CN113272021A - Water-in-oil type emulsion cosmetic for sunscreen - Google Patents
Water-in-oil type emulsion cosmetic for sunscreen Download PDFInfo
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- CN113272021A CN113272021A CN201980084732.4A CN201980084732A CN113272021A CN 113272021 A CN113272021 A CN 113272021A CN 201980084732 A CN201980084732 A CN 201980084732A CN 113272021 A CN113272021 A CN 113272021A
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- 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
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- 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
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- 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
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- 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
Abstract
The invention provides a sunscreen emulsified cosmetic which is less sticky after being coated and has excellent rub resistance. The water-in-oil type emulsion cosmetic for sunscreen of the present invention contains the following components (A), (B) and (C). (A) An alkyl-modified silicone wax (B) having a melting point of 60 ℃ or higher, a hydrophobizing agent for an ultraviolet scattering agent (C), and water.
Description
Technical Field
The present invention relates to a water-in-oil type emulsion cosmetic for sunscreen.
Background
Emulsion cosmetics for sunscreen are roughly classified into oil-in-water type cosmetics and water-in-oil type cosmetics. As an oil-in-water type emulsion cosmetic for sunscreen, for example, an oil-in-water type emulsion cosmetic is known in which oil droplets containing an ultraviolet absorber or the like and an alkyl dimethylsilyl polypropylsilsesquioxane are dispersed in water (patent documents 1 and 2).
(patent document 1) Japanese patent application laid-open No. 2007-532754
(patent document 2) pamphlet of International publication No. 2018/062469
Disclosure of Invention
The present invention provides a water-in-oil type emulsion cosmetic for sunscreen, which contains the following components (A), (B) and (C).
(A) Alkyl-modified silicone wax having a melting point of 60 ℃ or higher
(B) Hydrophobization treatment ultraviolet scattering agent
(C) Water (W)
Detailed Description
The oil-in-water emulsion cosmetic disclosed in patent document 2, which uses an alkyl dimethylsilyl polypropylsilsesquioxane or the like, is not likely to adhere again even when pressed from the skin with toilet paper or the like after the cosmetic is applied to the skin, but is insufficient in terms of abrasion resistance, and is likely to cause peeling of the coating film when the surface of the applied part is rubbed with a stronger force.
The invention relates to a sunscreen emulsified cosmetic which is less sticky after being coated and has excellent rub resistance.
The present inventors have found that a water-in-oil emulsion cosmetic prepared by combining an alkyl-modified silicone wax having a melting point of 60 ℃ or higher and a hydrophobized ultraviolet scattering agent is useful as a sunscreen and has a good feeling of use with little stickiness after coating and excellent rub resistance after coating, and have completed the present invention.
The water-in-oil type emulsion cosmetic for sunscreen of the present invention is excellent in rub resistance. In addition, the coating had a good feel in use with less stickiness after coating.
< Water-in-oil type emulsion cosmetic for sunscreen >
(component (A))
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 ℃ or higher.
The alkyl-modified silicone wax as the component (a) is preferably an alkyl-modified silicone wax having a melting point of 60 ℃ or higher among alkyl-modified silicone waxes obtained by modifying dimethylpolysiloxane with an alkyl group having 9 to 80 carbon atoms, from the viewpoint of abrasion resistance and feeling of use (no stickiness).
The alkyl group may be linear or branched. The number of carbon atoms 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 is preferably 70 or less, more preferably 60 or less, and particularly preferably 50 or less from the viewpoint of ease of production, feeling of use (no coating feeling), and the like. 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 alkyl group may have any substitution position, and the substitution form may be any of a single-terminal type, a double-terminal type, a random type, and the like. The number of substitution of the alkyl group is also arbitrary, and may be 1 or 2 or more in the molecule. When the number of substitution of the alkyl group is 2 or more, the 2 or more alkyl groups may be the same or different. Further, as the alkyl-modified silicone wax having a melting point of 60 ℃ or higher, a mixture of silicone waxes modified with different kinds of alkyl groups may be used.
The alkyl-modified silicone wax as the component (a) used in the present invention has a melting point of 60 ℃ or higher, and is preferably 61 ℃ or higher, more preferably 62 ℃ or higher from the viewpoints of abrasion resistance, feeling in use (no stickiness, smoothness), and the like, and is preferably 120 ℃ or lower, more preferably 90 ℃ or lower, more preferably 80 ℃ or lower, and particularly preferably 72 ℃ or lower from the viewpoints of ease of production, and the like. The specific range is preferably 60 ℃ to 90 ℃, more preferably 61 ℃ to 80 ℃, and particularly preferably 62 ℃ to 72 ℃.
In the present specification, the melting point refers to a melting point measured according to JISK 0064.
The alkyl-modified silicone wax having a melting point of 60 ℃ or higher as the component (a) is preferably an oil-soluble alkyl-modified silicone wax having a melting point of 60 ℃ or higher. Examples of such alkyl-modified silicone waxes include: alkyl methicone wax, alkyl dimethicone wax, silsesquioxane resin wax, and the like, and only 1 of these may be used, or 2 or more may be used in combination. Among these, from the viewpoints of abrasion resistance, feeling in use (no stickiness, smoothness, no coating feeling), and the like, an alkyl polymethylsiloxane wax and a silsesquioxane resin wax are preferable, and a silsesquioxane resin wax is particularly preferable. The silsesquioxane resin wax is preferably an alkyl (C30-45) dimethylsilylpropylsilsesquioxane.
The alkyl-modified silicone wax having a melting point of 60 ℃ or higher as component (a) may be a commercially available one, or may be one synthesized conventionally. Examples thereof include: alkyl (C26-28) polymethylsiloxane (BELSIL CM 7026VP, manufactured by Wacker Asahikasei Silicone Co., melting point 70 ℃ C.), alkyl (C30-45) polymethylsiloxane (AMS-C30 Cosmetic Wax, manufactured by Dow Corning Toray Co., Ltd., melting point 73-77 ℃ C.), alkyl (C30-45) polydimethylsiloxane (SF-1642, structural Materials Japan LLC., melting point 60-70 ℃ C.), alkyl (C30-45) dimethylpropylsiloxane (SW-8005C30 Wax, Dow Corning Toray Co., manufactured by Ltd, melting point 63-71 ℃ C.), and the like.
The alkyl-modified silicone wax having a melting point of 60 ℃ or higher may be used alone in 1 kind, or may be used in combination with 2 or more kinds.
The content of the alkyl-modified silicone wax having a melting point of 60 ℃ or higher in the water-in-oil emulsion cosmetic for sunscreen of the present invention is preferably 0.05% by mass or higher, more preferably 0.1% by mass or higher, even more preferably 0.15% by mass or higher, even more preferably 0.4% by mass or higher, and particularly preferably 0.8% by mass or higher, from the viewpoints of rubbing resistance, feeling in use (no sliminess, smoothness), and the like, and is preferably 16% by mass or lower, more preferably 12% by mass or lower, even more preferably 8% by mass or lower, and particularly preferably 4% by mass or lower, from the viewpoints of ease of production, feeling in use (no film coating feeling), and the like. In a specific range, in the water-in-oil type emulsion cosmetic for sunscreen of the present invention, it 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, further preferably 0.15% by mass or more and 8% by mass or less, further preferably 0.4% by mass or more and 8% by mass or less, and particularly preferably 0.8% by mass or more and 4% by mass or less.
