewpoint of suppressing stickiness during application and suppressing shine caused by sebum, it is preferably 10% by mass or less, more preferably 8% by mass or less, particularly preferably 6% by mass or less, and most preferably 5% by mass or less. More specifically, it is preferably 0.5 to 10% by mass, more preferably 0.7 to 8% by mass, particularly preferably 1 to 6% by mass, and most preferably 2 to 5% by mass.

<Ingredient (A2): Liquid Oil> This water-based oil-based emulsified cosmetic contains a liquid oil (A2) from the viewpoints of dissolving ingredient (A1), introducing ingredient (C), and ensuring good emulsification stability. Ingredient (A2) is, as described above, an oil that is fluid at 1 atmosphere and 25°C. In this water-based oil-based emulsified cosmetic, ingredient (A2) may also contain a liquid organic UV absorber from the viewpoint of further enhancing UV protection.

The liquid organic ultraviolet absorbers in component (A2) can include, for example: 2-ethylhexyl p-methoxycinnamate, 2-ethoxyethyl p-methoxycinnamate, a mixture of isopropyl p-methoxycinnamate and diisopropyl p-cinnamate, methyl bis(trimethylsiloxy)silyl isoamyl trimethoxycinnamate, and other cinnamic acid-based ultraviolet absorbers; p-(dimethylamino)benzoate amyl ester, p-(dimethylamino)benzoate 2-ethyl... Para-aminobenzoic acid-based UV absorbers such as hexyl ester; salicylic acid-based UV absorbers such as ethylene glycol salicylate, 2-ethylhexyl salicylate, butyl octyl salicylate, benzyl salicylate, and trimethylcyclohexyl salicylate; octocrylene; diethyl dimethylsilylbenzyl malonate; copolymers of adipic acid and neopentyl glycol terminated with octyldodecyl alcohol or diphenyl cyanide, etc. These liquid organic UV absorbers may contain one type alone or in suitable combinations of two or more types.

Commercially available liquid organic UV absorbers include, for example: "UVINUL MC80" (2-ethylhexyl p-methoxycinnamate) (manufactured by BASF); "PARSOL 340" (octocrylene) (manufactured by DSM Nutrition Japan Co., Ltd.); "PARSOL EHS" (2-ethylhexyl salicylate), "PARSOL HMS" (trimethylcyclohexyl salicylate), "PARSOL SLX" (polysilicone-15 (diethyl dimethylsilylbenzylmalonate)) (all manufactured by DSM); and "Polycrylene" (polyester-8 (a copolymer of adipic acid and neopentyl glycol, capped with octyldodecyl alcohol or diphenyl cyanide) (manufactured by Hallstar).

Among them, the combined content of 2-ethylhexyl p-methoxycinnamate and octocrylene in ingredient (A2) is, from the perspective of inhibiting stickiness during application and suppressing shine caused by sebum, less than 2% by mass, better than 1.5% by mass, more than 1% by mass, especially better than 0.7% by mass, best than 0.5% by mass, most best than 0.3% by mass, and even best than 0% by mass, meaning it does not contain 2-ethylhexyl p-methoxycinnamate and octocrylene.

From the perspectives of dissolving the component (A1), introducing the component (C), and ensuring good emulsification stability, component (A2) is preferably a liquid oil other than the aforementioned liquid organic UV absorber. This other liquid oil is provided to be liquid at 1 atmosphere and 25°C; otherwise, there are no particular limitations, and it can be, for example, oils commonly used in cosmetics. Preferably, the other liquid oil can be one or more selected from the group consisting of ester oils, polysiloxane oils, hydrocarbon oils, higher alcohols, and higher fatty acids. The aforementioned liquid oil may be contained individually or in suitable combinations of two or more.

Ester oils can be categorized as such as synthetic ester oils and natural oils, including esters of monocarboxylic acids and monohydric alcohols, esters of monocarboxylic acids and polyhydric alcohols, and esters of polycarboxylic acids and monohydric alcohols.

Esters of monocarboxylic acids and monohydric alcohols can be exemplified by the following general formula (1): ^R1 -COO- ^R2 (1) In general formula (1), ^R1 represents a straight-chain or branched-chain alkyl or alkenyl group with 1 or more carbon atoms and 25 or less that can be substituted by a hydroxyl group, or an aromatic hydrocarbon group with 6 or more carbon atoms and 24 or less; ^R2 represents a straight-chain or branched-chain alkyl or alkenyl group with 1 or more carbon atoms and 30 or less.

When ^R1 is an alkyl or alkenyl group, the number of carbon atoms in ^R1 is preferably 7 or more, more preferably 23 or less, even more preferably 21 or less, particularly preferably 19 or less, and most preferably 17 or less. When ^R1 contains an aromatic hydrocarbon group, the number of carbon atoms in ^R1 is preferably 6 or more, more preferably 22 or less, and even more preferably 20 or less. The number of carbon atoms in ^R2 is preferably 2 or more, more preferably 28 or less, even more preferably 24 or less, particularly preferably 22 or less, and most preferably 20 or less.

Specific examples of esters represented by general formula (1) include, for example, squalene isooctanoate (squalene 2-ethylhexanoate), stearyl isooctanoate, isononyl isononanoate, isotriacontane isononanoate, hexyl laurate, isostearyl laurate, butyl myristate, isopropyl myristate, decyl myristate, isotriacontane myristate, isoctyl myristate, isostearyl myristate, 2-octyl dodecyl myristate, isopropyl palmitate, 2-ethylhexyl palmitate, palmitate, etc. One or more of the following are selected from the group consisting of isostearyl palmitate, 2-hexyldecyl palmitate, 2-ethylhexyl stearate, 2-hexyldecyl stearate, isopropyl isostearate, 2-hexyldecyl isostearate, ethyl oleate, isodecyl oleate, oleic acid ester, 2-octyldodecyl oleate, ethyl linoleate, isopropyl linoleate, lanolin acetate, sunflower oil fatty acid methyl ester (methyl linoleate), and alkyl benzoate (alkyl carbon number 12-15).

Esters of monocarboxylic acids and monohydric alcohols can also be exemplified by the esters shown in the following general formula (2): ^R3 -COO-(AO) _n - ^R4 (2) In general formula (2), ^R3 represents a straight-chain or branched-chain alkyl or alkenyl group with 1 or more carbon atoms and 25 or less that can be substituted by a hydroxyl group; ^R4 represents an aromatic hydrocarbon group with 6 or more carbon atoms and 24 or less. AO represents an alkoxy group with 2 or more carbon atoms and 4 or less; n represents the average addition mole number with 1 or more carbon atoms and 50 or less. ^R3 is preferably an alkyl group with 7 or more carbon atoms, and more preferably 23 or less, more preferably 21 or less, and especially preferably 19 or less. ^R4 is preferably an aromatic hydrocarbon group with 6 or more carbon atoms, and more preferably 22 or less, more preferably 20 or less, and especially preferably 18 or less, and preferably benzyl. The alkoxy group represented by AO is preferably an alkoxy group, and n is preferably 1 or more and 10 or less, more preferably 1 or more and 5 or less. Specific examples of esters represented by general formula (2) include: esters of myristic acid and benzyl alcohol in a 3-molar addition of propylene oxide (manufactured by CRODA: CRODAMOL STS), esters of 2-ethylhexanoic acid and benzyl alcohol in a 3-molar addition of propylene oxide (manufactured by CRODA: CRODAMOL SFX), etc.

An ester system of a monocarboxylic acid and a polyol can be exemplified by the ester shown in the following general formula (3): ^R5- ( ^OCOR6 ) _p (3) In general formula (3), ^R5 represents a polyol residue, preferably an hydrocarbon with 2 or more carbon atoms and 10 or less; ^R6 represents a monocarboxylic acid residue with 1 or more carbon atoms and 25 or less; p represents an integer with 2 or more carbon atoms and 10 or less. In addition, ^R5 may also have an ether bond, preferably a straight-chain or branched-chain hydrocarbon with 2 or more carbon atoms and 10 or less. Also, p is preferably the same number as the hydroxyl group of the polyol mentioned above. ^R6 preferably has 5 or more carbon atoms, more preferably 7 or more carbon atoms, and from the same point of view as above, preferably 23 or less, more preferably 21 or less, particularly preferably 19 or less, and most preferably 17 or less alkyl groups.

Esters represented by general formula (3) can include, for example: propylene glycol didecanoate, propylene glycol dioleate, neopentyl glycol didecanoate, neopentyl glycol di(2-ethylhexanoate), propylene glycol di(octanoic acid/decanoic acid), propylene glycol diisostearate, ethylene glycol di(2-ethylhexanoate), triglycerides (octanoic acid/decanoic acid), triglycerides (2-ethylhexanoate), triglycerides (2-heptylundecanoate), tri(2-ethylhexanoate)trihydroxymethylpropane, trihydroxymethylpropane triisostearate, pentaerythritol tetra(2-ethylhexanoate), and natural oils. Natural oils can include, for example: avocado oil, olive oil, flaxseed oil, rice bran oil, sunflower oil, soybean oil, corn oil, rapeseed oil, castor oil, cottonseed oil, mink oil, and other triglycerides.

Esters of polycarboxylic acids and monohydric alcohols can also be exemplified by the ester shown in the following general formula (4): ^R7- ( ^COOR8 ) _q (4) In general formula (4), ^R7 represents a polycarboxylic acid residue with 2 or more and 10 or less carbon atoms; ^R8 represents a monohydric alcohol residue with 1 or more and 25 or less carbon atoms; and q is an integer with 2 or more and 10 or less. Preferably, q is the same number as the carboxyl group possessed by the aforementioned polycarboxylic acid. Preferably, ^R8 has 3 or more carbon atoms, and from the same viewpoint as above, preferably 23 or less, more preferably 21 or less, and especially preferably 19 or less. Specific examples include: diisostearyl malate, di(2-ethylhexyl) succinate, diisobutyl adipate, di(2-heptylundecane) adipate, di(2-ethylhexyl) sebacate, diisopropyl sebacate, and tri(2-ethylhexyl) trimellitate.

Among these, the aforementioned ester oils, from the viewpoints of dissolving components (A1), introducing components (C), and good emulsification stability, are preferably esters represented by general formula (1), general formula (3), or general formula (4), and more preferably monoesters of: straight-chain or branched-chain fatty acids having 8 or more and 18 carbons and straight-chain or branched-chain monohydric alcohols having 2 or more and 24 carbons; triesters of branched-chain fatty acids having 6 or more and 18 carbons and glycerol; tetraesters of branched-chain fatty acids having 6 or more and 18 carbons and pentaerythritol; diesters of branched-chain fatty acids having 6 or more and 18 carbons and branched-chain dihydric alcohols having 2 or more and 10 carbons; triesters of branched-chain monohydric alcohols having 6 or more and 18 carbons and trimellitic acid; and alkyl benzoate esters (C12-15) (e.g., "Finsolv TN" (Innospec Active Chemicals)). One or more of the following are selected from the group consisting of: whale ester of 2-ethylhexanoate, isononyl isononate, isotriadecyl isononate, 2-octyldodecyl myristate, isopropyl palmitate, triglycerides (2-ethylhexanoate), pentaerythritol tetra(2-ethylhexanoate), diisopropyl sebacate, tri(2-ethylhexyl trimellitate), and alkyl benzoates (C12-15).

