Classifications

• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
  • A61K8/04—Dispersions; Emulsions
  • A61K8/06—Emulsions
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
  • A61K8/27—Zinc; Compounds thereof
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
  • A61K8/29—Titanium; Compounds thereof
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
  • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
  • A61K8/89—Polysiloxanes
  • A61K8/891—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
  • A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations

Definitions

• the present invention relates to a water-in-oil type emulsion cosmetic for sunscreen.
• Emulsified cosmetics for sunscreen are roughly classified into oil-in-water type and water-in-oil type.
• an oil-in-water type sunscreen emulsion cosmetic for example, an oil-in-water emulsion cosmetic in which oil droplets containing an alkyldimethylsilylpolypropylsilsesquioxane together with an ultraviolet absorber and the like are dispersed in water is known. (Patent Documents 1 and 2).
• Patent Document 1 Japanese Patent Publication No. 2007-532754
• Patent Document 2 International Publication No. 2018/062469
• the present invention provides a water-in-oil type emulsion cosmetic for sunscreen containing the following components (A), (B) and (C).
• A Alkyl-modified silicone wax having a melting point of 60° C. or higher
• B Hydrophobized ultraviolet scattering agent
• C Water
• the oil-in-water emulsion cosmetic using alkyldimethylsilylpolypropylsilsesquioxane or the like disclosed in Patent Document 2 has a property that even when the cosmetic is applied to the skin and then tissue paper or the like is pressed from above. Although it is said that secondary adhesion is unlikely, it is insufficient in terms of abrasion resistance, and when the surface of the coated portion is rubbed with a stronger force, the coating film peels easily.
• the present invention relates to providing an emulsified cosmetic for sunscreen which has less stickiness after application and has excellent abrasion resistance.
• the present inventor uses the alkyl-modified silicone wax having a melting point of 60° C. or higher and a hydrophobized ultraviolet scattering agent to prepare a water-in-oil type emulsion cosmetic, which is useful as a sunscreen and has little stickiness after application.
• the present invention has been completed based on the finding that not only it has a good usability, but also has excellent abrasion resistance after coating.
• the water-in-oil type emulsion cosmetic for sunscreen of the present invention has excellent abrasion resistance. In addition, it has a good feeling of use that the stickiness after application is small.
• the water-in-oil type emulsion cosmetic for sunscreen of the present invention contains an alkyl-modified silicone wax having a melting point of 60°C or higher.
• the alkyl-modified silicone wax as the component (A) from the viewpoint of abrasion resistance and feeling of use (non-stickiness), among dimethyl silicones modified with an alkyl group having 9 to 80 carbon atoms, the melting point is 60° C. or higher.
• the alkyl group may be linear or branched.
• the carbon number of the alkyl group is preferably 16 or more, more preferably 20 or more, and particularly preferably 24 or more, from the viewpoint of abrasion resistance, and the ease of production, the feeling of use (no film feeling), and the like. From the viewpoint, it is preferably 70 or less, more preferably 60 or less, and particularly preferably 50 or less.
• the specific range is preferably 16 or more and 70 or less, more preferably 20 or more and 60 or less, and particularly preferably 24 or more and 50 or less.
• the position of substitution of this alkyl group is arbitrary, and the form of substitution may be one-terminal type, both-terminal type, random type or the like.
• the number of substituted alkyl groups is also arbitrary, and may be one or two or more in the molecule. When the number of substituted alkyl groups is 2 or more, the 2 or more alkyl groups may be the same or different.
• a mixture of silicone waxes modified with different alkyl groups may be used as the alkyl-modified silicone wax having a melting point of 60° C. or higher.
• the melting point of the component (A) alkyl-modified silicone wax used in the present invention is 60°C or higher, it is preferably 61°C or higher, more preferably 61°C or higher from the viewpoints of abrasion resistance, feeling of use (non-stickiness, smoothness) and the like.
• the specific range is preferably 60°C or higher and 90°C or lower, more preferably 61°C or higher and 80°C or lower, and particularly preferably 62°C or higher and 72°C or lower.
• the melting point means the melting point measured according to JIS K0064.
• an oil-soluble alkyl-modified silicone wax having a melting point of 60°C or higher is preferable.
• alkyl-modified silicone wax include alkyl methicone wax, alkyl dimethicone wax, silsesquioxane resin wax, and the like. Among these, one kind may be used alone or two or more kinds may be used in combination. Good.
• alkyl methicone wax and silsesquioxane resin wax are preferable, and silsesquioxane resin wax is particularly preferable, from the viewpoints of abrasion resistance, feeling of use (non-greasiness, smoothness, no film feeling) and the like. preferable.
• silsesquioxane resin wax alkyl(C30-45)dimethylsilylpolypropylsilsesquioxane is preferable.
• an alkyl-modified silicone wax having a melting point of 60° C. or higher may be a commercially available product or one obtained by synthesizing by a conventional method.
• alkyl (C26-28) methicone BELSIL CM 7026 VP, manufactured by Asahi Kasei Wacker Silicone, melting point 70° C.
• alkyl (C30-45) methicone AMS-C30 Cosmetic Wax, manufactured by Toray Dow Corning, melting point 73- 77° C.
• alkyl (C30-45) dimethylsilylpolypropylsilsesquioxane SW) -8005 C30 Resin Wax, manufactured by Toray Dow Corning Co., melting point 63-71° C.) and the like.
• the content of the alkyl-modified silicone wax having a melting point of 60° C. or higher is preferably in the sunscreen oil-in-water emulsified cosmetic composition of the present invention, from the viewpoints of abrasion resistance, feeling of use (non-greasiness, smoothness) and the like.