Further, when the content of the alkyl-modified silicone wax having a melting point of 60 ℃ or higher is 0.4% by mass or higher, the feeling of use (feeling of no coating) is particularly improved, and when the content is 0.8% by mass or higher, the abrasion resistance is further improved in addition to the feeling of use (feeling of no coating).
(component (B))
The water-in-oil type emulsion cosmetic for sunscreen of the present invention contains a hydrophobized ultraviolet scattering agent. The hydrophobized ultraviolet scattering agent is preferably a hydrophobized microparticle metal oxide.
The fine-particle metal oxide used for hydrophobizing the fine-particle metal oxide is preferably 1 or 2 or more kinds of fine-particle metal oxides selected from zinc oxide, titanium oxide, cerium oxide, iron oxide, and chromium oxide, from the viewpoint of easy acquisition. Among these fine particle metal oxides, from the viewpoint of the ultraviolet protection effect and the like, 1 or 2 or more kinds of fine particle metal oxides selected from zinc oxide, titanium oxide and cerium oxide are preferable, and 1 or 2 or more kinds of fine particle metal oxides selected from zinc oxide and titanium oxide are more preferable. These fine-particle metal oxides may contain trace elements having a valence of +2 or more, and the fine-particle metal oxides may contain 2 or more kinds of metals such as iron, zirconium, calcium, manganese, magnesium, and yttrium, either singly or in combination.
In addition, from the viewpoint of abrasion resistance and the like, it is preferable to use at least hydrophobized fine particulate zinc oxide as the hydrophobized fine particulate metal oxide. For example, it is preferable to use only hydrophobized particulate zinc oxide, or to use hydrophobized particulate zinc oxide in combination with other hydrophobized particulate metal oxides such as hydrophobized particulate titanium oxide or hydrophobized particulate cerium oxide.
The shape of the "fine particle metal oxide" is not particularly limited, and examples thereof include: spherical, plate, rod, spindle, needle, amorphous, and the like.
The average particle diameter of the "fine-particle metal oxide" is preferably 0.01 μm or more, more preferably 0.012 μm or more, further preferably 0.015 μm or more, and further preferably 1 μm or less, more preferably 0.8 μm or less, further preferably 0.5 μm or less. The specific range of the average particle diameter is preferably 0.01 μm or more and 1 μm or less, more preferably 0.012 μm or more and 0.8 μm or less, and particularly preferably 0.015 μm or more and 0.5 μm or less. When the average particle diameter is in such a range, a sufficient ultraviolet protection effect can be exhibited, and dispersion stability can be improved.
The average particle diameter of the fine-particle metal oxide means an average particle diameter measured by a laser diffraction/scattering method.
As the fine particle zinc oxide, for example, commercially available are: FINEX-25, FINEX-30, FINEX-50, FINEX-75(Sakai Chemical Industry Co., Ltd.); MZ500 series, MZ700 series (manufactured by TAYCA CORPORATION); ZnO-350(Sumitomo Osaka Cement Co., Ltd.), and the like. As the fine particulate titanium oxide, for example, TTO-55 series and TTO-51 series (manufactured by Stone industries, Ltd.) are commercially available; JR series, JA series (manufactured by TAYCA CORPORATION), and the like. As the microparticle cerium oxide, for example, high purity cerium sold by Nikki co., ltd, or SEIMI CHEMICAL co.
The hydrophobization treatment of the fine particle metal oxide can be carried out using a known surface treatment agent for hydrophobization, and examples thereof include: fluorine compound treatment, silicone treatment (silicone treatment), silicone resin treatment (silicone resin treatment), side chain treatment (pendant treatment), silane coupling agent treatment, titanium coupling agent treatment, oil treatment, N-acylated lysine treatment (N-acylated lysine treatment), polyacrylic acid treatment, metal soap treatment, amino acid treatment, inorganic compound treatment, plasma treatment, mechanochemical treatment, silane compound treatment, silazane compound treatment, and the like.
Among these treatments, from the viewpoint of dispersion stability and the like, treatments with silicone or silicone resin, treatments with silane compounds or silazane compounds, and treatments with metal soaps such as aluminum isostearate are preferable.
Examples of the silicone or silicone resin include: methyl polysiloxane, methylphenyl polysiloxane, methylhydrogenpolysiloxane-dimethylpolysiloxane copolymer, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, octamethyltrisiloxane, tetradecmethylhexasiloxane, dimethylsiloxane-methyl (polyoxyethylene) siloxane-methyl (polyoxypropylene) siloxane copolymer, dimethylsiloxane-methyl (polyoxyethylene) siloxane copolymer, dimethylsiloxane-methyl (polyoxypropylene) siloxane copolymer, dimethylsiloxane-methylcetyloxysiloxane copolymer, dimethylsiloxane-methylstearyloxysiloxane copolymer, and the like. The methylhydrogenpolysiloxane-dimethylpolysiloxane copolymer is preferably represented by the following formula (2).
[ in the formula (2), m and n are integers of 0 or more, and m + n is 1. ltoreq. m + n.ltoreq.60. ]
The silane compound or the silazane compound is preferably a silane compound or a 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, and more preferably a silane compound represented by the following formula (3) or a silazane compound represented by the following formula (4). Of these, 1 kind may be used alone, or 2 or more kinds may be used in combination.
R4(R5)pSi(Z)3-p……(3)
[ in the formula (3),
R4represents 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,
R5represents 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. ]
R6R7R8SiNHSiR9R10R11……(4)
[ in the formula (4), R6～R11Each independently 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.]
The silane compound is preferably an alkylalkoxysilane or a fluoroalkylalkoxysilane, and more preferably an alkyltrialkoxysilane or a fluoroalkyltrialkoxysilane, from the viewpoint of dispersion stability and the like. Specifically, there may be mentioned: hexyltrimethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, octadecyltrimethoxysilane, trifluoropropyltrimethoxysilane, heptadecafluorodecyltrimethoxysilane, etc. Of these, 1 kind may be used alone, or 2 or more kinds may be used in combination. Among these, octyltrimethoxysilane and octyltriethoxysilane are more preferable.
Specific examples of the silazane compound include hexamethyldisilazane.
The coating amount of the surface treatment agent used for the hydrophobization treatment is preferably 3 parts by mass or more and more preferably 5 parts by mass or more per 100 parts by mass of the fine particle metal oxide from the viewpoint of emulsion stability, dispersion stability and the like, and is preferably 15 parts by mass or less and more preferably 10 parts by mass or less per 100 parts by mass of the fine particle metal oxide from the viewpoint of emulsion stability, dispersion stability and the like.