From the perspectives of dissolving components (A1), introducing components (C), and good emulsification stability, the aforementioned polysiloxane is preferably dimethylpolysiloxane, and more preferably dimethylpolysiloxane with a kinematic viscosity at 25°C below 5,000 ^mm² /s. The kinematic viscosity at 25°C of the aforementioned polysiloxane can be measured using an UPOROD meter according to ASTM D 445-46T or JIS Z 8803. Commercially available polysiloxane oils include, for example, "KF-96A-6cs" (dimethyl polysiloxane), "KF-96A-10cs" (dimethyl polysiloxane), "KF-96A-20cs" (dimethyl polysiloxane), and "KF-96A-100cs" (dimethyl polysiloxane) manufactured by Shin-Etsu Chemical Industry Co., Ltd.

Specific examples of the aforementioned hydrocarbon oils include: liquid paraffin, hydrogenated polyisobutylene (fluid isoalkane, heavy liquid isoalkane), cycloalkanes, liquid ceresin, squalene, squalane, isoctadecane, α-olefin oligomers, polybutene, isohexadecane, etc. The aforementioned higher alcohols include, for example: 2-octyldodecyl alcohol, isostearyl alcohol, oleyl alcohol, etc., higher alcohols with 12 or more branched or unsaturated carbon atoms and 24 or fewer carbon atoms. Preferably, they are higher monohydric alcohols with 12 or more branched or unsaturated carbon atoms and 24 or fewer carbon atoms. The aforementioned higher fatty acids include, for example: oleic acid, isostearic acid, etc., fatty acids with 12 or more carbon atoms and 22 or fewer carbon atoms.

From the viewpoints of dissolving component (A1), introducing component (C), and ensuring good emulsification stability, component (A2) preferably contains one or more selected from the group consisting of ester oils and polysiloxane oils, more preferably contains one or more selected from the group consisting of esters represented by general formula (1), general formula (3) or general formula (4) and dimethyl polysiloxanes, and particularly preferably contains: straight-chain or branched-chain fatty acids having 8 or more and 18 carbon atoms and 2 or more and 24 carbon atoms. Monoesters of straight-chain or branched-chain monohydric alcohols; triesters of branched-chain fatty acids with 6 or more and 18 carbon atoms and glycerol; tetraesters of branched-chain fatty acids with 6 or more and 18 carbon atoms and pentaerythritol; diesters of branched-chain fatty acids with 6 or more and 18 carbon atoms and branched-chain diols with 2 or more and 10 carbon atoms; triesters of branched-chain monohydric alcohols with 6 or more and 18 carbon atoms and trimellitic acid; alkyl benzoate esters (C12-15); and a kinematic viscosity of 5,000 mmHg at 25°C. The product contains one or more of the following: a dimethyl polysiloxane with a viscosity of 5,000 ^mm² /s or less. Preferably, it contains one or more of the following: 2-ethylhexanoate cetyl ester, isononyl isononate, isotriadecyl isononate, 2-octyldodecyl myristate, isopropyl palmitate, triglycerides (2-ethylhexanoate), pentaerythritol tetra(2-ethylhexanoate), diisopropyl sebacate, tri(2-ethylhexyl trimellitate), alkyl benzoates (C12-15), and a dimethyl polysiloxane with a dynamic viscosity of 5,000 ^mm² /s or less at 25°C.

The content of component (A2) in the total amount of the water-based oil-based emulsified cosmetic of this invention, from the viewpoint of introducing component (C) and ensuring good emulsification stability, is preferably 5% by mass or more, more preferably 7% by mass or more, and particularly preferably 10% by mass or more. Furthermore, from the viewpoint of suppressing stickiness during application, ensuring good makeup adherence, and suppressing shine caused by sebum, it is preferably 30% by mass or less, more preferably 25% by mass or less, particularly preferably 20% by mass or less, and most preferably 17% by mass or less. More specifically, it is preferably 5-30% by mass, more preferably 7-25% by mass, particularly preferably 10-20% by mass, and most preferably 10-17% by mass.

When the liquid oil contained in component (A2), other than the liquid organic ultraviolet absorber, is selected from one or more of the group consisting of ester oil and polysiloxane oil, the total content of ester oil and polysiloxane oil in component (A2) is preferably 50% by mass or more, more preferably 70% by mass or more, especially preferably 80% by mass or more, most preferably 90% by mass or more, most preferably 95% by mass or more, and preferably less than 100% by mass.

In the water-based oil-based emulsified cosmetic of this invention, the mass ratio of component (A2) to component (A1) [(A2)/(A1)] (hereinafter also referred to as "mass ratio [(A2)/(A1)]") is preferably 1 or more, more preferably 2 or more, particularly better 3 or more, best 4 or more, and most preferably 5 or more, from the viewpoint of dissolving component (A1), introducing component (C), and ensuring good emulsification stability. Furthermore, from the viewpoint of improving UV protection effect, it is preferably 20 or less, more preferably 15 or less, particularly better 10 or less, and most preferably 7 or less. More specifically, it is preferably 1 to 20, more preferably 2 to 15, particularly better 3 to 10, best 4 to 10, most preferably 4 to 7, and even more preferably 5 to 7.

<Component (B): Acrylamide Polymer> This invention's water-based oil-based emulsion cosmetic contains an acrylamide polymer as component (B) from the perspectives of increasing the viscosity of the continuous aqueous phase, ensuring the stable existence of microparticle metal oxides in the oil phase, and improving emulsion stability. Component (B) preferably contains, from the same viewpoint as described above, a constituent unit derived from one or more acrylamide monomers selected from the group consisting of acrylamide and acrylamide dimethyl taurate (hereinafter also referred to as "AMPS"); more preferably, it contains one or more constituent units selected from the group consisting of acrylamide monomers, AMPS monomers and their salts, and copolymers containing constituent units derived from one or more acrylamide monomers selected from the group consisting of acrylamide and AMPS, and their salts; particularly preferably, it contains one or more constituent units selected from the group consisting of acrylamide monomers and copolymers containing constituent units derived from one or more acrylamide monomers selected from the group consisting of acrylamide and AMPS, and their salts.

Specific examples of component (B) include, for example: polyacrylamide (acrylamide monomers), (acrylamide/acrylic acid) copolymers, (AMPS/acrylic acid) copolymers, (AMPS/acrylamide) copolymers, (AMPS/acrylamide/acrylic acid) copolymers, (AMPS/dimethylacrylamide) copolymers, (AMPS/hydroxyethyl acrylate) copolymers, (AMPS/vinylpyrrolidone) copolymers, (AMPS/vinylformamide) copolymers, (AMPS/polyoxyethylene alkyl methacrylate (ethylene oxide average addition mole number: 10~30)) copolymers, and salts thereof. More specific examples of the aforementioned copolymers and their salts include, for instance: (Na acryloxyethyl taurate/Sodium Acryloyldimethyl Taurate Copolymer), (Na acryloxyethyl taurate/Na acrylate Copolymer) (Sodium Acrylate/Sodium Acryloyldimethyl Taurate Copolymer), (Na acryloxyethyl taurate/Na acrylate Copolymer) (Sodium Acrylate/Sodium Acryloyldimethyl Taurate Copolymer), (Na acryloxyethyl taurate/Na acrylate/Dimethylacrylamide Crosspolymer) (Sodium Acrylate/Acryloyldimethyltaurate/Dimethylacrylamide Crosspolymer), and (Ammonium acryloxyethyl taurate/Vinylpyrrolidone Copolymer) (Ammonium Acryloyldimethyltaurate/VP) Copolymers include: (Na acrylonitrile dimethyl taurate/acrylic acid/acrylamide/Na acrylate) copolymer (INCI name: Polyacrylate-13), (Ammonium acrylonitrile dimethyl taurate/dimethylacrylamide/lauryl methacrylate/lauryl methacrylate polyether-4) crosspolymer (INCI name: Polyacrylate Crosspolymer-6), (Ammonium acrylonitrile dimethyl taurate/beheneth-25 methacrylate polyether-25) crosspolymer (INCI name: Ammonium acrylonitrile dimethyl taurate/beheneth-25 methacrylate crosspolymer) and (Ammonium acrylonitrile dimethyl taurate/steearyl methacrylate polyether-25) crosspolymer (INCI name: Ammonium acrylonitrile dimethyl taurate/steearyl methacrylate polyether-25), etc.

Examples of commercially available products containing ingredient (B) include: "SEPIGEL 501" (polyacrylamide, polysorbate 85, mineral oil, isoalkylene), "SEPIGEL 305" (polyacrylamide, hydrogenated polyisobutylene (or (C13,14) isoalkylene), lauryl ether-7, water), "SIMULGEL EG" ((acrylamide dimethyl taurate Na/acrylate Na) copolymer, isohexadecane, polysorbate 80), "SEPIMAX ZEN" ((acrylamide dimethyl taurate ammonium/dimethylacrylamide/lauryl methacrylate/lauryl methacrylate-4) crosspolymer), "SEPINOV EMT" 10" ((Acryloyldimethyltaurate Na/hydroxyethyl acrylate) copolymer, sorbitan isostearate, polysorbate 60), "SIMULGEL NS" ((Acryloyldimethyltaurate Na/hydroxyethyl acrylate) copolymer, squalane, polysorbate 60, water), "SIMULGEL FL" ((Acryloyldimethyltaurate Na/hydroxyethyl acrylate) copolymer, isohexadecane, polysorbate 60, water), "SEPIPLUS S" ((Acryloyldimethyltaurate Na/hydroxyethyl acrylate) copolymer, polyisobutylene, PEG-7 trihydroxymethylpropane coconut oil alkyl ether, water), "SEPIPLUS" 400" ((Acryloyl dimethyl taurate Na/acrylic acid/acrylamide/acrylic acid Na) copolymer, polyisobutylene, polysorbate 20, water) (all manufactured by SEPPIC); "Aristoflex AVC" ((Acryloyl dimethyl taurate Ammonium/Vinylpyrrolidone) copolymer, butanol, water), "Aristoflex HMB" ((Acryloyl dimethyl taurate Ammonium/Behenyl methacrylate Polyether-25) crosspolymer, butanol, water), "Aristoflex HMS" ((Acryloyl dimethyl taurate Ammonium/Stearyl methacrylate Polyether-25) crosspolymer) (all manufactured by Clariant).

Of these, component (B) is preferably selected from one or more of the group consisting of: polyacrylamide, (Na acrylamide/Na acrylate) copolymer, (Na acrylamide/hydroxyethyl acrylate) copolymer, and (ammonium acrylamide/vinylpyrrolidone) copolymer.

The content of component (B) in the total amount of the water-based oil-based emulsion cosmetic of this invention, from the viewpoint of increasing the viscosity of the continuous aqueous phase, ensuring the stable existence of microparticle metal oxides in the oil phase, and improving emulsion stability, is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, particularly preferably 0.5% by mass or more, and even more preferably 3% by mass or less, more preferably 2% by mass or less, particularly preferably 1.5% by mass or less, and most preferably 1% by mass or less. More specifically, it is preferably 0.1 to 3% by mass, more preferably 0.3 to 2% by mass, particularly preferably 0.3 to 1.5% by mass, most preferably 0.5 to 1.5% by mass, and most preferably 0.5 to 1% by mass.