• water-in-oil water-in-oil type emulsion cosmetic for sunscreen of the present invention preferably 16% by mass or less, more preferably 12% by mass or less, and further preferably Is 8% by mass or less, particularly preferably 4% by mass or less.
• the sunscreen water-in-oil type emulsion cosmetic of the present invention preferably 0.05% by mass or more and 16% by mass or less, more preferably 0.1% by mass or more and 12% by mass or less, 0.1% by mass or more and 8% by mass or less is more preferable, 0.4% by mass or more and 8% by mass or less is further preferable, and 0.8% by mass or more and 4% by mass or less is particularly preferable.
• the content of the alkyl-modified silicone wax having a melting point of 60° C. or higher is 0.4% by mass or more, the feeling of use (no feeling of coating) is particularly improved, and when it is 0.8% by mass or more, In addition to the feeling of use (no film feeling), the abrasion resistance is further improved.
• the water-in-oil type emulsion cosmetic for sunscreen of the present invention contains a hydrophobized ultraviolet scattering agent.
• a hydrophobic treatment fine particle metal oxide is preferable.
• the fine particle metal oxide used for the hydrophobized fine particle metal oxide one or more fine particle metal oxides selected from zinc oxide, titanium oxide, cerium oxide, iron oxide and chromium oxide are used from the viewpoint of easy availability. The thing is preferable.
• these fine particle metal oxides one or more fine particle metal oxides selected from zinc oxide, titanium oxide and cerium oxide are preferable from the viewpoint of UV protection effect and the like, and selected from zinc oxide and titanium oxide.
• One or more particulate metal oxides are more preferred.
• these fine particle metal oxides can be made to contain a trace element having a valence of +2 or more, and a metal such as iron, zirconium, calcium, manganese, magnesium, yttrium, etc., alone or in combination of two or more, can be used as a fine particle metal. It can be contained in an oxide. From the viewpoint of abrasion resistance and the like, it is preferable to use at least hydrophobized fine particle zinc oxide as the hydrophobized fine particle metal oxide.
• hydrophobically treated fine particles of zinc oxide or using hydrophobically treated fine particles of zinc oxide in combination with other hydrophobically treated fine particles of metal oxide such as hydrophobically treated fine particles of titanium oxide or hydrophobically treated fine particles of cerium oxide. It is preferable.
• the shape of the “fine particle metal oxide” is not particularly limited, and examples thereof include a spherical shape, a plate shape, a rod shape, a spindle shape, a needle shape, and an irregular shape.
• the average particle size of the “fine particle metal oxide” is preferably 0.01 ⁇ m or more, more preferably 0.012 ⁇ m or more, still more preferably 0.015 ⁇ m or more, and preferably 1 ⁇ m or less, more preferably It is 0.8 ⁇ m or less, more preferably 0.5 ⁇ m or less.
• the average particle size of the fine particle metal oxide means the average particle size measured by the laser diffraction/scattering method.
• fine particle zinc oxide examples include FINEX-25, FINEX-30, FINEX-50, FINEX-75 (manufactured by Sakai Chemical Industry Co., Ltd.), MZ500 series, MZ700 series (manufactured by Teika), ZnO-350 (Sumitomo Osaka Cement Co., Ltd.). Products) are commercially available.
• the fine particle titanium oxide for example, TTO-55 series, TTO-51 series (manufactured by Ishihara Sangyo Co., Ltd.), JR series, JA series (manufactured by Teika), etc. are commercially available.
• the fine particle cerium oxide for example, high-purity cerium sold by Nikki or Seimi Chemical Co. may be used.
• the hydrophobic treatment of the above-mentioned fine particle metal oxide may be carried out by using a known surface treating agent which is made hydrophobic.
• a known surface treating agent which is made hydrophobic.
• treatment with silicone or silicone resin, treatment with silane compound or silazane compound, and treatment with metal soap such as aluminum isostearate are preferable from the viewpoint of dispersion stability.
• silicone or silicone resin examples include methylpolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, methylhydrogenpolysiloxane/dimethylpolysiloxane copolymer, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodeca.
• the methylhydrogenpolysiloxane/dimethylpolysiloxane copolymer is preferably represented by the following formula (2).
• n and n are integers of 0 or more, and 1 ⁇ m+n ⁇ 60. ]
• silane compound or silazane compound a silane compound or silazane compound having an alkyl group having 1 to 20 carbon atoms or a fluoroalkyl group having 1 to 20 carbon atoms and having reactivity with an inorganic oxide is preferable, and the following formula ( A silane compound represented by 3) or a silazane compound represented by the following formula (4) is more preferable. In addition, you may use these individually by 1 type or in combination of 2 or more types.
• R 4 represents a linear or branched alkyl group having 1 to 20 carbon atoms, or a linear or branched fluoroalkyl group having 1 to 20 carbon atoms
• R 5 represents a linear or branched alkyl group having 1 to 6 carbon atoms
• Z represents a halogen atom or an alkoxy group
• p represents 0 or 1.
• R 6 to R 11 are each independently a straight chain or branched chain alkyl group having 1 to 20 carbon atoms, or a straight chain or branched chain group having 1 to 20 carbon atoms. Is a fluoroalkyl group.
• the silane compound is preferably an alkylalkoxysilane or a fluoroalkylalkoxysilane, more preferably an alkyltrialkoxysilane or a fluoroalkyltrialkoxysilane.
• Specific examples include hexyltrimethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, octadecyltrimethoxysilane, trifluoropropyltrimethoxysilane, and heptadecafluorodecyltrimethoxysilane.
• silazane compound examples include hexamethyldisilazane.