The method of the hydrophobization treatment can be performed by appropriately selecting a conventionally known method. For example, as the treatment with silicone or silicone resin, the following methods can be mentioned as described in japanese patent No. 3187440: the surface of the fine particle metal oxide is coated with silicon oxide by coating the fine particle metal oxide with at least 1 or more of an organopolysiloxane and a silicone compound composed of a silicone resin (excluding the silane compound) in a non-gas phase state and then firing the coated fine particle metal oxide in an oxygen-containing atmosphere at a temperature of 600 to 950 ℃.
In addition, as a treatment method using a silane compound or a silazane compound, a chemical bonding method can be cited, and more specifically, the following method can be cited: the silane compound or the silazane compound and the fine-particle metal oxide are mixed with an organic solvent such as n-hexane, cyclohexane, or lower alcohol, and after finely pulverizing the mixture as needed, the organic solvent is removed by heating (for example, 80 to 250 ℃) or by reducing pressure. Further, the following methods can be mentioned as described in Japanese patent laid-open No. 2007-326902: after coating treatment with a polysiloxane compound, surface treatment with a silane compound in water was performed.
Further, the hydrophobization treatment ultraviolet scattering agent may be used alone in 1 kind, or may be used in combination with 2 or more kinds.
The content of the hydrophobized ultraviolet scattering agent in the water-in-oil emulsion cosmetic for sunscreen of the present invention is preferably 2 mass% or more, more preferably 6 mass% or more, further preferably 7.5 mass% or more, and particularly preferably 10 mass% or more from the viewpoints of rub resistance, feeling in use (no stickiness), ultraviolet protection effect, and the like, and is preferably 35 mass% or less, more preferably 30 mass% or less, further preferably 25 mass% or less, and particularly preferably 20 mass% or less from the viewpoints of feeling in use (no powdery feeling), formulation stability, and the like. In a specific range, in the water-in-oil type emulsion cosmetic for sunscreen of the present invention, it 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, still more preferably 7.5% by mass or more and 25% by mass or less, and particularly preferably 10% by mass or more and 20% by mass or less.
In addition, when the content of the hydrophobization-treated ultraviolet scattering agent is 7.5 mass% or more or 10 mass% or more, the abrasion resistance is particularly improved.
The content mass ratio [ (a)/(B) ] of the alkyl-modified silicone wax having a melting point of 60 ℃ or higher in the component (a) to the hydrophobized ultraviolet scattering agent in the component (B) is preferably 0.005 or more, more preferably 0.01 or more, further preferably 0.025 or more, still more preferably 0.05 or more, and particularly preferably 0.075 or more, from the viewpoints of abrasion resistance, feeling in use (no powdery feeling), and no skin whitening after application, and the like, and is preferably 1.67 or less, more preferably 1.1 or less, further preferably 0.7 or less, and 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, further preferably 0.025 or more and 0.7 or less, further preferably 0.05 or more and 0.3 or less, and particularly preferably 0.075 or more and 0.3 or less.
When the content mass ratio [ (a)/(B) ] is 0.025 or more, the feeling of use (feeling of no coating) is particularly improved, and when the content mass ratio is 0.075 or more, the abrasion resistance is further improved in addition to the feeling of use (feeling of no coating).
(component (C))
The water-in-oil type emulsion cosmetic for sunscreen of the present invention contains water.
The water content in the water-in-oil emulsion cosmetic for sunscreen of the present invention is preferably 1 mass% or more, more preferably 2.5 mass% or more, further preferably 5 mass% or more, and particularly preferably 10 mass% or more from the viewpoint of feeling of use (refreshing feeling, smoothness) and the like, and is preferably 50 mass% or less, more preferably 40 mass% or less, further preferably 30 mass% or less, and particularly preferably 20 mass% or less from the viewpoint of formulation stability, feeling of use (non-sliminess) and the like. In a specific range, in the water-in-oil type emulsion cosmetic for sunscreen of the present invention, it 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, still more preferably 5% by mass or more and 30% by mass or less, and particularly preferably 10% by mass or more and 20% by mass or less.
(component (D))
The water-in-oil type emulsion cosmetic for sunscreen of the present invention preferably further contains (D) an ultraviolet absorber in addition to the components (a) to (C) from the viewpoint of ultraviolet protection effect. As the ultraviolet absorber, an organic ultraviolet absorber is preferable from the viewpoints of water resistance, abrasion resistance, solubility, and the like.
Examples of the organic ultraviolet absorber include: benzoic acid-based ultraviolet absorbers, anthranilic acid-based ultraviolet absorbers, salicylic acid-based ultraviolet absorbers, cinnamic acid-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, triazine-based ultraviolet absorbers, and the like. Among these, 1 or 2 or more selected from benzoic acid-based ultraviolet absorbers, cinnamic acid-based ultraviolet absorbers and triazine-based ultraviolet absorbers are preferable. The organic ultraviolet absorber is preferably an oil-soluble organic ultraviolet absorber.
Examples of benzoic acid-based ultraviolet absorbers include: p-aminobenzoic acid (para-aminobenzoic acid: PABA), glyceryl PABA, ethyldihydroxypropyl PABA, ethyl N-ethoxylate PABA, ethyl N-dimethyl PABA, butyl N-dimethyl PABA, amyl N-dimethyl PABA, octyl dimethyl PABA, hexyl diethylaminohydroxybenzoyl benzoate, etc.
Examples of the anthranilic acid-based ultraviolet absorber include: N-Acetylanthranilic acid-trimethylcyclohexyl ester (homomenthyl-N-acetyl anthranilate), and the like.
Examples of the salicylic acid-based ultraviolet absorbers include: amyl salicylate, salicylic acid
Ester (menthyl salicylate), salicylic acid high
Esters (homomenthyl salicylates), octyl salicylate, phenyl salicylate, benzyl salicylate, phenyl p-isopropoxide salicylate, and the like.
Examples of the cinnamic acid ultraviolet absorbers include: octyl cinnamate, ethyl 4-isopropyl cinnamate, ethyl 2, 4-diisopropyl cinnamate, methyl 2, 4-diisopropyl cinnamate, propyl p-methoxycinnamate, isopropyl p-methoxycinnamate, isoamyl p-methoxycinnamate, 2-ethylhexyl p-methoxycinnamate, 2-ethoxyethyl p-methoxycinnamate, cyclohexyl p-methoxycinnamate, ethyl α -cyano- β -phenylcinnamate, 2-ethylhexyl α -cyano- β -phenylcinnamate, glycerol mono-2-ethylhexanoyl di-p-methoxycinnamate, and the like.
Examples of benzophenone-based ultraviolet absorbers include: 2, 4-dihydroxybenzophenone, 2' -dihydroxy-4-methoxybenzophenone, 2' -dihydroxy-4, 4' -dihydroxybenzophenone, 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-n-octyloxybenzophenone, 4-hydroxy-3-carboxybenzophenone and the like.
Examples of the triazine-based ultraviolet absorber include: 2,4, 6-tris [4- (2-ethylhexyloxycarbonyl) anilino ] -1,3, 5-triazine, dioctylbutylaminotriazinone, 2, 4-bis- [ {4- (2-ethylhexyloxy) -2-hydroxy } -phenyl ] -6- (4-methoxyphenyl) -1,3, 5-triazine, and the like.