<Component (C): Hydrophobically treated microparticle metal oxide> The water-based oil-based emulsion cosmetic of this invention, from the viewpoint of absorbing or scattering ultraviolet rays and enhancing the ultraviolet protection effect, contains a hydrophobically treated microparticle metal oxide as component (C). The microparticle metal oxide of component (C), from the viewpoint of absorbing or scattering ultraviolet rays and enhancing the ultraviolet protection effect, is preferably selected from one or more of the group consisting of microparticle zinc oxide, microparticle titanium oxide, and microparticle cerium oxide, and more preferably from one or more of the group consisting of microparticle zinc oxide and microparticle titanium oxide. Furthermore, these microparticle metal oxides may contain two or more metals, and may contain one or more of the following metals or their oxides: iron, zirconium, calcium, manganese, magnesium, yttrium, etc.

Hydrophobic treatment of component (C) can include, for example: polysiloxane treatment; alkylalkoxysilane treatment; fatty acid treatment; fluorinated compound treatment using perfluoroalkyl phosphates, perfluoroalcohols, etc.; amino acid treatment using N-acylglutamic acid, etc.; lecithin treatment; metal soap treatment; alkyl phosphate treatment; ASI treatment using N-acylamino acid metal salts (sodium lauryl aspartate), zinc chloride, and alkoxyalkyl titanium (titanium isopropyl triisostearate), etc. These surface treatments can be used individually or in combination of two or more. Among these, the hydrophobic treatment of component (C) is preferred from the perspectives of improving the dispersibility of component (C) in water-based oil-based emulsion cosmetics, enhancing UV protection and emulsion stability, and suppressing friction after application and improving makeup adhesion. It is best to select one or more from the group consisting of polysiloxane treatment, alkylalkoxysilane treatment, and fatty acid treatment.

Surface treatment agents used in polysiloxane treatment can include, for example: methyl polysiloxane, dimethyl polysiloxane (dimethylsiloxane), methylphenyl polysiloxane, methyl hydrogen polysiloxane, dimethylsiloxane/methyl hydrogen silicate copolymer (hydrogenated dimethylsiloxane), methyl cyclopolysiloxane, dodecyl cyclohexasiloxane, tetradecyl hexasiloxane, and dimethylsiloxane/methyl (polyoxyethylene)siloxane. Various polysiloxane oils, including alkyl/methyl (polyoxypropylene)siloxane copolymers, dimethylsiloxane/methyl (polyoxyethylene)siloxane copolymers, dimethylsiloxane/methyl (polyoxypropylene)siloxane copolymers, dimethylsiloxane/methyl cetoxysiloxane copolymers, dimethylsiloxane/methyl stearoxysiloxane copolymers, and (alkyl acrylate/dimethylsiloxane) copolymers. Among these, the surface treatment agent used in polysiloxane treatment is preferably dimethylpolysiloxane (dimethylsiloxane), methylhydrosiloxane, or dimethylsiloxane/methylhydrosiloxane copolymer (dimethylhydrosiloxane), and more preferably methylhydrosiloxane or dimethylsiloxane/methylhydrosiloxane copolymer (dimethylhydrosiloxane), from the perspectives of improving the dispersibility of component (C) in water-based oil-based emulsion cosmetics, enhancing UV protection and emulsion stability, and suppressing friction after application and improving makeup adhesion.

The surface treatment agent used in alkylalkoxysilane treatment is preferred from the perspectives of improving the dispersibility of component (C) in water-based oil-based emulsion cosmetics, enhancing UV protection and emulsion stability, suppressing friction after application, and improving makeup adhesion. It is preferably an alkylalkoxysilane with a straight-chain or branched-chain alkyl group having 6 or more and 20 carbon atoms. More preferably is octyltriethoxysilane (triethoxyoctylsilane), octyltrimethoxysilane (trimethoxyoctylsilane), and especially preferably is octyltriethoxysilane (triethoxyoctylsilane).

Surface treatment agents used in fatty acid treatment can be, for example, linear or branched higher fatty acids with 12 or more but less than 22 carbon atoms. Among these, surface treatment agents used in fatty acid treatment are preferred from the perspectives of improving the dispersibility of components (C) in water-based oil-based emulsion cosmetics, enhancing UV protection and emulsion stability, and suppressing friction after application and improving makeup adhesion. They are linear or branched higher fatty acids with 14 or more but less than 22 carbon atoms, more preferably linear or branched higher fatty acids with 16 or more but less than 20 carbon atoms, and especially stearic acid and isostearic acid.

As described above, the hydrophobic treatment of component (C) aims to improve the dispersibility of component (C) in water-based oil-based emulsion cosmetics, enhance UV protection and emulsion stability, suppress friction after application, and improve makeup adhesion. More preferably, it involves selecting one or more from the group consisting of methylhydrosiloxanes and dimethylsiloxane/methylhydrosiloxane copolymers, and using them as surface treatment agents from the group consisting of polysiloxane treatment, alkylalkoxysilane treatment, and fatty acid treatment. One or more of the following: preferably, a polysiloxane treatment using one or more of the following as a surface treatment agent, selected from the group consisting of methylhydrosiloxane and dimethylsiloxane/methylhydrosiloxane copolymers; an alkylalkoxysilane treatment using an alkylalkoxysilane having a straight-chain or branched-chain alkyl group having 6 or more and 20 or less carbon atoms; and a fatty acid treatment using a straight-chain or branched-chain higher fatty acid having 14 or more and 22 or less carbon atoms.

The aforementioned surface treatment agents can be used alone or in combination of two or more. Furthermore, when titanium oxide is used as the metal oxide in component (C), from the viewpoint of reducing photocatalytic activity, in addition to the surface treatment agents used for hydrophobic treatment mentioned above, treatment agents such as silicon dioxide, hydrated silicon dioxide, and hydrogen-containing oxides of metals such as aluminum can also be used in combination.

The amount of hydrophobic treatment applied to component (C) is preferably 0.1% by weight or more, more preferably 40% by weight or less, and even more preferably 30% by weight or less, from the perspectives of improving the dispersibility of component (C) in water-based oil-based emulsion cosmetics, enhancing UV protection and emulsion stability, and suppressing friction after application and improving makeup adhesion. Furthermore, in this invention, the mass of component (C) and the average primary particle size described below refer to the mass and average primary particle size containing the surface treatment agent.

The shape of component (C) can be, for example, spherical, flake, plate, rod, woven, needle-like, or irregular; any shape can be used. From the perspective of improving UV protection and emulsion stability, the average primary particle size of component (C) is preferably below 1 μm, more preferably below 800 nm, exceptionally preferably below 500 nm, best below 300 nm, most preferably below 200 nm, even better below 100 nm, exceptionally best below 90 nm, particularly good below 50 nm, and even better below 40 nm. Furthermore, from a generality perspective, it is preferably above 1 nm, more preferably above 5 nm, and exceptionally good above 10 nm. More specifically, the average primary particle size of component (C), from the same perspective as above, is preferably 1 nm to 1 μm, more preferably 1 to 800 nm, exceptionally good 5 to 500 nm, best 5 to 300 nm, most optimal 5 to 200 nm, even better 5 to 100 nm, exceptionally good 5 to 90 nm, particularly good 5 to 50 nm, even better 10 to 50 nm, and even more exceptionally good 10 to 40 nm.

The average primary particle size of component (C) of this invention can be obtained by observation of images using a transmission electron microscope (TEM). Specifically, the maximum minor diameter of 300 primary particles in the image is measured using TEM at a magnification of 50,000, and then the number average is calculated. Here, "maximum minor diameter" refers to the minor diameter with the longest length among the minor diameters orthogonal to the major diameter when component (C) has a shape other than a sheet or plate. Furthermore, when component (C) has a sheet or plate shape, the thickness of 300 primary particles in the image observed under the same conditions is measured, and then the number average is calculated. Specifically, the method described in the embodiments is used for measurement.

Component (C) is the microparticle metal oxide before hydrophobic treatment of component (C'), which can be prepared using the aforementioned surface treatment agent and a known method. For example, when using the above-mentioned polysiloxane oil for surface treatment, as described in Japanese Patent No. 3187440, microparticle metal oxides such as zinc oxide are coated in a non-gas phase using at least one of a polysiloxane compound (excluding silane compounds) composed of organic polysiloxanes and polysiloxane resins, and then calcined in an oxygen-containing gas environment at a temperature of 600~950°C, so that the surface of the silicon oxide coated with microparticle metal oxides can be prepared. Furthermore, the surface treatment using the aforementioned alkylalkoxysilane can be prepared as described in Japanese Patent Application Publication No. 2007-326902, by coating the microparticle metal oxide with a specific polysiloxane compound, followed by surface treatment with the alkylalkoxysilane in water. Additionally, the preferred state and measurement method for the average primary particle size of component (C') (the microparticle metal oxide before hydrophobic treatment) used in the aforementioned hydrophobication treatment are the same as those for component (C).

Commercially available hydrophobically treated microparticle zinc oxide products include, for example: the FINEX series (manufactured by Sakai Kagaku Kogyo Co., Ltd.); the MZ series and MZY series (all manufactured by TAYCA Co., Ltd.). Commercially available hydrophobically treated microparticle titanium oxide products include, for example: the STR series (manufactured by Sakai Kagaku Kogyo Co., Ltd.); the TTO-55 series and TTO-51 series (all manufactured by Ishihara Sangyo Co., Ltd.); the MT series and MTY series (all manufactured by TAYCA Co., Ltd.).

The content of component (C) in the total amount of the water-based oil-based emulsion cosmetic of this invention, from the viewpoint of improving the UV protection effect, is preferably 1% by mass or more, more preferably 3% by mass or more, particularly preferably 7% by mass or more, and best preferably 10% by mass or more. Furthermore, from the viewpoint of ensuring good emulsion stability, it is preferably 30% by mass or less, more preferably 27% by mass or less, particularly preferably 25% by mass or less, and best preferably 20% by mass or less. More specifically, from the viewpoints of improving the UV protection effect and ensuring good emulsion stability, it is preferably 1-30% by mass, more preferably 3-30% by mass, particularly preferably 7-27% by mass, best preferably 7-25% by mass, most preferably 10-25% by mass, and even more preferably 10-20% by mass.

In the water-based oil-based emulsified cosmetic of the present invention, the mass ratio of component (C) to the total content of components (A1) and (A2) [(C)/(A1+A2)] (hereinafter also referred to as "content mass ratio [(C)/(A1+A2)]") is preferably 0.25 or higher, more preferably 0.30 or higher, particularly better 0.40 or higher, best 0.50 or higher, and most preferably 0.60 or higher, from the perspective of improving UV protection and emulsification stability, as well as improving makeup adherence and suppressing shine caused by sebum. Furthermore, from the perspective of suppressing stickiness during application, it is preferably 1.8 or lower, more preferably 1.5 or lower, particularly better 1.3 or lower, best 1.0 or lower, and most preferably 0.80 or lower. More specifically, the better range is 0.30~1.5, the better range is 0.40~1.3, the excellent range is 0.50~1.0, the best range is 0.50~0.80, and the most excellent range is 0.60~0.80.

In addition to ingredients (A1), (A2), (B), and (C), the water-based oil-based emulsion cosmetic of this invention may appropriately contain any ingredients suitable for the cosmetic application, provided that such inclusions do not impair the effectiveness of the invention. Examples of such ingredients include, but are not limited to, ingredients (A1), (A2), (B), and (C), ultraviolet absorbers, oils, surfactants, water-soluble polymers, neutralizers, pH adjusters, bactericides, anti-inflammatory agents, preservatives, colorants, chelating agents, whitening agents, antiperspirants, insect repellents, physiologically active ingredients, salts, antioxidants, and fragrances.