• the coating amount of the surface treatment agent used for the hydrophobic treatment is preferably 3 parts by mass or more, and more preferably 5 parts by mass with respect to 100 parts by mass of the particulate metal oxide, from the viewpoint of emulsion stability, dispersion stability, and the like.
• the amount is preferably 15 parts by mass or less, and more preferably 10 parts by mass or less, relative to 100 parts by mass of the particulate metal oxide.
• a conventionally known method can be appropriately selected and performed.
• the treatment with the above-mentioned silicone or silicone resin at least one kind of silicone compound (excluding silane compound) consisting of organopolysiloxanes and silicone resin as described in Japanese Patent No. 3187440 is used.
• a method of coating the surface of the fine particle metal oxide with silicon oxide by coating the fine particle metal oxide in a non-vapor phase state and then baking at a temperature of 600 to 950° C. in an oxygen-containing atmosphere.
• a treatment method using a silane compound or a silazane compound includes a chemical bonding method, and more specifically, a silane compound or a silazane compound and a fine particle metal in an organic solvent such as n-hexane, cyclohexane, or lower alcohol.
• examples include a method of mixing with an oxide, finely pulverizing the mixture if necessary, and then removing the organic solvent by heating (for example, 80 to 250° C.) or reduced pressure.
• a method of performing a surface treatment with a silane compound in water after coating treatment with a polysiloxane compound can also be mentioned.
• the hydrophobized ultraviolet scattering agents may be used alone or in combination of two or more.
• the content of the hydrophobized ultraviolet scattering agent is preferably 2 mass in the sunscreen oil-in-water emulsified cosmetic composition of the present invention from the viewpoints of abrasion resistance, feeling of use (non-greasiness), ultraviolet protection effect, and the like.
• % Or more more preferably 6% by mass or more, further preferably 7.5% by mass or more, particularly preferably 10% by mass or more, and the viewpoint of use feeling (no powderiness), compounding stability, etc. Therefore, it is preferably 35% by mass or less, more preferably 30% by mass or less, still more preferably 25% by mass or less, and particularly preferably 20% by mass or less in the sunscreen oil-in-water emulsion cosmetic of the present invention.
• 2% by mass or more and 35% by mass or less is preferable, 6% by mass or more and 30% by mass or less is more preferable, and 7.5% by mass is 7.5% by mass in the water-in-oil type emulsion cosmetic for sunscreen of the present invention. It is more preferably 25% by mass or more and more preferably 10% by mass or more and 20% by mass or less.
• the content of the hydrophobized ultraviolet scattering agent is 7.5% by mass or more or 10% by mass or more, the abrasion resistance is particularly improved.
• the content ratio [(A)/(B)] of the component (A) alkyl-modified silicone wax having a melting point of 60° C. or more to the component (B) hydrophobized ultraviolet scattering agent is determined by abrasion resistance and feeling of use (smoothness).
• Etc. preferably 0.005 or more, more preferably 0.01 or more, further preferably 0.025 or more, further preferably 0.05 or more, particularly preferably 0.075 or more, and From the viewpoints of abrasion resistance, feeling of use (no powderyness), no white residue on the skin after application, etc., preferably 1.67 or less, more preferably 1.1 or less, still more preferably 0.7 or less. , Particularly preferably 0.3 or less.
• the specific range is preferably 0.005 or more and 1.67 or less, more preferably 0.01 or more and 1.1 or less, still more preferably 0.025 or more and 0.7 or less, and 0.05 or more and 0.3 or less. Is more preferable, and 0.075 or more and 0.3 or less is particularly preferable.
• the feeling of use no feeling of filming
• the feeling of use filming
• the water-in-oil type emulsion cosmetic for sunscreen of the present invention contains water.
• the content of water is preferably 1% by mass or more, and more preferably 2.5% by mass in the water-in-oil type sunscreen emulsion cosmetic composition of the present invention, from the viewpoint of feeling of use (freshness, smoothness) and the like.
• the above is more preferably 5% by mass or more, particularly preferably 10% by mass or more, and from the viewpoints of compounding stability, feeling of use (non-stickiness) and the like, the sunscreen water-in-oil type emulsified makeup of the present invention.
• the content is preferably 50% by mass or less, more preferably 40% by mass or less, further preferably 30% by mass or less, and particularly preferably 20% by mass or less.
• 1% by mass or more and 50% by mass or less is preferable, 2.5% by mass or more and 40% by mass or less is more preferable, and 5% by mass is 5% by mass in the water-in-oil emulsion cosmetic for sunscreen of the present invention.
• the amount is more preferably 30% by mass or less and particularly preferably 10% by mass or more and 20% by mass or less.
• Component (D) As the water-in-oil type emulsion cosmetic for sunscreen of the present invention, from the viewpoint of the ultraviolet protection effect, it is preferable to further contain (D) an ultraviolet absorber in addition to the components (A) to (C).
• an ultraviolet absorber As the ultraviolet absorber, an organic ultraviolet absorber is preferable from the viewpoint of water resistance, abrasion resistance, solubility and the like. Examples of organic ultraviolet absorbers include benzoic acid ultraviolet absorbers, anthranilic acid ultraviolet absorbers, salicylic acid ultraviolet absorbers, cinnamic acid ultraviolet absorbers, benzophenone ultraviolet absorbers, and triazine ultraviolet absorbers.
• benzoic acid type ultraviolet absorbers one or more selected from benzoic acid type ultraviolet absorbers, cinnamic acid type ultraviolet absorbers and triazine type ultraviolet absorbers are preferable.
• organic ultraviolet absorber an oil-soluble organic ultraviolet absorber is preferable.