Examples of other organic ultraviolet absorbers include: 3- (4 '-methylbenzenyl) -dl-camphor, 3-benzylenyl-dl-camphor, ethyl urocanate, 2-phenyl-5-methylbenzoxazole, 2' -hydroxy-5-methylbenzotriazole, 2- (2 '-hydroxy-5-tert-octylphenyl) benzotriazole, dibenzylhydrazine (dibenzylzalazin), dianisiloylmethane (dianisoyl methane), 4-methoxy-4' -tert-butylbenzoylmethane, 5- (3, 3-dimethyl-2-norbornene) -3-pentan-2-one (5- (3, 3-dimethyl-2-norbonylene) -3-pentan-2-one), benzene-bis-1 described in Japanese patent laid-open No. 2-212579, 3-diketone derivatives, benzoyl tert-butyl ethanone (benzoylpinacolone) derivatives described in Japanese patent laid-open No. 3-220153, and the like.
The organic ultraviolet absorber can be roughly classified into an organic ultraviolet absorber that is solid at 25 ℃ under 1 atmosphere and an organic ultraviolet absorber that is liquid at 25 ℃ under 1 atmosphere. In the present invention, it is preferable to use, as the ultraviolet absorber, an organic ultraviolet absorber which is solid at 25 ℃ under 1 atmosphere. In this case, an organic ultraviolet absorber that is solid at 25 ℃ under 1 atmosphere and an organic ultraviolet absorber that is liquid at 25 ℃ under 1 atmosphere may be used in combination.
Further, for example, hexyl diethylaminohydroxybenzoyl benzoate, 2, 4-bis- [ {4- (2-ethylhexyloxy) -2-hydroxy } -phenyl ] -6- (4-methoxyphenyl) -1,3, 5-triazine, 2,4, 6-tris [4- (2-ethylhexyloxycarbonyl) anilino ] -1,3, 5-triazine and the like exemplified above are organic ultraviolet absorbers which are solid at 25 ℃ under 1 atmosphere. In addition, isopropyl p-methoxycinnamate, 2-ethylhexyl p-methoxycinnamate, 2-ethoxyethyl p-methoxycinnamate, and the like listed above are organic ultraviolet absorbers which are liquid at 25 ℃ under 1 atmosphere.
Further, only 1 kind of the ultraviolet absorber may be used alone, or 2 or more kinds may be used in combination.
The content of the ultraviolet absorber in the water-in-oil type emulsion cosmetic for sunscreen of the present invention is preferably 1 mass% or more, more preferably 3 mass% or more, further preferably 6 mass% or more, and particularly preferably 9 mass% or more from the viewpoint of ultraviolet protection effect and the like, and the content of the ultraviolet absorber in the water-in-oil type emulsion cosmetic for sunscreen of the present invention is preferably 30 mass% or less, more preferably 25 mass% or less, further preferably 20 mass% or less, and particularly preferably 15 mass% or less from the viewpoint of use feeling (non-stickiness). In a specific range, in the water-in-oil type emulsion cosmetic for sunscreen of the present invention, it 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, still more preferably 6% by mass or more and 20% by mass or less, and particularly preferably 9% by mass or more and 15% by mass or less.
In addition, in the case of using an organic ultraviolet absorber that is solid at 25 ℃ under 1 atmosphere as an ultraviolet absorber, the content of the organic ultraviolet absorber that is solid at 25 ℃ under 1 atmosphere is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, further preferably 0.5% by mass or more, and particularly preferably 1% by mass or more in the water-in-oil emulsion cosmetic for sunscreen of the present invention from the viewpoint of the ultraviolet protection effect, and is preferably 10% by mass or less, more preferably 8% by mass or less, further preferably 6% by mass or less, and particularly preferably 4% by mass or less in the water-in-oil emulsion cosmetic for sunscreen of the present invention from the viewpoint of the feeling of use (non-sliminess). In a specific range, in the water-in-oil type emulsion cosmetic for sunscreen of the present invention, it is 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, further 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.
In addition, in the case of using an organic ultraviolet absorber that is liquid at 25 ℃ under 1 atmosphere as an ultraviolet absorber, the content of the organic ultraviolet absorber that is liquid at 25 ℃ under 1 atmosphere is preferably 1% by mass or more, more preferably 3% by mass or more, further preferably 5.5% by mass or more, and particularly preferably 8% by mass or more in the water-in-oil emulsion cosmetic for sunscreen of the present invention from the viewpoint of the ultraviolet protection effect, and in the water-in-oil emulsion cosmetic for sunscreen of the present invention, from the viewpoint of the feeling of use (non-stickiness), is preferably 20% by mass or less, more preferably 17% by mass or less, further preferably 14% by mass or less, and particularly preferably 10% by mass or less. In a specific range, in the water-in-oil type emulsion cosmetic for sunscreen of the present invention, it is preferably 1% by mass or more and 20% by mass or less, more preferably 3% by mass or more and 17% by mass or less, still more preferably 5.5% by mass or more and 14% by mass or less, and particularly preferably 8% by mass or more and 10% by mass or less.
The total content of the (B) hydrophobized ultraviolet scattering agent and the (D) ultraviolet absorber in the water-in-oil type emulsion cosmetic for sunscreen of the present invention is preferably 12 mass% or more, more preferably 15 mass% or more, further preferably 18 mass% or more, and particularly preferably 21 mass% or more from the viewpoints of rub resistance, feeling in use (no stickiness), and the like, and is preferably 40 mass% or less, more preferably 36 mass% or less, further preferably 32 mass% or less, and particularly preferably 28 mass% or less from the viewpoints of rub resistance, feeling in use, and the like. In a specific range, in the water-in-oil type emulsion cosmetic for sunscreen of the present invention, it is preferably 12% by mass or more and 40% by mass or less, more preferably 15% by mass or more and 36% by mass or less, still more preferably 18% by mass or more and 32% by mass or less, and particularly preferably 21% by mass or more and 28% by mass or less.
The content mass ratio [ (a)/(D) ] of the alkyl-modified silicone wax having a melting point of 60 ℃ or higher of the component (a) to the ultraviolet absorber of the component (D) is preferably 0.01 or more, more preferably 0.02 or more, further preferably 0.04 or more, and particularly preferably 0.06 or more, and is preferably 0.32 or less, more preferably 0.24 or less, further preferably 0.2 or less, and particularly preferably 0.16 or less, from the viewpoints of abrasion resistance, feeling in use (no stickiness), ultraviolet protection effect, and the like. The specific range is preferably 0.01 to 0.32, more preferably 0.02 to 0.24, still more preferably 0.04 to 0.2, and particularly preferably 0.06 to 0.16.