<Ingredient (D): Polyols> This invention's water-based oil-based emulsified cosmetic, from the viewpoint of suppressing stickiness during application and improving makeup adherence, preferably further contains polyols, specifically ingredient (D). Ingredient (D) can be, for example: ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol (average molecular weight less than 650), 1,2-propanediol, 1,3-propanediol, dipropylene glycol, polypropylene glycol (average molecular weight less than 650), isopentyl glycol, 1,3-butanediol, and other diols; glycerin, diglycerides, polyglycerol, and other ternary or higher polyols. Of these, component (D) is preferably a polyol with 2 or more carbon atoms and 12 or fewer carbon atoms, more preferably a polyol with 2 or more carbon atoms and 6 or fewer carbon atoms, particularly preferably one or more selected from the group consisting of ethylene glycol, diethylene glycol, propylene glycol, 1,2-propanediol, dipropylene glycol, 1,3-butanediol, and glycerol, and most preferably one or more selected from the group consisting of propylene glycol, dipropylene glycol, 1,3-butanediol, and glycerol. These alcohols may be used alone or in combination of two or more.

The content of component (D) in the total amount of the water-based oil-based emulsion cosmetic of this invention, from the viewpoint of suppressing stickiness during application and ensuring good makeup adhesion, is preferably 0.5% by weight or more, more preferably 1% by weight or more, particularly preferably 2% by weight or more, best preferably 3% by weight or more, most preferably 4% by weight or more, and even more preferably 5% by weight or more; furthermore, it is preferably 15% by weight or less, more preferably 13% by weight or less, and particularly preferably 10% by weight or less. More specifically, it is preferably 0.5~15% by weight, more preferably 1~13% by weight, particularly preferably 2~13% by weight, best preferably 3~10% by weight, most preferably 4~10% by weight, and even more preferably 5~10% by weight. The content of component (D) in the total amount of the water-based oil-based emulsion cosmetic of this invention, from the viewpoints of suppressing stickiness during application, ensuring good makeup adherence, and suppressing shine caused by sebum, is preferably 0.5% by weight or more, more preferably 1% by weight or more, particularly preferably 2% by weight or more, and most preferably 3% by weight or more; furthermore, it is preferably 15% by weight or less, more preferably 13% by weight or less, particularly preferably 10% by weight or less, best preferably 7% by weight or less, and most preferably 5% by weight or less. More specifically, it is preferably 0.5 to 15% by weight, more preferably 1 to 13% by weight, particularly preferably 2 to 13% by weight, best preferably 3 to 10% by weight, most preferably 3 to 7% by weight, and even more preferably 3 to 5% by weight.

<Ingredient (E): Surfactant> From the viewpoint of achieving good emulsification stability, the water-based oil-based emulsion cosmetic of this invention preferably further contains an ingredient (E) as a surfactant. Ingredient (E) is not particularly limited and can be any of the following: nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants. One or more of these can be used alone.

Among these, component (E) is preferably a nonionic surfactant, such as: sorbitan fatty acid ester, polyoxyalkylene hardened sunflower oil, polyoxyalkylene sorbitan fatty acid ester, polyoxyalkylene alkyl ether, polyether modified polysiloxane, etc. Specific examples include: sorbitan monostearate, sorbitan monoisostearate, polyoxyethylene cured sunflower oil (average EO addition mole number 60), polyoxyethylene cured sunflower oil (average EO addition mole number 40), polyoxyethylene sorbitan monolaurate (average EO addition mole number 20), polyoxyethylene sorbitan monostearate (average EO addition mole number 20), polyoxyethylene sorbitan oleate (average EO addition mole number 20), polyoxyethylene (average EO addition mole number 7) lauryl ether, polyoxyethylene (average EO addition mole number 7) trihydroxymethylpropane coconut oil alkyl ether, dimethylsiloxane copolyol, etc. These nonionic surfactants can be used alone or in combination of two or more.

The content of component (E) in the total amount of the water-based oil-based emulsified cosmetic of the present invention is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and particularly preferably 0.5% by mass or more; furthermore, it is preferably 3% by mass or less, more preferably 2% by mass or less, and particularly preferably 1% by mass or less. More specifically, it is preferably 0.1 to 3% by mass, more preferably 0.3 to 2% by mass, and particularly preferably 0.5 to 1% by mass.

<Ingredient (F): Other Water-Soluble Polymers> From the viewpoint of achieving good emulsification stability, the water-based oil-based emulsion cosmetic of this invention preferably contains other water-soluble polymers with thickening properties besides ingredient (B) that further include ingredient (F). Ingredient (F) is used within the scope of conventional cosmetics, but there are no other restrictions; it can be any of natural polymers, semi-synthetic polymers, or synthetic polymers other than ingredient (B).

Examples of natural polymers include: carrageenan, galangal, and alginate. Among these, carrageenan is preferred for its good emulsification stability. Semi-synthetic polymers include: modified polysaccharides such as hydroxycellulose, hydroxypropylcellulose, sodium carboxymethylcellulose, methylcellulose, hydroxymethylcellulose, and cationic cellulose. Synthetic polymers other than component (B) include: acrylic polymers other than component (B), such as carboxyethylene polymers (crosslinked polyacrylic acid), polyacrylic acid, sodium polyacrylate, and (acrylic acid/alkyl methacrylate) copolymers; polyvinylpyrrolidone, polyvinyl alcohol, and cationic polyvinylpyrrolidone.

Commercially available carboxyethylene polymers include, for example, "Carbopol 910," "Carbopol 934," "Carbopol 940," "Carbopol 941," "Carbopol 980," and "Carbopol 981" (all manufactured by Lubrizol Advanced Materials). Commercially available (acrylic acid/alkyl methacrylate) copolymers include, for example, "Carbopol 1382," "Carbopol ETD2020," "PEMULEN TR-1," and "PEMULEN TR-2" (all manufactured by Lubrizol Advanced Materials).

The content of component (F) in the total amount of the water-based oil-based emulsified cosmetic of the present invention, from the viewpoint of obtaining good emulsification stability, is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and particularly preferably 0.07% by mass or more. Furthermore, from the viewpoint of good user experience, it is preferably 5% by mass or less, more preferably 3% by mass or less, and particularly preferably 1% by mass or less. More specifically, it is preferably 0.01 to 5% by mass, more preferably 0.05 to 3% by mass, and particularly preferably 0.07 to 1% by mass.

(Aqueous Medium) The water-based oil-based emulsified cosmetic of the present invention contains at least water, in addition to the aqueous medium component (D). In the present invention, the aqueous medium other than component (D) and water may further contain, for example, saturated monohydric alcohols with 1 or more carbon atoms and 3 or fewer carbon atoms, such as ethanol, propanol, and isopropanol. The content of the aqueous medium other than component (D) in the total amount of the water-based oil-based emulsified cosmetic of the present invention is within the range that allows it to form a water-based oil-based emulsified cosmetic. From the viewpoint of improving emulsification stability, it is preferably 40% by mass or more, more preferably 45% by mass or more, particularly preferably 50% by mass or more, best preferably 55% by mass or more, most preferably 60% by mass or more, and preferably 90% by mass or less, more preferably 80% by mass or less, and particularly preferably 75% by mass or less. More specifically, better is 40-90% quality, even better is 45-80% quality, excellent is 50-75% quality, best is 55-75% quality, and most excellent is 60-75% quality.

The water-based oil-emulsified cosmetic of this invention is widely used in hair cosmetics such as shampoos, conditioners, and hair creams; and skin cosmetics such as face washes, makeup removers, sunscreens, face masks, and massage products. Among these, the water-based oil-emulsified cosmetic of this invention, due to its excellent UV protection effect, is suitable for sun protection applications, such as sunscreens (toners, creams, lotions, serums, etc.), tanning agents, base makeup products, and foundations. The water-based oil-based emulsified cosmetic formulation of this invention is applicable to various forms, including liquid, emulsion, cream, paste, solid, and multilayer forms, and is also suitable for sheet formulations, sprays, and mousses.

(Method for Manufacturing Water-Based Oil-Based Emulsified Cosmetics) The method for manufacturing water-based oil-based emulsified cosmetics of this invention is not particularly limited. It can be adapted to the formulation of the water-based oil-based emulsified cosmetic by using appropriate known methods. For example, it includes a method that involves uniformly mixing components (A1), (A2), (B), (C), and any other aforementioned components as needed, using a homogenizing mixer or similar device.

The method for manufacturing an oil-based emulsified cosmetic in water according to the present invention, particularly from the perspectives of improving the dispersibility of component (C) in the oil-based emulsified cosmetic, enhancing the UV protection effect and emulsification stability, and suppressing stickiness during application, ensuring good makeup adherence, and suppressing shine caused by sebum, preferably includes the following steps: a dispersion in component (C) containing components (A1), components (A2), and, if necessary, an oil phase component containing any of the aforementioned oil-soluble components, and a formulation containing component (B), an aqueous medium, and, if necessary, an aqueous phase component containing any of the aforementioned water-soluble components, and then mixing and emulsifying the mixture. More preferably, this method includes steps I to III as described below. Step I: Add components (A1), (A2), and any other oil-soluble components as needed to component (C), and mix thoroughly to obtain dispersion (i) that disperses component (C). Step II: Mix component (B), an aqueous medium, and an aqueous phase containing any of the aforementioned water-soluble components as needed to obtain formulation (ii). Step III: Add the dispersion (i) obtained in Step I to the formulation (ii) obtained in Step II, and mix thoroughly to emulsify it, thereby obtaining an oil-based emulsion cosmetic in water.

Step I, from the viewpoint of improving the dispersibility of component (C) in water-based oil-based emulsion cosmetics, preferably includes the following steps I-1 and I-2. Step I-1: The step of uniformly mixing component (A1), component (A2), and an oil phase component containing any of the aforementioned oil-soluble components as needed, to obtain a formulation (i'). Step I-2: The step of adding component (C) to the formulation (i') obtained in Step I-1, and uniformly mixing to obtain a dispersion (i) that disperses component (C).

The mixing of the oil phase component in step I-1 and the mixing of the aqueous phase component in step II are preferably performed by heating and stirring simultaneously within a temperature range of 20°C to 90°C. In step II, the obtained formulation (ii) is preferably obtained by cooling to a temperature range of 15°C to 35°C and then uniformly mixing. Furthermore, in step III, it is preferable to add the dispersion (i) obtained in step I while stirring the formulation (ii) obtained in step II, maintaining a temperature range of 30°C to 90°C, and then uniformly mixing to emulsify it.

Regarding the above-mentioned embodiments, the present invention further discloses the following embodiments. <1> An oil-in-water emulsion cosmetic contains the following components (A1), (A2), (B), and (C): Component (A1): A non-water-soluble organic ultraviolet absorber that is solid at 25°C Component (A2): A liquid oil Component (B): One or more selected from the group consisting of acrylamide monomers, copolymers containing constituent units derived from acrylamide monomers, and their salts; wherein the acrylamide monomer is one or more selected from the group consisting of acrylamide and acrylamide dimethyl taurate Component (C): One or more selected from the group consisting of hydrophobically treated microparticle zinc oxide and microparticle titanium oxide. The mass ratio of component (C) to the total mass of components (A1) and (A2) [(C)/(A1+A2)] is 0.30 or higher and 1.5 or lower; The total mass content of component (A2) of 2-ethylhexyl p-methoxycinnamate and octocrylene is less than 2% by mass in the total amount of the water-oil emulsion cosmetic.