• Benzoic acid-based UV absorbers include para-aminobenzoic acid (PABA), glyceryl PABA, ethyldihydroxypropyl PABA, N-ethoxylate PABA ethyl ester, N-dimethyl PABA ethyl ester, N-dimethyl PABA butyl ester. , N-dimethyl PABA amyl ester, octyl dimethyl PABA, hexyl diethylaminohydroxybenzoyl benzoate and the like.
• Examples of the anthranilic acid-based ultraviolet absorber include homomenthyl-N-acetylanthranilate.
• salicylic acid-based ultraviolet absorbers examples include amyl salicylate, menthyl salicylate, homomenthyl salicylate, octyl salicylate, phenyl salicylate, benzyl salicylate, p-isopropanol phenyl salicylate and the like. ..
• octyl cinnamate As cinnamic acid-based UV absorbers, octyl cinnamate, ethyl-4-isopropyl cinnamate, ethyl-2,4-diisopropyl cinnamate, methyl-2,4-diisopropyl cinnamate, propyl-p-methoxy cinnamate, isopropyl -P-methoxycinnamate, isoamyl-p-methoxycinnamate, 2-ethylhexyl-p-methoxycinnamate, 2-ethoxyethyl-p-methoxycinnamate, cyclohexyl-p-methoxycinnamate, ethyl- ⁇ -cyano- Examples thereof include ⁇ -phenylcinnamate, 2-ethylhexyl- ⁇ -cyano- ⁇ -phenylcinnamate, gly
• benzophenone-based ultraviolet absorber examples include 2,4-dihydroxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4,4′-dihydroxybenzophenone, and 2-hydroxy-4-methoxybenzophenone.
• 2-hydroxy-4-methoxy-4'-methylbenzophenone 2-hydroxy-4-methoxybenzophenone
• 4-phenylbenzophenone 2-ethylhexyl-4'-phenylbenzophenone-2-carboxylate
• 2-hydroxy-4- Examples thereof include n-octoxybenzophenone and 4-hydroxy-3-carboxybenzophenone.
• Examples of the triazine-based UV absorber include 2,4,6-tris[4-(2-ethylhexyloxycarbonyl)anilino]-1,3,5-triazine, dioctylbutamide triazone, 2,4-bis- Examples include [ ⁇ 4-(2-ethylhexyloxy)-2-hydroxy ⁇ -phenyl]-6-(4-methoxyphenyl)-1,3,5-triazine.
• organic UV absorbers include 3-(4'-methylbenzylidene)-dl-camphor, 3-benzylidene-dl-camphor, urocanic acid ethyl ester, 2-phenyl-5-methylbenzoxazole, 2,2 '-Hydroxy-5-methylphenylbenzotriazole, 2-(2'-hydroxy-5-t-octylphenyl)benzotriazole, dibenzalazine, dianisoylmethane, 4-methoxy-4'-t-butyldibenzoylmethane, 5 -(3,3-Dimethyl-2-norbornylidene)-3-pentan-2-one, benzenebis-1,3-diketone derivative described in JP-A-2-212579, and JP-A-3-220153 Examples thereof include benzoylpinacolone derivatives.
• the organic ultraviolet absorber can be roughly classified into a solid organic ultraviolet absorber at 1 atm and 25° C. and a liquid organic ultraviolet absorber at 1 atm and 25° C.
• an organic ultraviolet absorber which is solid at 25° C. under 1 atmosphere may be used in combination with an organic ultraviolet absorber which is liquid at 25° C. under 1 atmosphere.
• isopropyl-p-methoxycinnamate, 2-ethylhexyl-p-methoxycinnamate, 2-ethoxyethyl-p-methoxycinnamate, etc. are organic UV absorbers that are liquid at 1°C and 25°C. is there.
• the UV absorbers may be used alone or in combination of two or more.
• the content of the ultraviolet absorber is preferably 1% by mass or more, more preferably 3% by mass or more, still more preferably 6% in the sunscreen oil-in-water emulsion cosmetic of the present invention from the viewpoint of the ultraviolet protection effect and the like.
• the water-in-oil water-in-water emulsion cosmetic of the present invention preferably 30% by mass or less, and more preferably 9% by mass or more, particularly preferably 9% by mass or more, and from the viewpoint of feeling of use (non-greasiness). It is preferably 25% by mass or less, more preferably 20% by mass or less, and particularly preferably 15% by mass or less.
• 1% by mass or more and 30% by mass or less is preferable, 3% by mass or more and 25% by mass or less is more preferable, and 6% by mass or more and 20% in the water-in-oil type emulsion cosmetic for sunscreen of the present invention. It is more preferably not more than 9% by mass, and particularly preferably not less than 9% by mass and not more than 15% by mass.
• the content of the organic ultraviolet absorber that is solid at 25° C. under 1 atmosphere is from the viewpoint of the ultraviolet protection effect. It is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, still more preferably 0.5% by mass or more, particularly preferably 1% by mass or more in the water-in-oil type emulsion cosmetic for sunscreen. From the viewpoint of feeling of use (non-greasiness), the water-in-oil type sunscreen emulsion cosmetic of the present invention preferably contains 10% by mass or less, more preferably 8% by mass or less, and further preferably 6% by mass. It is particularly preferably 4% by mass or less.
• the sunscreen water-in-oil type emulsion cosmetic of the present invention preferably 0.05% by mass or more and 10% by mass or less, more preferably 0.1% by mass or more and 8% by mass or less, 0 It is more preferably 0.5% by mass or more and 6% by mass or less, and particularly preferably 1% by mass or more and 4% by mass or less.