The content mass ratio [ (B)/(D) ] of the hydrophobized ultraviolet scattering agent of the component (B) to the ultraviolet absorber of the component (D) is preferably 0.1 or more, more preferably 0.3 or more, further preferably 0.5 or more, and particularly preferably 1 or more from the viewpoints of feeling of use (non-stickiness), ultraviolet protection effect, and the like, and is preferably 3 or less, more preferably 2.6 or less, further preferably 2.3 or less, and particularly preferably 2 or less from the viewpoints of feeling of use (non-stickiness), 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 may contain, in addition to the above components, a liquid oil other than an organic ultraviolet absorber which is liquid at 25 ℃ under 1 atm (hereinafter, also referred to as "other liquid oil"), a surfactant, a powder other than component (B), waxes other than component (a), a lower alcohol, a preservative, a perfume, a pH adjuster, a humectant, a coating film forming agent, and the like. Of these, only 1 species may be used alone, or 2 or more species may be used in combination. In addition to these, a thickener (thickner) as described in wo 2018/062469 pamphlet may be used, and the content of the thickener in the water-in-oil type emulsion cosmetic for sunscreen of the present invention is preferably 0 to 1% by mass, more preferably 0 to 0.1% by mass, even more preferably 0 to 0.01% by mass, and particularly preferably 0 to 0.001% by mass, from the viewpoints of feeling of use (no stickiness), coatability, and the like. According to the present invention, even when the content of the thickener is in such a range, excellent abrasion resistance can be obtained.
The other liquid oil is a liquid oil other than the organic ultraviolet absorber in the oil which is liquid at 25 ℃ under 1 atmosphere, and may be a volatile oil or a non-volatile oil. In addition, only 1 kind can be used alone, can also be combined with more than 2 kinds. The volatile oil agent is an oil agent exhibiting volatility at room temperature (25 ℃), and the non-volatile oil agent is an oil agent exhibiting no volatility at room temperature (25 ℃).
As the volatile oil agent, there can be exemplified: light isoparaffin, decamethylcyclopentasiloxane, octamethylcyclotetrasiloxane, dodecamethylcyclohexasiloxane, methylpolytrimethicone, decamethyltetrasiloxane, ethyltrisiloxane, volatile methylpolysiloxane, and the like.
As commercial products of light isoparaffins, there can be mentioned: ISOPAR H (manufactured by Esso Chemical Limited); isododecane (manufactured by Bayer corporation); isohexadecane (manufactured by Uniqema corporation); IP SOLVENT 1620MU, IP SOLVENT 2028MU, IP SOLVENT 2835 (all of which are manufactured by Dakko Kogyo Co., Ltd.). As a commercially available product of decamethylcyclopentasiloxane, there can be mentioned: TFS405(Momentive Performance Materials Japan llc.); SH245, DC345 (manufactured by Dow Corning Toray co., ltd.); KF-995 (manufactured by shin-Etsu chemical industries, Ltd.), and the like. Commercially available methylpolytrimethylsiloxane may be mentioned, for example, SILICONE TMF-1.5 (manufactured by shin-Etsu chemical Co., Ltd.). As a commercially available product of decamethyltetrasiloxane, KF-96L-1.5CS (manufactured by shin-Etsu chemical industries, Ltd.) and the like are exemplified. Commercially available ethyl trisiloxane includes SILSOFTETS (Momentive Performance Materials Japan LLC.), and the like. As a commercially available product of volatile methylpolysiloxane, KF-96L-2CS (manufactured by shin-Etsu chemical industries, Ltd.) or the like can be mentioned.
Examples of the nonvolatile oil agent include: nonvolatile hydrocarbon oils such as light liquid paraffin, heavy liquid isoparaffin, and squalane; nonvolatile silicone oils such as nonvolatile dimethylpolysiloxane and nonvolatile methylphenylpolysiloxane; nonvolatile fatty acid ester oils such as cetyl 2-ethylhexanoate, isononyl isononanoate, isotridecyl isononanoate, isopropyl myristate, isopropyl palmitate, 2-ethylhexyl stearate, and stearyl stearate; alkyl (C12-15) benzoate and the like. As the nonvolatile fatty acid ester oil, fatty acid triglycerides such as glycerol tri (caprylic/capric acid) and glycerol tri (2-ethylhexanoate); esters of neopentyl glycol with fatty acids such as neopentyl glycol dicaprate and neopentyl glycol diethyl hexanoate; polyol fatty acid ester oils, and the like.
Examples of commercially available liquid paraffin include PARLEAM 4 (manufactured by japan oil corporation). As a commercially available product of the nonvolatile dimethylpolysiloxane, KF-96A-10CS (manufactured by shin-Etsu chemical industries, Ltd.) or the like can be mentioned. Examples of commercially available isopropyl palmitate include EXCEPARL IPP (manufactured by Kao corporation). As a commercially available product of alkyl benzoate (C12-15), FINSOLV TN (Innospec Active Chemicals) and the like can be mentioned. As a commercially available product of neopentyl glycol dicaprate, Estemol N-01 (manufactured by Nisshin OilliO Group Co., Ltd.) and the like can be cited.
The content of the other liquid oil agent in the water-in-oil type emulsion cosmetic for sunscreen of the present invention is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 20% by mass or more, and particularly preferably 30% by mass or more, and in the water-in-oil type emulsion cosmetic for sunscreen of the present invention, it is preferably 80% by mass or less, more preferably 70% by mass or less, further preferably 65% by mass or less, and particularly preferably 60% by mass or less. In a specific range, in the water-in-oil type emulsion cosmetic for sunscreen of the present invention, it is preferably 5% by mass or more and 80% by mass or less, more preferably 10% by mass or more and 70% by mass or less, still more preferably 20% by mass or more and 65% by mass or less, and particularly preferably 30% by mass or more and 60% by mass or less.
From the viewpoint of abrasion resistance, ease of production, and the like, the content mass ratio of the alkyl-modified silicone wax having a melting point of 60 ℃ or higher as the component (a) to the total of the nonvolatile oil components contained in the cosmetic (in addition to the organic ultraviolet absorber that is liquid at 25 ℃ under 1 atmosphere, in the case where the nonvolatile oil agent is used as the "other liquid oil agent", the total of the organic ultraviolet absorber that is liquid at 25 ℃ under 1 atmosphere and the nonvolatile oil agent) is preferably 0.001 or more, more preferably 0.005 or more, further preferably 0.01 or more, and particularly preferably 0.02 or more, and from the viewpoint of abrasion resistance, preferably 0.4 or less, more preferably 0.2 or less, further preferably 0.1 or less, and particularly preferably 0.05 or less. The specific range is preferably 0.001 to 0.4, more preferably 0.005 to 0.2, still more preferably 0.01 to 0.1, and particularly preferably 0.02 to 0.05.
The surfactant may be a known surfactant such as an anionic surfactant, a cationic surfactant, a nonionic surfactant, or an amphoteric surfactant, and in order to stably produce a water-in-oil type emulsion cosmetic, a nonionic surfactant having an HLB of 8 or less is preferably used, and a nonionic surfactant having an HLB of 3 to 6 (particularly, HLB3 to 5) is more preferably used. Herein, HLB is an index indicating a hydrophilic-lipophilic Balance (Hydrophile-Lipophile Balance), and is defined by the following formula from the field, temple, and the like.
HLB (Σ inorganic value/Σ organic value) × 10
The nonionic surfactant having HLB of 8 or less is preferably a polyether-modified silicone for stable production of a water-in-oil emulsion cosmetic. The polysiloxane chain of the polyether-modified silicone may be either linear or branched.