<2> The water-based oil-based emulsified cosmetic as described in <1> above further contains a polyol of component (D). <3> The water-based oil-based emulsified cosmetic as described in <2> above, wherein the content of component (D) in the total amount of the water-based oil-based emulsified cosmetic is 1% by mass or more and 13% by mass or less. <4> The water-based oil-based emulsified cosmetic as described in <2> or <3> above, wherein the content of component (D) in the total amount of the water-based oil-based emulsified cosmetic is 3% by mass or more and 10% by mass or less.

<5> In any of the water-based oil-based emulsified cosmetics described in <1> to <4> above, the combined content of 2-ethylhexyl p-methoxycinnamate and octocrylene is less than 0.7% by mass in the total amount of the water-based oil-based emulsified cosmetic. <6> In any of the water-based oil-based emulsified cosmetics described in <1> to <4> above, the combined content of 2-ethylhexyl p-methoxycinnamate and octocrylene is less than 0.3% by mass in the total amount of the water-based oil-based emulsified cosmetic. <7> In the water-based oil-based emulsified cosmetic described in any of <1> to <6> above, the mass ratio of the content of component (C) to the total content of components (A1) and (A2) [(C)/(A1+A2)] is 0.40 or more and 1.3 or less.

<8> In the water-based oil-based emulsified cosmetic as described in any of <1> to <7> above, the hydrophobic treatment of component (C) is selected from one or more of the group consisting of polysiloxane treatment, alkylalkoxysilane treatment, and fatty acid treatment. <9> In the water-based oil-based emulsified cosmetic as described in any of <1> to <7> above, the hydrophobic treatment of component (C) is selected from: one or more of the group consisting of polysiloxane treatment, alkylalkoxysilane treatment, and fatty acid treatment selected as surface treatment agents, comprising methylhydropolysiloxane and dimethylsiloxane/methylhydrosiloxane copolymer (dimethylhydrosiloxane hydroxide). <10> In any of the above-described oil-in-water emulsified cosmetics (1> to <9>), the average primary particle size of component (C) is 1 nm or more and 800 nm or less. <11> In any of the above-described oil-in-water emulsified cosmetics (1> to <9>), the average primary particle size of component (C) is 5 nm or more and 100 nm or less. <12> In any of the above-described oil-in-water emulsified cosmetics (1> to <11>), the content of component (C) in the total amount of the oil-in-water emulsified cosmetic is 3% by mass or more and 30% by mass or less. <13> In any of the above-described oil-in-water emulsified cosmetics (1> to <11>), the content of component (C) in the total amount of the oil-in-water emulsified cosmetic is 7% by mass or more and 25% by mass or less. <14> In any of the above-described oil-in-water emulsified cosmetics (1> to <13>), the content of component (B) in the total amount of the oil-in-water emulsified cosmetic is 0.1% by mass or more and 3% by mass or less. <15> In any of the above-described oil-in-water emulsified cosmetics (1> to <13>), the content of component (B) in the total amount of the oil-in-water emulsified cosmetic is 0.3% by mass or more and 2% by mass or less.

<16> The water-based oil-based emulsified cosmetic as described in any of <1> to <15> above, wherein component (B) is selected from one or more of the group consisting of: polyacrylamide, (Na acrylamide/Na acrylate) copolymer, (Na acrylamide/hydroxyethyl acrylate) copolymer, and (ammonium acrylamide/vinylpyrrolidone) copolymer. <17> The water-based oil-based emulsified cosmetic as described in any of <1> to <16> above, wherein component (A2) contains one or more of the group consisting of ester oils and polysiloxane oils. <18> An oil-in-water emulsion cosmetic as described in any of <1> to <17> above, wherein component (A1) is selected from one or more of the following groups: 4-tert-butyl-4'-methoxydibenzoylmethane, 2-(4-diethylamino-2-hydroxybenzoyl)hexyl benzoate, 2,4,6-tris[4-(2-ethylhexyloxycarbonyl)aniline]-1,3,5-tris(2-ethylhexyloxy)aniline, 2-hydroxy-4-methoxydiphenyl ketone, cresoltrazolium trisiloxane, and 2,4-bis{[4-(2-ethylhexyloxy)-2-hydroxy]phenyl}-6-(4-methoxyphenyl)-1,3,5-tris ...6-(4-ethylhexyloxy)-6-(4-ethylhexyloxy)-6-(4-ethylhexyloxy)-6-(4-ethylhexyloxy)-6-(4-ethylhexyloxy)-6-(4-ethyl <19> Water-based oil-based emulsified cosmetics as described in any of <1> to <18> above are intended for use in sun protection.

<20> A water-based oil-based emulsion cosmetic, used for sun protection, contains: the following ingredients (A1), (A2), (B), (C), and (D): Ingredient (A1): A non-water-soluble organic ultraviolet absorber that is solid at 25°C Ingredient (A2): A liquid oil Ingredient (B): One or more selected from the group consisting of acrylamide monomers, copolymers containing constituent units derived from acrylamide monomers, and their salts; wherein the acrylamide monomer is one or more selected from the group consisting of acrylamide and acrylamide dimethyl taurate. Component (C): One or more selected from the group consisting of hydrophobically treated microparticles of zinc oxide and titanium oxide with an average primary particle size of 1 nm or more and 800 nm or less. Component (D): Polyol Wherein, the mass ratio of the content of component (C) to the total content of components (A1) and (A2) [(C)/(A1+A2)] is 0.30 or more and 1.5 or less; The total content of p-methoxycinnamic acid-2-ethylhexyl ester and octocrylene in component (A2) is 2% or less by mass in the total amount of the water-oil emulsion cosmetic; The content of component (D) is 1% or more by mass and 13% or less by mass.

<21> A water-based oil-based emulsion cosmetic, used for sun protection, contains: the following ingredients (A1), (A2), (B), (C), and (D): Ingredient (A1): A non-water-soluble organic ultraviolet absorber that is solid at 25°C Ingredient (A2): A liquid oil Ingredient (B): One or more selected from the group consisting of acrylamide monomers, copolymers containing constituent units derived from acrylamide monomers, and their salts; wherein the acrylamide monomer is one or more selected from the group consisting of acrylamide and acrylonitrile dimethyl taurate. Component (C): One or more selected from a group consisting of hydrophobically treated microparticles of zinc oxide and titanium oxide with an average primary particle size of 5 nm to 100 nm. Component (D): Polyol. The mass ratio of the content of component (C) to the total content of components (A1) and (A2) [(C)/(A1+A2)] is 0.40 or more and 1.3 or less; The total content of p-methoxycinnamic acid-2-ethylhexyl ester and octocrylene in component (A2) is 2% by mass or less in the total amount of the water-oil emulsion cosmetic; The content of component (D) is 3% by mass or more and 10% by mass or less.

<22> A water-based oil-based emulsion cosmetic, used for sun protection, contains: the following ingredients (A1), (A2), (B), and (C): Ingredient (A1): A non-water-soluble organic ultraviolet absorber that is solid at 25°C Ingredient (A2): A liquid oil Ingredient (B): One or more selected from the group consisting of acrylamide monomers, copolymers containing constituent units derived from acrylamide monomers, and their salts; wherein the acrylamide monomer is one or more selected from the group consisting of acrylamide and acrylamide dimethyl taurate. Component (C): One or more selected from a group consisting of hydrophobically treated microparticles of zinc oxide and titanium oxide with an average primary particle size of 5 nm to 100 nm. The mass ratio of the content of component (C) to the total content of component (A1) and component (A2) [(C)/(A1+A2)] is 0.40 or more and 1.3 or less; The total content of component (A2) of 2-ethylhexyl p-methoxycinnamate and octocrylene is 2% by mass or less in the total amount of the water-oil emulsion cosmetic. The hydrophobic treatment of component (C) is selected from one or more of the following groups: polysiloxane treatment, alkylalkoxysilane treatment, and fatty acid treatment, all selected from the group consisting of methylhydrosiloxane, dimethylsiloxane/methylhydrosiloxane copolymer (dimethylhydrosiloxane hydrogenation).

<23> A water-based oil-based emulsion cosmetic, used for sun protection, contains: the following ingredients (A1), (A2), (B), (C), and (D): Ingredient (A1): A non-water-soluble organic ultraviolet absorber that is solid at 25°C Ingredient (A2): A liquid oil Ingredient (B): One or more selected from the group consisting of acrylamide monomers, copolymers containing constituent units derived from acrylamide monomers, and their salts; wherein the acrylamide monomer is one or more selected from the group consisting of acrylamide and acrylonitrile dimethyl taurate. Component (C): One or more selected from a group consisting of hydrophobically treated microparticles of zinc oxide and titanium oxide with an average primary particle size of 5 nm to 100 nm. Component (D): Polyol. The mass ratio of component (C) to the total content of components (A1) and (A2) [(C)/(A1+A2)] is 0.40 or more and 1.3 or less; The total content of 2-ethylhexyl p-methoxycinnamate and octocrylene in component (A2) is 2% by mass or less in the total amount of the water-oil emulsion cosmetic. The hydrophobic treatment of component (C) is selected from one or more of the following: a polysiloxane treatment, alkylalkoxysilane treatment, and fatty acid treatment selected from the group consisting of methylhydrosiloxane, dimethylsiloxane/methylhydrosiloxane copolymer (dimethylhydrosiloxane hydroxide), used as a surface treatment agent; The content of component (D) is 1% by mass or more and 13% by mass or less.

<24> In any of the above-described items <20> to <23>, the total content of 2-ethylhexyl p-methoxycinnamate and octocrylene is 0.7% by mass or less in the total amount of the water-based oil-based emulsified cosmetic. <25> In any of the above-described items <20> to <23>, the total content of 2-ethylhexyl p-methoxycinnamate and octocrylene is 0.3% by mass or less in the total amount of the water-based oil-based emulsified cosmetic. <26> In any of the above-described items <20> to <25>, the content of component (C) in the total amount of the water-based oil-based emulsified cosmetic is 3% by mass or more and 30% by mass or less. <27> The water-based oil-based emulsified cosmetic described in any of <20> to <25> above, wherein the content of component (C) in the total amount of the water-based oil-based emulsified cosmetic is 7% by mass or more and 25% by mass or less. <28> The water-based oil-based emulsified cosmetic described in any of <20> to <27> above, wherein the content of component (B) in the total amount of the water-based oil-based emulsified cosmetic is 0.1% by mass or more and 3% by mass or less. <29> The water-based oil-based emulsified cosmetic described in any of <20> to <27> above, wherein the content of component (B) in the total amount of the water-based oil-based emulsified cosmetic is 0.3% by mass or more and 2% by mass or less.

<30> The water-based oil-based emulsified cosmetic as described in any of <20> to <29> above, wherein component (B) is selected from one or more of the group consisting of: polyacrylamide, (Na acrylamide/Na acrylate) copolymer, (Na acrylamide/hydroxyethyl acrylate) copolymer, and (ammonium acrylamide/vinylpyrrolidone) copolymer. <31> The water-based oil-based emulsified cosmetic as described in any of <20> to <30> above, wherein component (A2) contains one or more of the group consisting of ester oil and polysiloxane oil. <32> An oil-in-water emulsion cosmetic as described in any of <20> to <31> above, wherein component (A1) is selected from one or more of the following groups: 4-tert-butyl-4'-methoxydibenzoylmethane, 2-(4-diethylamino-2-hydroxybenzoyl)hexyl benzoate, 2,4,6-tris[4-(2-ethylhexyloxycarbonyl)anilino]-1,3,5-tris(2-ethylhexyloxy ...