• the content of the organic ultraviolet absorber that is liquid at 25° C. under 1 atm is from the viewpoint of ultraviolet protection effect.
• the sunscreen oil-in-water emulsion cosmetic of the present invention preferably 20 mass% or less, more preferably 17 mass% or less, still more preferably 14 mass% or less, particularly preferably Is 10% by mass or less.
• 1% by mass or more and 20% by mass or less is preferable, 3% by mass or more and 17% by mass or less is more preferable, and 5.5% by mass is 5.5% by mass in the water-in-oil type emulsion cosmetic for sunscreen of the present invention.
• the amount is more preferably 14% by mass or less and particularly preferably 8% by mass or more and 10% by mass or less.
• the total content of (B) the hydrophobized ultraviolet scattering agent and (D) the ultraviolet absorbing agent is the water-in-oil emulsion for sunscreen of the present invention.
• the cosmetic preferably 12% by mass or more, more preferably 15% by mass or more, further preferably 18% by mass or more, particularly preferably 21% by mass or more, and abrasion resistance and feeling of use (non-greasy).
• the sunscreen water-in-oil type emulsion cosmetic of the present invention preferably 40 mass% or less, more preferably 36 mass% or less, further preferably 32 mass% or less, particularly preferably 28 mass% or less. Is.
• the sunscreen water-in-oil type emulsion cosmetic of the present invention 12% by mass or more and 40% by mass or less is preferable, 15% by mass or more and 36% by mass or less is more preferable, and 18% by mass or more 32
• the content is more preferably not more than mass%, particularly preferably not less than 21 mass% and not more than 28 mass%.
• the content ratio [(A)/(D)] of the component (A) alkyl modified silicone wax having a melting point of 60° C. or more to the component (D) ultraviolet absorber is such as abrasion resistance and usability (smoothness). From the viewpoint, it is preferably 0.01 or more, more preferably 0.02 or more, still more preferably 0.04 or more, and particularly preferably 0.06 or more, and the abrasion resistance, the feeling of use (non-stickiness), From the viewpoint of the ultraviolet protection effect and the like, it is preferably 0.32 or less, more preferably 0.24 or less, still more preferably 0.2 or less, and particularly preferably 0.16 or less. As a specific range, 0.01 or more and 0.32 or less are preferable, 0.02 or more and 0.24 or less are more preferable, 0.04 or more and 0.2 or less are more preferable, 0.06 or more and 0.16 or less Is particularly preferable.
• the content ratio [(B)/(D)] of the component (B) hydrophobized ultraviolet scattering agent to the component (D) ultraviolet absorber is from the viewpoint of feeling in use (non-greasy), ultraviolet protection effect, and the like.
• the specific range is preferably 0.1 or more and 3 or less, more preferably 0.3 or more and 2.6 or less, still more preferably 0.5 or more and 2.3 or less, and particularly preferably 1 or more and 2 or less.
• the water-in-oil type emulsion cosmetic for sunscreen of the present invention is, in addition to the above-mentioned components, a liquid oil agent other than the organic ultraviolet absorber that is liquid at 25° C. under 1 atmosphere (hereinafter, also referred to as “other liquid oil agent”).
• a powder other than the component (B), waxes other than the component (A), a lower alcohol, a preservative, a fragrance, a pH adjuster, a moisturizing agent, a film forming agent, and the like In addition, only one of these may be used alone, or two or more thereof may be used in combination.
• a thickener as described in International Publication No.
• the content of the thickener may vary depending on the feeling of use (non-greasiness), applicability and the like. From the viewpoint, in the water-in-oil type emulsion cosmetic for sunscreen of the present invention, 0 to 1% by mass is preferable, 0 to 0.1% by mass is more preferable, 0 to 0.01% by mass is further preferable, and 0 It is particularly preferably about 0.001% by mass. According to the present invention, excellent abrasion resistance can be obtained even when the content of the thickener is in such a range.
• liquid oils refer to oils that are liquid at 1°C and 25°C other than organic UV absorbers, and may be volatile oils or non-volatile oils. Further, only one kind may be used alone, or two or more kinds may be used in combination.
• the volatile oil agent is an oil agent that exhibits volatility at room temperature (25° C.)
• the non-volatile oil agent is an oil agent that does not exhibit volatility at room temperature (25° C.).
• volatile oil agent examples include light isoparaffin, decamethylcyclopentasiloxane, octamethylcyclotetrasiloxane, dodecamethylcyclohexasiloxane, methyltrimethicone, decamethyltetrasiloxane, ethyltrisiloxane, and volatile methylpolysiloxane.
• Light isoparaffins include Isopar H (manufactured by Esso Kagaku), isododecane (manufactured by Bayer), isohexadecane (manufactured by Unichema), IP solvent 1620MU, IP solvent 2028MU, IP solvent 2835 (above, manufactured by Idemitsu Kosan Co., Ltd.). ) And the like.
• Commercially available products of decamethylcyclopentasiloxane include TFS405 (manufactured by Momentive Performance Materials Japan LLC), SH245, DC345 (manufactured by Toray Dow Corning), KF-995 (manufactured by Shin-Etsu Chemical Co., Ltd.) and the like.
• Examples of commercially available methyltrimethicone include silicone TMF-1.5 (manufactured by Shin-Etsu Chemical Co., Ltd.).
• Examples of commercially available decamethyltetrasiloxane include KF-96L-1.5CS (produced by Shin-Etsu Chemical Co., Ltd.).
• Examples of commercial products of ethyltrisiloxane include SILSOFTETS (manufactured by Momentive Performance Materials Japan LLC).
• Examples of commercially available volatile methyl polysiloxanes include KF-96L-2CS (produced by Shin-Etsu Chemical Co., Ltd.).