Examples of the polyether-modified silicone include: polyoxyethylene-methylpolysiloxane copolymers, poly (oxyethylene-oxypropylene) methylpolysiloxane copolymers, alkyl chain branched polyoxyethylene methylpolysiloxane copolymers, alkyl chain-polysiloxane branched polyoxyethylene methylpolysiloxane copolymers, and the like. Among these, from the viewpoint of emulsion stability, a polyoxyethylene-methylpolysiloxane copolymer is preferable.
Further, commercially available polyoxyethylene-methylpolysiloxane copolymers include: KF-6015(HLB4.5), KF-6017(HLB4.5) (manufactured by shin-Etsu chemical industries, Ltd.); SH3775M (HLB5, manufactured by Dow Corning Toray co., ltd.) and the like. As a commercially available poly (oxyethylene-oxypropylene) methylpolysiloxane copolymer, KF-6012(HLB7, manufactured by shin-Etsu chemical industries, Ltd.) and the like can be cited. Examples of commercially available products of the alkyl chain branched polyoxyethylene methylpolysiloxane copolymer include KF-6028(HLB4.0, manufactured by shin-Etsu chemical Co., Ltd.). Examples of commercially available products of the alkyl chain-polysiloxane branched polyoxyethylene methylpolysiloxane copolymer include KF-6038(HLB3.0, manufactured by shin-Etsu chemical Co., Ltd.).
The content of such a surfactant in the water-in-oil type emulsion cosmetic for sunscreen of the present invention is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, further preferably 0.3% by mass or more, and particularly preferably 0.5% by mass or more, and in the water-in-oil type emulsion cosmetic for sunscreen of the present invention, it is preferably 10% by mass or less, more preferably 5% by mass or less, further preferably 3% by mass or less, and particularly preferably 1% by mass or less. In a specific range, in the water-in-oil type emulsion cosmetic for sunscreen of the present invention, it 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, still 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.
The formulation of the water-in-oil type emulsion cosmetic for sunscreen of the present invention includes: the liquid, emulsion, cream, paste, gel or other non-solid state, preferably liquid, emulsion, cream.
The viscosity of the water-in-oil emulsion cosmetic for sunscreen of the present invention at 25 ℃ is preferably 50mPa · s or more, more preferably 100mPa · s or more, further preferably 300mPa · s or more, and particularly preferably 500mPa · s or more, from the viewpoint of ease of application, and is preferably 30000mPa · s or less, more preferably 10000 mPa · s or less, further preferably 5000mPa · s or less, and particularly preferably 3000mPa · s or less, from the viewpoint of ease of application. The water-in-oil type emulsion cosmetic for sunscreen of the present invention has excellent rub resistance after application even in such a viscosity range that it is easy to apply.
Further, the above viscosity at 25 ℃ can be measured by a Brookfield viscometer (type B viscometer).
The water-in-oil type emulsion cosmetic for sunscreen of the present invention can be applied to the skin (preferably skin other than scalp, more preferably face, body, hands and feet) for use as sunscreen. The method of use is not particularly limited, and the coating is preferably carried out by hand or using an applicator.
The water-in-oil type emulsion cosmetic for sunscreen of the present invention can be manufactured according to the conventional practice. For example, an oily component (water-insoluble component) such as the component (a) or the component (B) is heated, stirred and mixed, and a water-soluble component such as the component (C) is separately heated, stirred and mixed. The obtained oily component mixture and water-soluble component mixture are mixed, sufficiently stirred by a homogenizer, and then cooled, whereby a water-in-oil type emulsion cosmetic for sunscreen can be produced.
In the above embodiment, the present invention further discloses the following cosmetics and the like.
<1> a water-in-oil type emulsion cosmetic for sunscreen comprising the following components (A), (B) and (C).
(A) Alkyl-modified silicone wax having a melting point of 60 ℃ or higher
(B) Hydrophobization treatment ultraviolet scattering agent
(C) Water (W)
<2> the water-in-oil type emulsion cosmetic for sunscreen according to <1>, wherein the melting point of the alkyl-modified silicone wax of the component (A) is preferably 61 ℃ or higher, more preferably 62 ℃ or higher, and further preferably 120 ℃ or lower, more preferably 90 ℃ or lower, still more preferably 80 ℃ or lower, and particularly preferably 72 ℃ or lower.
<3> the water-in-oil type emulsion cosmetic for sun protection according to <1> or <2>, wherein the alkyl-modified silicone wax of component (A) is preferably an oil-soluble alkyl-modified silicone wax, more preferably 1 or 2 or more selected from the group consisting of an alkyl polymethylsiloxane wax, an alkyl polydimethylsiloxane wax and a silsesquioxane resin wax, still more preferably 1 or 2 or more selected from the group consisting of an alkyl polymethylsiloxane wax and a silsesquioxane resin wax, still more preferably a silsesquioxane resin wax, and particularly preferably an alkyl (C30-45) dimethylsilylpolypropylsilsesquioxane.
<4> the water-in-oil emulsion cosmetic for sunscreen according to any one of <1> to <3>, wherein the content of the component (A) in the water-in-oil emulsion cosmetic for sunscreen is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, further preferably 0.15% by mass or more, further preferably 0.4% by mass or more, and particularly preferably 0.8% by mass or more, and in the water-in-oil emulsion cosmetic for sunscreen, is preferably 16% by mass or less, more preferably 12% by mass or less, further preferably 8% by mass or less, and particularly preferably 4% by mass or less.
<5> the water-in-oil type emulsion cosmetic for sunscreen according to any one of <1> to <3>, wherein the content of the component (A) in the water-in-oil type emulsion cosmetic for sunscreen 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, further preferably 0.15% by mass or more and 8% by mass or less, further preferably 0.4% by mass or more and 8% by mass or less, particularly preferably 0.8% by mass or more and 4% by mass or less.
<6> the water-in-oil type emulsion cosmetic preparation for sun-screening according to any one of <1> to <5>, wherein the component (B) is preferably a hydrophobized particulate metal oxide, more preferably a hydrophobized particulate metal oxide obtained by hydrophobizing 1 or 2 or more particulate metal oxides selected from the group consisting of zinc oxide, titanium oxide, cerium oxide, iron oxide and chromium oxide, still more preferably a hydrophobized particulate metal oxide obtained by hydrophobizing 1 or 2 or more particulate metal oxides selected from the group consisting of zinc oxide, titanium oxide and cerium oxide, and particularly preferably a hydrophobized particulate metal oxide obtained by hydrophobizing 1 or 2 or more particulate metal oxides selected from the group consisting of zinc oxide and titanium oxide.
<7> the water-in-oil type emulsion cosmetic for sun protection according to any one of <1> to <6>, wherein the hydrophobizing treatment of the component (B) is preferably a hydrophobizing treatment selected from the group consisting of a fluoride treatment, a silicone resin treatment, a side chain treatment, a silane coupling agent treatment, a titanium coupling agent treatment, an oil treatment, an 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, more preferably a hydrophobizing treatment selected from the group consisting of a silicone treatment, a silicone resin treatment, a silane compound treatment, a silazane compound treatment and a metal soap treatment, and still more preferably a hydrophobizing treatment selected from the group consisting of a silicone treatment and a silane compound treatment.