The invention will now be described in detail with reference to embodiments and comparative examples; however, the invention is not limited to these examples.

(Average Primary Particle Size of Components (C) and (C')) The average primary particle size of components (C) and (C') was determined according to the following method: When the test sample has a shape other than flake or plate, the pre-prepared test sample dispersion was placed on the stage of a transmission electron microscope (TEM) (trade name "JEM1400Plus", manufactured by Nippon Electronics Co., Ltd.). After air drying, the image was observed using the TEM at a magnification of 50,000. The maximum minor diameter of 300 primary particle sizes in the observed image was measured, and the numerical average was set as the average primary particle size for each particle. Here, "maximum minor diameter" refers to the minor diameter orthogonal to the major diameter that has the longest length. When the test sample has a sheet-like or plate-like shape, the thickness of 300 primary particle sizes in the observed image, observed under the same method and magnification conditions as described above, is measured, and the numerical average is set as the average primary particle size for each. Additionally, the dispersion of the test sample is prepared by adding 95g of ethanol as a solvent to 5g of the test sample and then ultrasonically dispersing it.

Example 1 (Preparation of Dimethylsiloxane-Treated Microparticle Zinc Oxide C1): 88 parts by weight of microparticle zinc oxide (slightly spherical, average primary particle size 25 nm) of component (C') and 12 parts by weight of dimethylpolysiloxane (dimethylsiloxane) (kinematic viscosity 20 ^mm² /s, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) as a surface treatment agent were added to toluene. After thorough stirring, the toluene was removed by heating under reduced pressure. The obtained powder was pulverized using an ultrafine pulverizer. Next, it was calcined in air at 800°C for 2 hours in a high-temperature furnace to obtain dimethylsiloxane-treated microparticle zinc oxide C1 of component (C).

Example 2 (Preparation of Methylhydropolysiloxane-Treated Microparticle Zinc Oxide C2) A slurry was prepared from: 93 parts by mass of microparticle zinc oxide (slightly spherical, average primary particle size 35 nm) of component (C'), 7 parts by mass of methylhydropolysiloxane (Shin-Etsu Chemical Industry Co., Ltd. "KF-99P") as a surface treatment agent, and isopropanol. After thorough stirring and pulverization, the solvent was removed by heating under reduced pressure. The mixture was then heated in air at 150°C for 4 hours to obtain methylhydropolysiloxane-treated microparticle zinc oxide C2 of component (C).

Example 3 (Preparation of Triethoxyoctylsilane-Treated Microparticle Zinc Oxide C3) A slurry was prepared from: 93 parts by mass of microparticle zinc oxide (slightly spherical, average primary particle size 35 nm) of component (C'), 7 parts by mass of octyltriethoxysilane (triethoxyoctylsilane) as a surface treatment agent, and toluene. The slurry was pulverized and crushed using a bead mill (SHINMARU ENTERPRISES bead mill). Next, after removing toluene under reduced pressure and heating, the slurry was heat-treated at 150°C for 4 hours using a forced-airflow dryer to obtain triethoxyoctylsilane-treated microparticle zinc oxide C3 of component (C).

Preparation Example 4 (Preparation of Dimethylsiloxane-Treated Microparticle Titanium Oxide C4): 88 parts by weight of microparticle titanium oxide (slightly spherical, average primary particle size 10 nm) of component (C') and 12 parts by weight of dimethylpolysiloxane (dimethylsiloxane) (kinematic viscosity 20 ^mm² /s, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) as a surface treatment agent were added to toluene. After thorough stirring, the toluene was removed by heating under reduced pressure. The obtained powder was pulverized using an ultrafine pulverizer. Then, it was calcined in air at 800°C for 2 hours using a high-temperature furnace to obtain dimethylsiloxane-treated microparticle titanium oxide C4 of component (C).

[Examples 1-26, Comparative Examples 1-6, Reference Example 1] Following the formulations shown in Tables 1-4, various water-based oil-based emulsified cosmetics were obtained using the following method: Ingredients 1-21 and 46 shown in Tables 1-4 were uniformly mixed and heated to 80°C to dissolve, obtaining formulation (i') (Step I-1). Next, while maintaining the obtained formulation (i') at 80°C, ingredients 27-33 shown in Tables 1-4 were added and uniformly mixed to disperse, obtaining dispersion (i) (Step I-2). Additionally, ingredients 22-26, 34-45, 49, and 50 shown in Tables 1-4 are heated to 40°C and dissolved. After naturally cooling to 25°C, ingredients 47 and 48 are added and mixed thoroughly to obtain formulation (ii) (Step II). While stirring the obtained formulation (ii), dispersion (i) is added while maintaining the temperature at 80°C. The mixture is then homogenized using a homogenizer to emulsify the mixture and obtain an oil-based emulsion cosmetic (Step III).

The obtained water-based oil-emulsified cosmetics were evaluated for the following: (1) UV protection capability, (2) emulsion stability, and (3) user experience (non-sticky feel upon application, good makeup adherence immediately after application, and no oily shine due to sebum after 3 hours). Comparative Examples 2 and 3, because they were immediately uneven and separated into oil and water phases after preparation, were only evaluated for emulsion stability; UV protection capability and user experience were not evaluated. The results are shown in Tables 1-4.

(1) UV Protection Capability: The water-based oil-based emulsified cosmetics shown in Tables 1-4 were evenly applied to a square PMMA plate (HelioScreen HD6) at a concentration of 1.3 mg/ ^cm² , and allowed to air dry for 15 minutes to form test samples. Each prepared sample was irradiated with UV light from a certain distance (10 mm) using an SPF analyzer (Optometices). The transmitted UV light was then measured at 10 locations within the wavelength range of 290-400 nm using the SPF analyzer, and the averaged spectrum was obtained to calculate the SPF value. From each SPF value, the improvement rate of UV protection capability relative to Reference Example 1 (where component (A1) in the formulation of Example 1 is replaced with purified water) without component (A1) is calculated according to the following formula, and the evaluation is carried out according to the following evaluation criteria. Improvement rate of UV protection capability (%) = [(SPF value of Example or Comparative Example) / (SPF value of Reference Example 1)] × 100 [Evaluation criteria for improvement rate of UV protection capability] 5: 250% or more 4: 200% or more but less than 250% 3: 150% or more but less than 200% 2: 100% or more but less than 150% 1: Less than 100%

(2) Emulsion Stability The emulsion state of the water-oil emulsion cosmetics shown in Tables 1-4 after preparation was observed using a microscope and visually, and evaluated according to the following criteria. [Criteria] 5: Component (C) enters the inner phase (oil phase), and the emulsion particle size exhibits a very narrow distribution in the range of 10-50 μm, forming slightly spherical, aesthetically pleasing emulsion particles without aggregation. Even under visual observation, it still exhibits a vibrant and attractive appearance. 4: Component (C) enters the inner phase (oil phase), and the emulsion particle size exhibits a narrow distribution in the range of 10-100 μm, forming slightly spherical, aesthetically pleasing emulsion particles without aggregation. Even under visual inspection, it presents a beautiful appearance without roughness. 3: Component (C) enters the inner phase (oil phase). Although emulsion particles are formed, they aggregate the day after preparation. 2: Although component (C) enters the inner phase (oil phase), the emulsion particles are uneven, and they aggregate immediately after preparation. A slightly rough appearance is also observed during visual inspection. 1: Component (C) leaks into the outer phase (aqueous phase) or does not form emulsion particles, separating into oil and water phases. Uneven appearance is observed during visual inspection.

(3) User Experience (No stickiness upon application, good makeup adherence immediately after application, and no oily shine due to sebum after 3 hours) Ten professional cosmetic reviewers conducted usage tests on the water-oil emulsion cosmetics shown in Tables 1-4. Each reviewer used the cosmetic and evaluated it according to the following evaluation criteria in five stages for "no stickiness upon application," "good makeup adherence immediately after application," and "no oily shine due to sebum after 3 hours." The scores from the ten reviewers were summed to calculate the average. The average scores for each evaluation are shown in Tables 1-4. The higher the average value, the better the effect. An average value above 4.0 is rated as very good; an average value below 4.0 but above 3.0 is rated as good; an average value below 3.0 but above 2.0 is rated as slightly poor; and an average value below 2.0 is rated as poor. Additionally, the "makeup adherence immediately after application" is evaluated by assessing the adherence of each water-oil emulsion cosmetic after applying it to the skin and then applying foundation on top. The "no shine due to sebum after 3 hours" is evaluated by assessing the absence of shine due to sebum after applying each water-oil emulsion cosmetic to the skin and then applying foundation on top, 3 hours later. [Evaluation Criteria] 5: Good 4: Slightly Better 3: Average 2: Slightly Poor 1: Poor

[Table 1] Table 1 Element Implementation Examples No. Kind 1 2 3 4 5 6 7 8 9 Formulation (by weight) of water-based oil-based emulsified cosmetics 1 (A1) 4-tertiary butyl-4'-methoxydiphenylmethane*1 0.5 0.5 0.5 2 2-(4-Diethylamino-2-hydroxybenzoyl)hexyl benzoate*2 0.5 0.5 0.5 0.5 0.5 0.5 3 2,4,6-Tris[4-(2-ethylhexyloxycarbonyl)anilino]-1,3,5-tris ... 1 1 1 1 1 1 1 1 1 4 2-Hydroxyl-4-methoxydiphenyl ketone*4 5 Cresoltrazol trisiloxane*5 6 2,4-Bis{[4-(2-ethylhexyloxy)-2-hydroxy]phenyl}-6-(4-methoxyphenyl)-1,3,5-tris(2-ethylhexyloxy)-2-hydroxy]phenyl}-6-(4-methoxyphenyl)-1,3,5-tris(2-ethylhexyloxy)-6 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 7 (A2) Tri(2-ethylhexanoic acid) glyceride 3 3 3 3 3 3 3 3 3 8 diisopropyl sebacate 7 7 7 7 7 7 7 7 7 9 Alkyl benzoate (C12-15) 2 2 2 2 2 2 2 2 2 10 Isopropyl palmitate 11 Octyl dodecyl myristate 12 Isononyl isononanoate 13 Isotridecane isononanoate 14 Pentaerythritol tetra(2-ethylhexanoate) 15 2-Ethylhexanoate whale ester 16 Tris(2-ethylhexyl) trimellitate 17 Dimethylpolysiloxane*7 1 1 1 1 1 1 1 1 1 18 Hydrogenated polyisobutylene ((C13,14) isoalkylene) 19 Isohexadecane 0.45 0.45 0.45 0.45 0.45 0.45 0.45 0.45 0.45 20 Liquid organic 2-Ethylhexyl p-methoxycinnamic acid*8 twenty one UV absorber Octylene twenty two (B) Polyacrylamide*9 twenty three (Acryloyldimethyltaurate Na/Acrylic acid Na) copolymer*10 0.75 0.75 0.75 0.75 0.75 0.75 0.75 0.75 0.75 twenty four (Acryloyldimethyl taurate Na/hydroxyethyl acrylate) copolymer*11 25 (Ammonium acrylamide dimethyl taurate/vinylpyrrolidone) copolymer*12 26 (B') acrylate/C10-30 alkyl acrylate crosspolymer *13 27 (C) Dimethylsiloxane treatment of microparticle zinc oxide C1*14 10 28 Methylhydrosiloxane-treated microparticles of zinc oxide C2*15 10 29 Triethoxyoctylsilane treatment of microparticle zinc acid C3 *16 10 4 16 25 30 Dimethylsiloxane-treated titanium oxide microparticles C4*17 7 31 Hydrogenated dimethylsiloxane treatment of microparticle titanium oxide C5*18 7 32 Triethoxyoctylsilane treatment of microparticles of titanium oxide C6*19 7 33 Stearic acid treated microparticles of titanium oxide C7*20 34 (D) 1,3-Butanediol 1 1 1 1 1 1 1 1 1 35 dipropylene glycol 1 1 1 1 1 1 1 1 1 36 glycerin 2 2 2 2 2 2 2 2 2 37 Propylene glycol 38 (E) Polyoxyethylene monostearate (20) sorbitan ester 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 39 Sorbitan monostearate 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 40 Laureth-7 41 Polysorbate 80 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 42 Oleic sorbitan 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 43 Sorbitan isostearate 44 Polysorbate 60 45 (F) Three Immortals Glue 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 46 Alkyl (C30-40) methylsiloxanes/C30-C45 olefins*21 47 Potassium hydroxide 48 ethanol 10 10 10 10 10 10 10 10 10 49 disodium ethylenediaminetetraacetate 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 50 Purified water Residual Residual Residual Residual Residual Residual Residual Residual Residual Total content (by mass) of 2-ethylhexyl p-methoxycinnamate and octocrylene 0 0 0 0 0 0 0 0 0 Content (mass %) of ingredient (B) 0.75 0.75 0.75 0.75 0.75 0.75 0.75 0.75 0.75 Content (mass %) of ingredient (D) 4 4 4 4 4 4 4 4 4 Contains a mass ratio of [(C)/(A1+A2)] 0.65 0.26 1.04 1.62 0.65 0.65 0.45 0.45 0.45 Contains a mass ratio of [(A2)/(A1)] 6.7 6.7 6.7 6.7 6.7 6.7 6.7 6.7 6.7 Evaluation UV protection capability 5 3 5 5 3 5 3 5 5 Emulsion stability 5 4 5 4 3 5 3 5 5 No stickiness 4.7 4.8 4.3 3.8 4.4 4.7 4.5 4.7 4.5 Good makeup adherence 4.6 3.3 4.6 4.5 3.3 4.3 3.8 4.7 4.6 No oily shine caused by sebum 4.5 3.3 4.8 4.2 3.8 4.4 3.4 4.1 4.1