• non-volatile hydrocarbon oil such as light liquid paraffin, liquid paraffin, heavy liquid isoparaffin, squalane, etc.
• non-volatile silicone oil such as non-volatile dimethyl polysiloxane, non-volatile methylphenyl polysiloxane
• 2-ethylhexane Non-volatile fatty acid ester oils such as cetyl acid, isononyl isononanoate, isotridecyl isononanoate, isopropyl myristate, isopropyl palmitate, 2-ethylhexyl palmitate, 2-ethylhexyl stearate, stearyl stearate; alkyl benzoate (C12-15) Etc.
• non-volatile fatty acid ester oils fatty acid triglycerides such as glyceryl tri(caprylic acid/capric acid) and glyceryl tri(2-ethylhexanoic acid); fatty acids such as neopentyl glycol dicaprate, neopentyl glycol diethylhexanoate and neo Esters with pentyl glycol; polyhydric alcohol fatty acid ester oils and the like may be used.
• examples of commercially available liquid paraffin include Pearlream 4 (manufactured by NOF CORPORATION).
• non-volatile dimethyl polysiloxanes examples include KF-96A-10CS (produced by Shin-Etsu Chemical Co., Ltd.).
• examples of commercially available isopropyl palmitate include Exepearl IPP (manufactured by Kao Corporation).
• Examples of commercial products of alkyl benzoate (C12-15) include FINSOLV TN (manufactured by Innospec Active Chemicals).
• Examples of commercially available neopentyl glycol dicaprate examples include Estemol N-01 (manufactured by Nisshin Oillio Group).
• the content of the other liquid oil agent is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 20% by mass or more, particularly preferably in the water-in-oil type emulsion cosmetic for sunscreen of the present invention.
• 5% by mass or more and 80% by mass or less is preferable, 10% by mass or more and 70% by mass or less is more preferable, and 20% by mass or more and 65% in the sunscreen water-in-oil emulsion cosmetic of the present invention.
• the content is more preferably less than or equal to mass%, and particularly preferably 30% or more and less than or equal to 60% by mass.
• the total amount of nonvolatile oil contained in the cosmetic is 25 at 1 atm.
• the content mass ratio of the component (A) an alkyl-modified silicone wax having a melting point of 60° C. or more to the total of the organic ultraviolet absorber and the non-volatile oily liquid which are liquids at 0° C. is preferably from the viewpoint of abrasion resistance, easiness of production and the like.
• 0.001 or more and 0.4 or less are preferable, 0.005 or more and 0.2 or less are more preferable, 0.01 or more and 0.1 or less are further preferable, 0.02 or more and 0.05 or less Is particularly preferable.
• nonionic surfactant As the above-mentioned surfactant, known ones such as anionic surfactant, cationic surfactant, nonionic surfactant and amphoteric surfactant may be used, but a water-in-oil emulsion cosmetic preparation is stably prepared. Therefore, it is preferable to use a nonionic surfactant having an HLB of 8 or less, and it is more preferable to use a nonionic surfactant having an HLB of 3 to 6 (particularly preferably HLB of 3 to 5).
• HLB is an index showing a hydrophilic-lipophilic balance (Hydrophile-Lipophile Balance), and is defined by the following equation by Oda and Teramura.
• HLB ( ⁇ inorganic value / ⁇ organic value) ⁇ 10
• a polyether-modified silicone is preferable in order to stably prepare a water-in-oil type emulsion cosmetic.
• the silicone chain of the polyether-modified silicone may be linear or branched.
• the polyether-modified silicone include polyoxyethylene/methylpolysiloxane copolymer, poly(oxyethylene/oxypropylene)methylpolysiloxane copolymer, alkyl chain branched polyoxyethylenemethylpolysiloxane copolymer, and alkyl Chain/silicone chain branched type polyoxyethylene methyl polysiloxane copolymer and the like.
• a polyoxyethylene/methylpolysiloxane copolymer is preferable from the viewpoint of emulsion stability.
• Commercially available products of polyoxyethylene/methylpolysiloxane copolymer include KF-6015 (HLB4.5), KF-6017 (HLB4.5) (above, manufactured by Shin-Etsu Chemical Co., Ltd.), SH3775M (HLB5, Toray). -Dow Corning) and the like.
• Examples of commercially available poly(oxyethylene/oxypropylene)methylpolysiloxane copolymers include KF-6012 (HLB7, manufactured by Shin-Etsu Chemical Co., Ltd.).
• Examples of commercial products of the alkyl chain-branched polyoxyethylene methyl polysiloxane copolymer include KF-6028 (HLB 4.0, manufactured by Shin-Etsu Chemical Co., Ltd.).
• Examples of commercial products of the alkyl chain/silicone chain branched type polyoxyethylene methyl polysiloxane copolymer include KF-6038 (HLB3.0, manufactured by Shin-Etsu Chemical Co., Ltd.).
• the content of such a surfactant in the sunscreen water-in-oil type emulsion cosmetic of the present invention is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and even more preferably 0.
• 3 mass% or more, particularly preferably 0.5 mass% or more, and in the sunscreen oil-in-water emulsion cosmetic of the present invention preferably 10 mass% or less, more preferably 5 mass% or less, It is preferably 3% by mass or less, and particularly preferably 1% by mass or less.
• the specific range is preferably 0.01% by mass or more and 10% by mass or less, more preferably 0.1% by mass or more and 5% by mass or less in the sunscreen water-in-oil type emulsion cosmetic of the present invention. It is more preferably 0.3% by mass or more and 3% by mass or less, and particularly preferably 0.5% by mass or more and 1% by mass or less.