<8> the water-in-oil type emulsion cosmetic for sunscreen according to any one of <1> to <7>, wherein the content of the component (B) in the 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, and particularly preferably 10% by mass or more, and in the water-in-oil type emulsion cosmetic for sunscreen, the content is preferably 35% by mass or less, more preferably 30% by mass or less, further preferably 25% by mass or less, and particularly preferably 20% by mass or less.
<9> the water-in-oil type emulsion cosmetic for sunscreen according to any one of <1> to <7>, wherein 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, further preferably 7.5% by mass or more and 25% by mass or less, and particularly preferably 10% by mass or more and 20% by mass or less.
<10> the water-in-oil type emulsion cosmetic for sun protection according to any one of <1> to <9>, wherein 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, further preferably 0.025 or more, further preferably 0.05 or more, particularly preferably 0.075 or more, further preferably 1.67 or less, more preferably 1.1 or less, further preferably 0.7 or less, particularly preferably 0.3 or less.
<11> the water-in-oil type emulsion cosmetic for sun protection according to any one of <1> to <9>, wherein the content 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, further preferably 0.025 or more and 0.7 or less, further preferably 0.05 or more and 0.3 or less, and particularly preferably 0.075 or more and 0.3 or less.
<12> the water-in-oil type emulsion cosmetic for sunscreen according to any one of <1> to <11>, wherein 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, and particularly preferably 10% by mass or more, and in the water-in-oil type emulsion cosmetic for sunscreen, 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.
<13> the water-in-oil type emulsion cosmetic for sunscreen according to any one of <1> to <11>, wherein the content of the component (C) in the water-in-oil type emulsion cosmetic for sunscreen 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, further preferably 5% by mass or more and 30% by mass or less, and particularly preferably 10% by mass or more and 20% by mass or less.
<14> the water-in-oil type emulsion cosmetic for sun protection according to any one of <1> to <13>, which further comprises (D) an ultraviolet absorber.
<15> the water-in-oil type emulsion cosmetic for sun protection as described in <14>, wherein the component (D) is a combination of an organic ultraviolet absorber which is solid at 25 ℃ under 1 atm and an organic ultraviolet absorber which is liquid at 25 ℃ under 1 atm.
<16> the water-in-oil type emulsion cosmetic for sunscreen according to <14> or <15>, wherein the component (D) is a combination of 1 or more than 1 atmospheric pressure organic ultraviolet absorbers which are solid at 25 ℃ and selected from 1 or more than 2 of diethylaminohydroxybenzoyl hexyl benzoate, 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, and 1 atmospheric pressure organic ultraviolet absorbers which are liquid at 25 ℃ and selected from isopropyl p-methoxycinnamate, 2-ethylhexyl p-methoxycinnamate and 2-ethoxyethyl p-methoxycinnamate.
<17> the water-in-oil type emulsion cosmetic for sunscreen according to any one of <14> to <16>, wherein the content of the component (D) in the water-in-oil type emulsion cosmetic for sunscreen is preferably 1% by mass or more, more preferably 3% by mass or more, further preferably 6% by mass or more, and particularly preferably 9% by mass or more, and the content of the component (D) in the water-in-oil type emulsion cosmetic for sunscreen is preferably 30% by mass or less, more preferably 25% by mass or less, further preferably 20% by mass or less, and particularly preferably 15% by mass or less.
<18> the water-in-oil type emulsion cosmetic for sunscreen according to any one of <14> to <16>, wherein the content of the component (D) in the water-in-oil type emulsion cosmetic for sunscreen 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, further preferably 6% by mass or more and 20% by mass or less, and particularly preferably 9% by mass or more and 15% by mass or less.
<19> the water-in-oil emulsion cosmetic for sunscreen according to any one of <14> to <18>, wherein the total content of the component (B) and the component (D) in the water-in-oil emulsion cosmetic for sunscreen is preferably 12% by mass or more and 40% by mass or less, more preferably 15% by mass or more and 36% by mass or less, still more preferably 18% by mass or more and 32% by mass or less, and particularly preferably 21% by mass or more and 28% by mass or less.
<20> the water-in-oil emulsion cosmetic for sunscreen according to any one of <14> to <19>, wherein 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, still more preferably 0.04 or more and 0.2 or less, and particularly preferably 0.06 or more and 0.16 or less.
<21> the water-in-oil type emulsion cosmetic for sun protection according to any one of <14> to <20>, wherein the content 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, further preferably 0.5 or more and 2.3 or less, and particularly preferably 1 or more and 2 or less.
<22> the water-in-oil type emulsion cosmetic for sun protection according to any one of <1> to <21>, which further comprises 1 or 2 or more selected from the group consisting of a liquid oil agent other than an organic ultraviolet absorber which is liquid at 25 ℃ under 1 atmosphere, a surfactant, a powder other than component (B), a wax other than component (A), a lower alcohol, a preservative, a perfume, a pH adjuster, a humectant and a coating film forming agent.
[ examples ]
The present invention will be described in further detail below with reference to examples, but the present invention is not limited to the scope of the examples. In the present example, various measurements and evaluations were performed by the following methods.
Evaluation method
(1) Abrasion resistance
Mixing the above cosmetics to give a mixture of 0.93mg/cm2After being applied uniformly to HelioPlates HD6 (manufactured by Labsphere), the SPF value was measured using an SPF (Sun protection factors) analyzer (UV-2000S, manufactured by Labsphere). Thereafter, the molten steel was placed at a height of 20gf/cm2The cotton of the weight of (a), is wiped in one direction at a speed of about 25 mm/s. After standing at room temperature for 5min, the SPF of the wiped area was measured again, and the SPF was calculated from the ratio of the SPF before and after wiping [ { (SPF after rubbing)/(SPF before rubbing) } × 100 { (SPF after rubbing) } { (SPF after rubbing)/(SPF before rubbing) } { (SPF after rubbing) } x 100]The abrasion resistance was evaluated. It can be said that the higher the value, the higher the friction resistance.
(2) Feeling of use
The non-sticky feeling after coating was evaluated by 10 professional functional inspectors. The evaluation criteria are as follows.
(evaluation criteria for feeling of use)
A: there were 10 functional inspectors who responded no stickiness.
B: there were 7-9 functional inspectors who responded without stickiness.
C: there were 4-6 functional inspectors who responded without stickiness.
D: there were 1-3 functional inspectors who responded without stickiness.
E: no functional inspector responded no stickiness.
(3)SPF
Mixing the above cosmetics to give a mixture of 0.93mg/cm2In a uniform mannerThe resulting solution was applied to Helioplates HD6 (manufactured by Labsphere) and an SPF value was measured using an SPF analyzer (UV-2000S, manufactured by Labsphere).
Examples 1 to 8 and comparative examples 1 to 5
Water-in-oil emulsion cosmetics of examples 1 to 8 and comparative examples 1 to 5 were produced by a conventional method, and were evaluated for rub resistance and feeling of use. The results are shown in tables 1 to 2.