[Table 2] Table 2 Element Implementation Examples No. Kind 10 11 12 13 14 15 16 17 Formulation (by weight) of water-based oil-based emulsified cosmetics 1 (A1) 4-tertiary butyl-4'-methoxydiphenylmethane*1 2 2-(4-Diethylamino-2-hydroxybenzoyl)hexyl benzoate*2 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 3 2,4,6-Tris[4-(2-ethylhexyloxycarbonyl)anilino]-1,3,5-tris ... 1 1 1 1 1 1.5 1.5 1.5 4 2-Hydroxyl-4-methoxydiphenyl ketone*4 1 1 1 5 Cresoltrazol trisiloxane*5 1 1 1 6 2,4-Bis{[4-(2-ethylhexyloxy)-2-hydroxy]phenyl}-6-(4-methoxyphenyl)-1,3,5-tris ...6-hydroxy[4-ethylhexyloxy]-2-hydroxy[4-ethylhexyloxy]-2-hydroxy[4-ethylhexyl 0.5 0.5 0.5 0.5 0.5 1 1 1 7 (A2) Tri(2-ethylhexanoic acid) glyceride 3 3 3 7 2 3 3 3 8 diisopropyl sebacate 7 7 7 3 3 7 7 7 9 Alkyl benzoate (C12-15) 2 2 2 2 7 2 2 2 10 Isopropyl palmitate 11 Octyl dodecyl myristate 12 Isononyl isononanoate 13 Isotridecane isononanoate 14 Pentaerythritol tetra(2-ethylhexanoate) 15 2-Ethylhexanoate whale ester 16 Tris(2-ethylhexyl) trimellitate 17 Dimethylpolysiloxane*7 1 1 1 1 1 1 1 1 18 Hydrogenated polyisobutylene ((C13,14) isoalkylene) 0.36 19 Isohexadecane 0.45 0.45 0.45 0.45 0.45 20 Liquid organic 2-Ethylhexyl p-methoxycinnamic acid*8 2 1 twenty one UV absorber Octylene 2 twenty two (B) Polyacrylamide*9 0.6 twenty three (Acryloyldimethyltaurate Na/Acrylic acid Na) copolymer*10 0.75 0.75 0.75 0.75 0.75 twenty four (Acryloyldimethyl taurate Na/hydroxyethyl acrylate) copolymer*11 1.34 25 (Ammonium acrylamide dimethyl taurate/vinylpyrrolidone) copolymer*12 1 26 (B') acrylate/C10-30 alkyl acrylate crosspolymer *13 27 (C) Dimethylsiloxane treatment of microparticle zinc oxide C1*14 28 Methylhydrosiloxane-treated microparticles of zinc oxide C2*15 29 Triethoxyoctylsilane treatment of microparticle zinc acid C3 *16 10 10 10 10 10 10 10 10 30 Dimethylsiloxane-treated titanium oxide microparticles C4*17 31 Hydrogenated dimethylsiloxane treatment of microparticle titanium oxide C5*18 32 Triethoxyoctylsilane treatment of microparticles of titanium oxide C6*19 33 Stearic acid treated microparticles of titanium oxide C7*20 34 (D) 1,3-Butanediol 1 1 1 1 1 1 1 1 35 dipropylene glycol 1 1 1 1 1 1 1 1 36 glycerin 2 2 2 2 2 2 2 2 37 Propylene glycol 38 (E) Polyoxyethylene monostearate (20) sorbitan ester 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 39 Sorbitan monostearate 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 40 Laureth-7 0.09 41 Polysorbate 80 0.15 0.15 0.15 0.15 0.15 42 Oleic sorbitan 0.05 0.05 0.05 0.05 0.05 43 Sorbitan isostearate 0.08 44 Polysorbate 60 0.08 45 (F) Three Immortals Glue 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 46 Alkyl (C30-40) methylsiloxanes/C30-C45 olefins*21 47 Potassium hydroxide 48 ethanol 10 10 10 10 10 10 10 10 49 disodium ethylenediaminetetraacetate 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 50 Purified water Residual Residual Residual Residual Residual Residual Residual Residual Total content (by mass) of 2-ethylhexyl p-methoxycinnamate and octocrylene 0 0 0 0 0 2 2 1 Content (mass%) of ingredient (B) 0.60 1.34 1.00 0.75 0.75 0.75 0.75 0.75 Content (mass %) of ingredient (D) 4 4 4 4 4 4 4 4 Contains a mass ratio of [(C)/(A1+A2)] 0.65 0.67 0.67 0.65 0.65 0.49 0.49 0.51 Contains a mass ratio of [(A2)/(A1)] 6.7 6.5 6.5 6.7 6.7 3.1 3.1 2.9 Evaluation UV protection capability 5 5 5 5 5 5 5 5 Emulsion stability 5 5 5 5 5 5 5 5 No stickiness 4.6 4.7 4.8 4.4 4.2 3.4 3.2 3.8 Good makeup adherence 4.3 4.4 4.5 4.3 4.1 4.2 4.3 4.5 No oily shine caused by sebum 4.6 4.7 4.5 4.6 3.8 3.1 3.4 3.9

[Table 3] Table 3 Element Implementation Examples No. Kind 18 19 20 twenty one twenty two twenty three twenty four 25 26 Formulation (by weight) of water-based oil-based emulsified cosmetics 1 (A1) 4-tertiary butyl-4'-methoxydiphenylmethane*1 2 2-(4-Diethylamino-2-hydroxybenzoyl)hexyl benzoate*2 0.5 0.5 0.5 0.5 0.5 1 0.5 0.5 0.5 3 2,4,6-Tris[4-(2-ethylhexyloxycarbonyl)anilino]-1,3,5-tris ... 1 1 1 1 0.5 1 1 1 2 4 2-Hydroxyl-4-methoxydiphenyl ketone*4 5 Cresoltrazol trisiloxane*5 1 6 2,4-Bis{[4-(2-ethylhexyloxy)-2-hydroxy]phenyl}-6-(4-methoxyphenyl)-1,3,5-tris ...6-hydroxy[4-ethylhexyloxy]-2-hydroxy[4-ethylhexyloxy]-2-hydroxy[4-ethylhexyl 0.5 0.5 0.5 0.5 1 0.5 0.5 1 7 (A2) Tri(2-ethylhexanoic acid) glyceride 3 3 3 3 3 3 3 8 diisopropyl sebacate 7 7 7 7 7 7 7 9 Alkyl benzoate (C12-15) 2 2 2 2 2 2 3 2 10 Isopropyl palmitate 3 11 Octyl dodecyl myristate 2 2 12 Isononyl isononanoate 2 2 13 Isotridecane isononanoate 2 2 14 Pentaerythritol tetra(2-ethylhexanoate) 2 15 2-Ethylhexanoate whale ester 2 16 Tris(2-ethylhexyl) trimellitate 2 17 Dimethylpolysiloxane*7 1 1 1 1 1 1 1 1 1 18 Hydrogenated polyisobutylene ((C13,14) isoalkylene) 19 Isohexadecane 0.45 0.45 0.45 0.45 0.45 0.45 0.45 0.45 0.45 20 Liquid organic 2-Ethylhexyl p-methoxycinnamic acid*8 twenty one UV absorber Octylene twenty two (B) Polyacrylamide*9 twenty three (Acryloyldimethyltaurate Na/Acrylic acid Na) copolymer*10 0.75 0.75 0.75 0.75 0.75 0.75 0.75 0.75 0.75 twenty four (Acryloyldimethyl taurate Na/hydroxyethyl acrylate) copolymer*11 25 (Ammonium acrylamide dimethyl taurate/vinylpyrrolidone) copolymer*12 26 (B') acrylate/C10-30 alkyl acrylate crosspolymer *13 27 (C) Dimethylsiloxane treatment of microparticle zinc oxide C1*14 28 Methylhydrosiloxane-treated microparticles of zinc oxide C2*15 29 Triethoxyoctylsilane treatment of microparticle zinc acid C3 *16 10 10 10 10 10 10 10 10 7 30 Dimethylsiloxane-treated titanium oxide microparticles C4*17 31 Hydrogenated dimethylsiloxane treatment of microparticle titanium oxide C5*18 32 Triethoxyoctylsilane treatment of microparticles of titanium oxide C6*19 33 Stearic acid treated microparticles of titanium oxide C7*20 3 34 (D) 1,3-Butanediol 1 1 2 1 1 1 1 1 35 dipropylene glycol 1 3 1 1 1 1 1 36 glycerin 1 2 1 2 2 2 2 2 37 Propylene glycol 2 4 38 (E) Polyoxyethylene monostearate (20) sorbitan ester 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 39 Sorbitan monostearate 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 40 Laureth-7 41 Polysorbate 80 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 42 Oleic sorbitan 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 43 Sorbitan isostearate 44 Polysorbate 60 45 (F) Three Immortals Glue 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 46 Alkyl (C30-40) methylsiloxanes/C30-C45 olefins*21 0.1 0.1 0.1 47 Potassium hydroxide 48 ethanol 10 10 10 10 10 10 10 10 10 49 disodium ethylenediaminetetraacetate 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 50 Purified water Residual Residual Residual Residual Residual Residual Residual Residual Residual Total content (by mass) of 2-ethylhexyl p-methoxycinnamate and octocrylene 0 0 0 0 0 0 0 0 0 Content (mass %) of ingredient (B) 0.75 0.75 0.75 0.75 0.75 0.75 0.75 0.75 0.75 Content (mass %) of ingredient (D) 0 2 6 10 4 4 4 4 4 Contains a mass ratio of [(C)/(A1+A2)] 0.65 0.65 0.65 0.65 0.69 0.61 0.65 0.65 0.39 Contains a mass ratio of [(A2)/(A1)] 6.7 6.7 6.7 6.7 13.5 4.5 6.7 6.7 3.0 Evaluation UV protection capability 5 5 5 5 4 5 5 5 5 Emulsion stability 5 5 5 5 5 5 5 5 4 No stickiness 3.2 3.6 4.3 4.1 4.5 4.2 4.2 4.4 4.3 Good makeup adherence 3.1 4.0 4.1 4.2 4.2 4.1 4.3 4.1 4.5 No oily shine caused by sebum 4.1 4.3 4.4 4.3 4.6 4.4 4.4 4.5 4.4