• Examples of the dosage form of the water-in-oil type emulsion cosmetic for sunscreen of the present invention include non-solid forms such as liquid, emulsion, cream, paste and gel, and liquid, emulsion and cream are preferred. ..
• the viscosity of the sunscreen water-in-oil type emulsion cosmetic of the present invention at 25° C. is preferably 50 mPa ⁇ s or more, more preferably 100 mPa ⁇ s or more, still more preferably 300 mPa ⁇ s or more, from the viewpoint of ease of application.
• the water-in-oil type emulsion cosmetic for sunscreen of the present invention is excellent in abrasion resistance after application even in such a viscosity range that is easy to apply.
• the viscosity at 25°C can be measured with a Brookfield viscometer (B-type viscometer).
• water-in-oil type emulsion cosmetic for sunscreen of the present invention can be applied to the skin (preferably the skin excluding the scalp, more preferably the face, body, limbs, etc.) to be used as a sunscreen.
• the method of use is not particularly limited, but application by hand or an application tool is preferred.
• the sunscreen water-in-oil type emulsified cosmetic composition of the present invention can be produced by a conventional method.
• an oily component water-insoluble component
• a water-soluble component such as the component (C) is separately heated and stirred and mixed. It can be produced by mixing the obtained oily component mixture with the water-soluble component mixture, thoroughly stirring with a homogenizer, and then cooling.
• a water-in-oil type emulsion cosmetic for sunscreen containing the following components (A), (B) and (C).
• the melting point of the component (A) alkyl-modified silicone wax is preferably 61° C. or higher, more preferably 62° C. or higher, and preferably 120° C. or lower, more preferably 90° C. or lower, and further preferably 80.
• the water-in-oil type emulsion cosmetic for sunscreen according to ⁇ 1> which has a temperature of not higher than 0°C, particularly preferably not higher than 72°C.
• the alkyl-modified silicone wax of component (A) is preferably an oil-soluble alkyl-modified silicone wax, more preferably one or two selected from alkyl methicone wax, alkyl dimethicone wax and silsesquioxane resin wax.
• the water-in-oil type emulsion cosmetic for sunscreen according to ⁇ 1> or ⁇ 2>, which is dimethylsilylpolypropylsilsesquioxane.
• the content of the component (A) in the water-in-oil type water-in-sun emulsion cosmetic for sunscreen is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and further preferably 0.15% by mass.
• % Or more more preferably 0.4% by mass or more, particularly preferably 0.8% by mass or more, and preferably 16% by mass or less, more preferably 12% by mass in a sunscreen oil-in-water emulsion cosmetic.
• the water-in-oil type emulsion cosmetic for sunscreen according to any one of ⁇ 1> to ⁇ 3>, which is not more than 8% by mass, more preferably not more than 8% by mass, particularly preferably not more than 4% by mass.
• the content of the component (A) in the sunscreen oil-in-water emulsion cosmetic is preferably 0.05% by mass or more and 16% by mass or less, more preferably 0.1% by mass or more and 12% by mass or less.
• the component (B) is preferably a hydrophobized fine particle metal oxide, and more preferably one or more fine particle metal particles selected from zinc oxide, titanium oxide, cerium oxide, iron oxide and chromium oxide.
• the oxide is hydrophobized, more preferably one or more particulate metal oxides selected from zinc oxide, titanium oxide and cerium oxide are hydrophobized, and particularly preferably zinc oxide.
• a water-in-oil type emulsion cosmetic for sunscreen according to any one of ⁇ 1> to ⁇ 5>, which is one or two or more kinds of fine particle metal oxides selected from titanium oxide and subjected to a hydrophobic treatment.
• the hydrophobic treatment of the component (B) is preferably fluorine compound treatment, silicone treatment, silicone resin treatment, pendant treatment, silane coupling agent treatment, titanium coupling agent treatment, oil agent treatment, N-acylated lysine treatment.
• a polyacrylic acid treatment, a metal soap treatment, an amino acid treatment, an inorganic compound treatment, a plasma treatment, a mechanochemical treatment, a silane compound treatment and a silazane compound treatment are hydrophobic treatments selected, more preferably a silicone treatment, a silicone resin treatment, ⁇ 1> to ⁇ 6>, which is a hydrophobic treatment selected from silane compound treatment, silazane compound treatment, and metal soap treatment, and more preferably a hydrophobic treatment selected from silicone treatment and silane compound treatment.
• Water-in-oil type emulsion cosmetic for sunscreen is preferably 2% by mass or more, more preferably 6% by mass or more, further preferably 7.5% by mass or more, particularly It is preferably 10% by mass or more, and in the water-in-oil water-based sunscreen emulsion cosmetic, preferably 35% by mass or less, more preferably 30% by mass or less, further preferably 25% by mass or less, particularly preferably 20% by mass.
• the water-in-oil type emulsion cosmetic for sunscreen according to any one of ⁇ 1> to ⁇ 7>, which is not more than mass %.
• the content of the component (B) in the water-in-oil type emulsion cosmetic for sunscreen is preferably 2% by mass or more and 35% by mass or less, more preferably 6% by mass or more and 30% by mass or less, and further preferably The water-in-oil type emulsion cosmetic for sunscreen according to any one of ⁇ 1> to ⁇ 7>, which is 7.5% by mass or more and 25% by mass or less, particularly preferably 10% by mass or more and 20% by mass or less.
• the content mass ratio [(A)/(B)] of the component (A) to the component (B) is preferably 0.005 or more, more preferably 0.01 or more, still more preferably 0.025 or more, More preferably 0.05 or more, particularly preferably 0.075 or more, preferably 1.67 or less, more preferably 1.1 or less, still more preferably 0.7 or less, particularly preferably 0.3 or less.