[ Table 1]
In the table, the parenthesized values indicate the content of the active ingredient in the cosmetic.
[ Table 2]
Comparative examples 6 to 7
The oil-in-water type emulsion cosmetics of comparative examples 6 to 7 were produced by a conventional method, and the SPF, rub resistance, and feeling of use were evaluated. The results are shown in Table 3.
[ Table 3]
The symbols in the table represent the following meanings.
*1: SW-8005C30 Resin Wax (melting point: 63-71 ℃, manufactured by Dow Corning Toray Co., Ltd.)
*2: AMS-C30 Cosmetic Wax (melting point: 73-77 ℃, manufactured by Dow Corning Toray Co., Ltd.); 55 mass% of the active ingredient
*3: 670Fluid (manufactured by Dow Corning Toray co., ltd.); 50% by mass of the active ingredient
*4: SILICONE KSG-16 (manufactured by shin-Etsu chemical industries, Inc.); 25% by mass of the active ingredient
*5: MZX-304OTS (average particle diameter: 0.035 μm, manufactured by TAYCA CORPORATION)
*6: MZ-504R3M (average particle size: 0.025 μm, manufactured by TAYCA CORPORATION)
*7: uvinul MC-80 (manufactured by BASF corporation)
*8: uvinul A PLUS GRANULAR (manufactured by BASF corporation)
*9: TINOSORB S (BASF corporation)
*10: KF-96A-10CS (manufactured by shin-Etsu chemical industries Co., Ltd.)
*11: EXCEPARL IPP (manufactured by Huawang company)
*12: PARLEAM 4 (manufactured by Nichiya oil Co., Ltd.)
*13: estemol N-01 (manufactured by Nisshin OilliO Group Co., Ltd.)
*14: FINSOLV TN (Innospec Active Chemicals Co., Ltd.)
*15: DOWFSIL SH3775M FLUID (manufactured by Dow Corning Corp.)
*16: TSF405A (Momentive Performance Materials Japan LLC., Ltd.)
*17: SIMULGEL EG (manufactured by SEPPIC S.A. Inc.)
*18: RHEODOL TW-S120V (manufactured by Huawang Co., Ltd.)
Next, formulation examples of the water-in-oil type emulsion cosmetic of the present invention will be shown. The obtained water-in-oil emulsion cosmetic is less sticky after application, has excellent rub resistance, and is excellent as a sunscreen cosmetic.
[ Table 4]
The symbols in the table represent the following meanings.
*1: SW-8005C30 Resin Wax (melting point: 63-71 ℃, manufactured by Dow Corning Toray Co., Ltd.)
*5: MZX-304OTS (average particle diameter: 0.035 μm, manufactured by TAYCA CORPORATION)
*7: uvinul MC-80 (manufactured by BASF corporation)
*8: uvinul A PLUS GRANULAR (manufactured by BASF corporation)
*9: TINOSORB S (BASF corporation)
*10: KF-96A-10CS (manufactured by shin-Etsu chemical industries Co., Ltd.)
*11: EXCEPARL IPP (manufactured by Huawang company)
*12: PARLEAM 4 (manufactured by Nichiya oil Co., Ltd.)
*13: estemol N-01 (manufactured by Nisshin OilliO Group Co., Ltd.)
*14: FINSOLV TN (Innospec Active Chemicals Co., Ltd.)
*15: DOWFSIL SH3775M FLUID (manufactured by Dow Corning Corp.)
*16: TSF405A (manufactured by Momentive Performance Materials Japan LLC)
*19: MT-100TV (average particle size: 0.015. mu.m, manufactured by TAYCA CORPORATION)
*20: SA-Talc JA-68R (manufactured by Sanhaohai chemical Co., Ltd.)
*21: tospearl 145 (produced by Momentive Performance Materials Japan LLC)
*22: KF-96A-6CS (manufactured by shin-Etsu chemical industries Co., Ltd.)
*23: KF-6015 (manufactured by shin-Etsu chemical industries, Ltd.).
Claims (8)
1. A water-in-oil type emulsion cosmetic for sunscreen, wherein,
comprises the following components (A), (B) and (C):
(A) an alkyl-modified silicone wax having a melting point of 60 ℃ or higher;
(B) hydrophobization treatment of the ultraviolet scattering agent;
(C) and (3) water.
2. A water-in-oil type emulsion cosmetic for sunscreen according to claim 1, wherein,
the alkyl-modified silicone wax of component (a) is 1 or 2 or more selected from an alkyl methicone wax, an alkyl dimethicone wax, and a silsesquioxane resin wax.
3. The water-in-oil type emulsion cosmetic for sun protection according to claim 1 or 2,
the component (B) is a hydrophobized particulate metal oxide.
4. The water-in-oil type emulsion cosmetic for sunscreen according to any one of claims 1 to 3, wherein,
the component (B) is a substance obtained by hydrophobizing 1 or 2 or more types of fine-particle metal oxides selected from zinc oxide, titanium oxide, and cerium oxide.
5. The water-in-oil type emulsion cosmetic for sunscreen according to any one of claims 1 to 4, wherein,
the content of the component (B) in the cosmetic is 6 to 30% by mass.
6. The water-in-oil type emulsion cosmetic for sunscreen according to any one of claims 1 to 5, wherein,
the content mass ratio (A)/(B) of the component (A) to the component (B) is 0.005 to 1.67.
7. The water-in-oil type emulsion cosmetic for sunscreen according to any one of claims 1 to 6, wherein,
further contains (D) an ultraviolet absorber.
8. A water-in-oil type emulsion cosmetic for sunscreen according to claim 7, wherein,
the content of the component (D) in the cosmetic is 6 to 20 mass%.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2018236643 | 2018-12-18 | ||
| JP2018-236643 | 2018-12-18 | ||
| PCT/JP2019/049525 WO2020130011A1 (en) | 2018-12-18 | 2019-12-18 | Water-in-oil emulsion cosmetic composition for sunscreen |
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| Publication Number | Publication Date |
|---|---|
| CN113272021A true CN113272021A (en) | 2021-08-17 |
| CN113272021B CN113272021B (en) | 2023-07-28 |
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| CN201980084732.4A Active CN113272021B (en) | 2018-12-18 | 2019-12-18 | Water-in-oil type emulsified cosmetic for sunscreening |
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| Country | Link |
|---|---|
| JP (1) | JP7410704B2 (en) |
| CN (1) | CN113272021B (en) |
| TW (1) | TWI820275B (en) |
| WO (1) | WO2020130011A1 (en) |
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| KR20230132388A (en) | 2022-03-08 | 2023-09-15 | 니치유 가부시키가이샤 | Cosmetic base material, cosmetics containing the same, and oil-in-wet type sunscreen cosmetics |
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Also Published As
| Publication number | Publication date |
|---|---|
| JP2020097576A (en) | 2020-06-25 |
| WO2020130011A1 (en) | 2020-06-25 |
| CN113272021B (en) | 2023-07-28 |
| JP7410704B2 (en) | 2024-01-10 |
| TWI820275B (en) | 2023-11-01 |
| TW202033175A (en) | 2020-09-16 |
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