[Table 4] Table 4 Element Comparative example Reference Example 1 No. Kind 1 2 3 4 5 6 Formulation (by weight) of water-based oil-based emulsified cosmetics 1 (A1) 4-tertiary butyl-4'-methoxydiphenylmethane*1 2 2-(4-Diethylamino-2-hydroxybenzoyl)hexyl benzoate*2 0.5 0.5 0.5 0.5 0.5 0.5 3 2,4,6-Tris[4-(2-ethylhexyloxycarbonyl)anilino]-1,3,5-tris ... 1 1 1 1 1 1 4 2-Hydroxyl-4-methoxydiphenyl ketone*4 5 Cresoltrazol trisiloxane*5 6 2,4-Bis{[4-(2-ethylhexyloxy)-2-hydroxy]phenyl}-6-(4-methoxyphenyl)-1,3,5-tris ...6-hydroxy[4-ethylhexyloxy]-2-hydroxy[4-ethylhexyloxy]-2-hydroxy[4-ethylhexyl 0.5 0.5 0.5 0.5 0.5 0.5 7 (A2) Tri(2-ethylhexanoic acid) glyceride 3 3 3 3 3 3 8 diisopropyl sebacate 7 7 7 4 7 9 Alkyl benzoate (C12-15) 2 2 2 2 2 2 2 10 Isopropyl palmitate 11 Octyl dodecyl myristate 12 Isononyl isononanoate 13 Isotridecane isononanoate 14 Pentaerythritol tetra(2-ethylhexanoate) 15 2-Ethylhexanoate whale ester 16 Tris(2-ethylhexyl) trimellitate 17 Dimethylpolysiloxane*7 1 1 1 1 1 1 1 18 Hydrogenated polyisobutylene ((C13,14) isoalkylene) 19 Isohexadecane 0.45 0.45 0.45 0.45 0.45 0.45 20 Liquid organic 2-Ethylhexyl p-methoxycinnamic acid*8 10 3 twenty one UV absorber Octylene 7 twenty two (B) Polyacrylamide*9 twenty three (Acryloyldimethyltaurate Na/Acrylic acid Na) copolymer*10 0.75 0.75 0.75 0.75 0.75 0.75 twenty four (Acryloyldimethyl taurate Na/hydroxyethyl acrylate) copolymer*11 25 (Ammonium acrylamide dimethyl taurate/vinylpyrrolidone) copolymer*12 26 (B') acrylate/C10-30 alkyl acrylate crosspolymer *13 0.3 27 (C) Dimethylsiloxane treatment of microparticle zinc oxide C1*14 28 Methylhydrosiloxane-treated microparticles of zinc oxide C2*15 29 Triethoxyoctylsilane treatment of microparticle zinc acid C3 *16 2.5 30 10 10 10 10 10 30 Dimethylsiloxane-treated titanium oxide microparticles C4*17 31 Hydrogenated dimethylsiloxane treatment of microparticle titanium oxide C5*18 32 Triethoxyoctylsilane treatment of microparticles of titanium oxide C6*19 33 Stearic acid treated microparticles of titanium oxide C7*20 34 (D) 1,3-Butanediol 1 1 1 1 1 1 1 35 dipropylene glycol 1 1 1 1 1 1 1 36 glycerin 2 2 2 2 2 2 2 37 Propylene glycol 38 (E) Polyoxyethylene monostearate (20) sorbitan ester 0.2 0.2 0.2 0.2 0.2 0.2 0.2 39 Sorbitan monostearate 0.3 0.3 0.3 0.3 0.3 0.3 0.3 40 Laureth-7 41 Polysorbate 80 0.15 0.15 0.15 0.15 0.15 0.15 42 Oleic sorbitan 0.05 0.05 0.05 0.05 0.05 0.05 43 Sorbitan isostearate 44 Polysorbate 60 45 (F) Three Immortals Glue 0.1 0.1 0.1 0.1 0.1 0.1 0.1 46 Alkyl (C30-40) methylsiloxanes/C30-C45 olefins*21 47 Potassium hydroxide 0.15 48 ethanol 10 10 10 10 10 10 10 49 disodium ethylenediaminetetraacetate 0.01 0.01 0.01 0.01 0.01 0.01 0.01 50 Purified water Residual Residual Residual Residual Residual Residual Residual Total content (by mass) of 2-ethylhexyl p-methoxycinnamate and octocrylene 0 0 0 10 7 3 0 Content (mass %) of ingredient (B) 0.75 0.75 0.75 0.75 0.75 0.75 Content (mass %) of ingredient (D) 4 4 4 4 4 4 4 Contains a mass ratio of [(C)/(A1+A2)] 0.16 1.94 0.67 0.65 0.65 0.65 0.74 Contains a mass ratio of [(A2)/(A1)] 6.7 6.7 6.5 6.7 6.7 6.7 - Evaluation UV protection capability 2 - - 5 5 5 - Emulsion stability 2 1 1 5 5 5 5 No stickiness 4.7 - - 2.3 1.6 2.7 4.8 Good makeup adherence 2.4 - - 4.2 4.1 4.2 4.3 No oily shine caused by sebum 2.8 - - 1.2 1.6 1.9 4.2

The detailed ingredients used in Tables 1-4 are shown below: *1: DSM's "PARSOL 1789" *2: BASF's "UVINUL A PLUS" *3: BASF's "UVINUL T-150" *4: BASF's "UVINUL M40" *5: UFC CORPORATION's "Mosacare A440" *6: BASF's "TINOSORB S" *7: Shin-Etsu Chemical Industry Co., Ltd.'s "KF-96A-6cs" *8: BASF's "UVINUL MC80" *9: SEPPIC's "SEPIGEL 305" (polyacrylamide, 40% by weight, effective fraction) *10: SEPPIC's "SIMULGEL" *11: "EG" ((Na acrylamide dimethyl taurate/Na acrylate) copolymer, effective fraction 37.5% by mass) *12: "SEPINOV EMT 10" ((Na acrylamide dimethyl taurate/hydroxyethyl acrylate) copolymer, effective fraction 89.3% by mass) *13: "Aristoflex AVC" ((Ammonium acrylamide dimethyl taurate/vinylpyrrolidone) copolymer, effective fraction 100% by mass) *14: "PEMULEN TR-1" (Lubrizol Advanced Materials) *15: Dimethylsiloxane-treated zinc oxide C1 obtained in Preparation Example 1 *16: Methylhydrogenated polysiloxane-treated zinc oxide C2 obtained in Preparation Example 2 *16: Triethoxyoctylsilane-treated microparticle zinc oxide C3 obtained in Preparation Example 3 *17: Dimethylsiloxane-treated microparticle titanium oxide C4 obtained in Preparation Example 4 *18: "STR-100W-LP" (average primary particle size 10nm) manufactured by Sakai Kagaku Kogyo Co., Ltd. *19: "STR-100W-OTS" (average primary particle size 10nm) manufactured by Sakai Kagaku Kogyo Co., Ltd. *20: "Microparticle titanium oxide MT-N1" (average primary particle size 7nm) manufactured by TAYCA Co., Ltd. *21: "DOWSIL AMS-C30 COSMETIC WAX" (alkyl-modified (C30) polysiloxane) manufactured by Dow‧Toray Co., Ltd.

As shown in Tables 1 to 4, the water-based oil-based emulsified cosmetics of the present invention have superior UV protection capabilities compared to the water-based oil-based emulsified cosmetics of the comparative examples. They also exhibit excellent emulsification stability, produce less stickiness during application, adhere well to the makeup, and suppress shine caused by sebum.

Claims (7)

An oil-in-water emulsion cosmetic contains the following components (A1), (A2), (B), (C), and (D): Component (A1): a non-water-soluble organic ultraviolet absorber that is solid at 25°C; Component (A2): a liquid oil; Component (B): an acrylamide polymer; Component (C): a hydrophobically treated microparticle metal oxide; Component (D): a polyol. Wherein, the mass ratio of component (C) to the total content of components (A1) and (A2) [(C)/(A1+A2)] is 0.25 or more and 1.8 or less; the total content of 2-ethylhexyl p-methoxycinnamate and octocrylene in component (A2) is less than 2% by mass in the total amount of the oil-in-water emulsion cosmetic. Component (A1) is selected from one or more of the following groups: 4-tert-butyl-4'-methoxydibenzoylmethane, 2-(4-diethylamino-2-hydroxybenzoyl)hexyl benzoate, 2,4,6-tris[4-(2-ethylhexyloxycarbonyl)anilino]-1,3,5-tris(A1), 2-hydroxy-4-methoxydiphenyl ketone, cresoltrazolium trisiloxane, and 2,4-bis{[4-(2-ethylhexyloxy)-2-hydroxy]phenyl}-6-(4-methoxyphenyl)-1,3,5-tris(A1); Component (C) is a microparticle metal oxide selected from one or more of the following groups: microparticle zinc oxide and microparticle titanium oxide. The content of component (D) is 0.5% by mass or more but less than 3% by mass, or more than 5% by mass but less than 15% by mass. For example, in the water-based oil-based emulsion cosmetic of claim 1, the hydrophobic treatment of component (C) is selected from one or more of the group consisting of polysiloxane treatment, alkylalkoxysilane treatment, and fatty acid treatment. For example, in the water-based oil-based emulsion cosmetic of claim 1 or 2, the hydrophobic treatment of component (C) is selected from: one or more of the following selected as surface treatment agents: polysiloxane treatment, alkylalkoxysilane treatment, and fatty acid treatment, selected from the group consisting of methylhydrosiloxane and dimethylsiloxane/methylhydrosiloxane copolymers. For example, in water-based oil-based emulsified cosmetics as requested in item 1 or 2, the content of ingredient (C) is 3% by mass or more and 30% by mass or less. For example, in the water-based oil-based emulsion cosmetics of claim 1 or 2, component (A2) contains one or more selected from the group consisting of ester oils and polysiloxane oils. For example, in the water-based oil-based emulsion cosmetic of claim 1 or 2, component (B) is selected from one or more of the following groups: acrylamide monomers, copolymers containing constituent units derived from acrylamide monomers, and their salts; and the acrylamide monomer is selected from one or more of the following groups: acrylamide and acrylamide dimethyl taurate. For example, the water-based oil-based emulsified cosmetics in request item 1 or 2 are intended for use in sun protection.