• the water-in-oil type emulsion cosmetic for sunscreen according to any one of ⁇ 1> to ⁇ 9>.
• the mass ratio [(A)/(B)] of the component (A) to the component (B) is preferably 0.005 or more and 1.67 or less, more preferably 0.01 or more and 1.1 or less, More preferably 0.025 or more and 0.7 or less, further preferably 0.05 or more and 0.3 or less, particularly preferably 0.075 or more and 0.3 or less, and described in any of ⁇ 1> to ⁇ 9>.
• Water-in-oil type emulsion cosmetic for sunscreen is preferably 0.005 or more and 1.67 or less, more preferably 0.01 or more and 1.1 or less, More preferably 0.025 or more and 0.7 or less, further preferably 0.05 or more and 0.3 or less, particularly preferably 0.075 or more and 0.3 or less, and described in any of ⁇ 1> to ⁇ 9>.
• Water-in-oil type emulsion cosmetic for sunscreen is preferably 0.005 or more and 1.67 or less, more preferably 0.01 or more and 1.1 or less, More preferably 0.0
• the content of the component (C) in the water-in-oil type emulsion cosmetic for sunscreen is preferably 1% by mass or more, more preferably 2.5% by mass or more, further preferably 5% by mass or more, particularly It is preferably 10% by mass or more, and in the water-in-oil type emulsion cosmetic for sunscreen, preferably 50% by mass or less, more preferably 40% by mass or less, further preferably 30% by mass or less, particularly preferably 20% by mass.
• the water-in-oil type emulsion cosmetic for sunscreen according to any one of ⁇ 1> to ⁇ 11>, which is not more than mass %.
• the content of the component (C) in the sunscreen oil-in-water emulsion cosmetic is preferably 1% by mass or more and 50% by mass or less, more preferably 2.5% by mass or more and 40% by mass or less, and
• Component (D) is hexyl diethylaminohydroxybenzoylbenzoate, 2,4-bis-[ ⁇ 4-(2-ethylhexyloxy)-2-hydroxy ⁇ -phenyl]-6-(4-methoxyphenyl) -1,3,5-triazine and 2,4,6-tris[4-(2-ethylhexyloxycarbonyl)anilino]-1,3,5-triazine selected from the group consisting of 1, 2 or more under 1 atm pressure 25
• Organic UV absorber which is solid at 0°C, and one or more atmospheric pressures selected from isopropyl-p-methoxycinnamate, 2-ethylhexyl-p-methoxycinnamate and 2-ethoxyethyl-p-methoxycinnamate
• Water-in-oil type emulsion cosmetic for sunscreen according to ⁇ 14> or ⁇ 15>, which is a combination with an organic ultraviolet absorber that is liquid
• the content of the component (D) in the sunscreen oil-in-water emulsion cosmetic is preferably 1% by mass or more, more preferably 3% by mass or more, further preferably 6% by mass or more, and particularly preferably It is 9% by mass or more, and in the water-in-oil type emulsion cosmetic for sunscreen, preferably 30% by mass or less, more preferably 25% by mass or less, further preferably 20% by mass or less, particularly preferably 15% by mass.
• the water-in-oil type emulsion cosmetic for sunscreen according to any of ⁇ 14> to ⁇ 16>, which is as follows.
• the content of the component (D) in the sunscreen oil-in-water emulsion cosmetic is preferably 1% by mass or more and 30% by mass or less, more preferably 3% by mass or more and 25% by mass or less, and further preferably The water-in-oil type emulsion cosmetic for sunscreen according to any one of ⁇ 14> to ⁇ 16>, which is 6% by mass or more and 20% by mass or less, particularly preferably 9% by mass or more and 15% by mass or less.
• the total content of the component (B) and the component (D) is preferably 12% by mass or more and 40% by mass or less, more preferably 15% by mass or more 36 in the water-in-oil sunscreen emulsion cosmetic.
• the content mass ratio [(A)/(D)] of the component (A) to the component (D) is preferably 0.01 or more and 0.32 or less, more preferably 0.02 or more and 0.24 or less,
• the mass ratio [(B)/(D)] of the component (B) to the component (D) is preferably 0.1 or more and 3 or less, more preferably 0.3 or more and 2.6 or less, and further preferably Is 0.5 or more and 2.3 or less, particularly preferably 1 or more and 2 or less, and the water-in-oil type emulsion cosmetic for sunscreen according to any one of ⁇ 14> to ⁇ 20>.
• a liquid oil agent other than an organic ultraviolet absorber which is liquid at 25° C. under 1 atmosphere, a surfactant, a powder other than the component (B), a wax other than the component (A), a lower alcohol, a preservative,
• the sunscreen water-in-oil type emulsified cosmetic composition according to any one of ⁇ 1> to ⁇ 21>, containing one or more selected from perfumes, pH adjusters, humectants and film-forming agents.
• Examples 1-8 and Comparative Examples 1-5 The water-in-oil type emulsified cosmetics of Examples 1 to 8 and Comparative Examples 1 to 5 were produced by a conventional method, and the abrasion resistance and the feeling of use were evaluated. The results are shown in Tables 1 and 2.
• Comparative Examples 6-7 The oil-in-water emulsified cosmetics of Comparative Examples 6 to 7 were produced by a conventional method, and the SPF, abrasion resistance and feeling of use were evaluated. The results are shown in Table 3.
• the resulting water-in-oil type emulsion cosmetic has little stickiness after application, has excellent abrasion resistance, and is excellent as a sunscreen cosmetic.

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