Skin topical products

Abstract

The present invention provides a skin external preparation which is not easy to drip when applied, has a less oily or oppressive feeling, and has an excellent ultraviolet protection effect by easily and evenly distributing an oil-soluble ultraviolet absorber on the skin surface after application. The skin external preparation contains the following components (A), (B) and (C), (A) an oil-soluble ultraviolet absorber; (B) an oil gelling agent of 0.5% by mass or more and 20% by mass or less; and (C) a non-aqueous volatile component of 50% by mass or more.

Description

Technical Field

[0001] The present invention relates to a skin external preparation. Background Art

[0002] In order to obtain the ultraviolet protection effect, many skin external preparations containing ultraviolet absorbers have been developed. As such skin external preparations, for example, specific skin cosmetics containing ultraviolet absorbers, polymers having as structural units a hydrophilic segment having N-acylalkyleneimine as a repeating unit and an organopolysiloxane segment, an alcohol having 1 to 4 carbon atoms, a powder having a number average particle size of 1 to 10 μm, a powder having a number average particle size of more than 10 μm and not more than 25 μm, and a propellant are known, and the ultraviolet protection effect is excellent in durability (Patent Document 1).

[0003] (Patent Document 1) Japanese Patent Application Publication No. 2016-6029 Summary of the invention

[0004] The present invention provides a skin external preparation comprising the following components (A), (B) and (C),

[0005] (A) Oil-soluble UV absorber;

[0006] (B) 0.5 mass % or more and 20 mass % or less of an oil gelling agent;

[0007] (C) Non-aqueous volatile components: 50% by mass or more. BRIEF DESCRIPTION OF THE DRAWINGS

[0008] Figure 1 These are images of the coating films of the stock solutions of Example 7 and Comparative Example 1 photographed by VISIA-CR (manufactured by Canfield Scientific). DETAILED DESCRIPTION

[0009] The present inventors have conducted studies and found that after the skin cosmetic of Patent Document 1 is applied to the skin, the cosmetics on the skin surface fall into the wrinkles and textures of the skin, and the distribution of the ultraviolet absorber tends to become uneven, resulting in insufficient ultraviolet protection effect.

[0010] In addition, skin external preparations using an oil-soluble ultraviolet absorber are required to have less oily feeling (greasy feeling) or less oppressive feeling, and are also required to be less likely to drip on the skin surface.

[0011] The present invention provides a skin external preparation which is less likely to drip when applied, has a less oily or oppressive feel, and can easily and evenly distribute an oil-soluble ultraviolet absorber on the skin surface after application, and has an excellent ultraviolet protection effect.

[0012] The present inventors have discovered that a skin external preparation that combines a specific amount of an oil gelling agent with an oil-soluble ultraviolet absorber and a high content of a non-aqueous volatile component does not easily drip when applied, has a less oily or oppressive feel, and after application to the skin, the oil-soluble ultraviolet absorber is easily evenly distributed on the skin surface and has an excellent ultraviolet protection effect, thereby completing the present invention.

[0013] The skin external preparation of the present invention is less likely to drip when applied, has a less oily or oppressive feel, and after application to the skin, the oil-soluble ultraviolet absorber is easily evenly distributed on the skin surface, thereby having an excellent ultraviolet protection effect.

[0014] <Ingredients (A)>

[0015] The external preparation for skin of the present invention contains (A) an oil-soluble ultraviolet absorber.

[0016] In the present specification, the oil-soluble ultraviolet absorber refers to an ultraviolet absorber having a solubility in water of less than 0.01% by mass.

[0017] Examples of the oil-soluble ultraviolet absorber include benzoic acid oil-soluble ultraviolet absorbers, anthranilic acid oil-soluble ultraviolet absorbers, salicylic acid oil-soluble ultraviolet absorbers, cinnamic acid oil-soluble ultraviolet absorbers, benzoylmethane oil-soluble ultraviolet absorbers, triazine oil-soluble ultraviolet absorbers, benzophenone oil-soluble ultraviolet absorbers, hydantoin oil-soluble ultraviolet absorbers, etc. Among these, one or more selected from benzoic acid oil-soluble ultraviolet absorbers, cinnamic acid oil-soluble ultraviolet absorbers and triazine oil-soluble ultraviolet absorbers are preferred.

[0018] Examples of the benzoic acid-based oil-soluble ultraviolet absorber include p-aminobenzoic acid, glyceryl p-aminobenzoic acid, ethyl dihydroxypropyl p-aminobenzoic acid, octyl dimethyl p-aminobenzoic acid, amyl p-dimethylaminobenzoate, and diethylaminohydroxybenzoyl hexyl benzoate.

[0019] Examples of the anthranilic acid-based oil-soluble ultraviolet absorber include methyl anthranilate and the like.

[0020] Examples of the salicylic acid-based oil-soluble ultraviolet absorber include homomenium salicylate, 2-ethylhexyl salicylate, and triethanolamine salicylate.

[0021] Examples of the cinnamic acid-based oil-soluble ultraviolet absorber include 2-ethylhexyl p-methoxycinnamate, di-p-methoxycinnamic acid mono-2-ethylhexanoin, methyl 2,5-diisopropylcinnamate, methyl trimethoxycinnamate bis(trimethylsiloxy)silylisoamyl ester, isopropyl p-methoxycinnamate, a mixture of isopropyl p-methoxycinnamate and diisopropyl cinnamate, 2-ethoxyethyl p-methoxycinnamate, and diethanolamine p-methoxycinnamate.

[0022] Examples of the benzoylmethane oil-soluble ultraviolet absorber include 4-isopropyldibenzoylmethane and 4-tert-butyl-4′-methoxydibenzoylmethane.

[0023] Examples of the triazine-based oil-soluble ultraviolet absorber include 2,4,6-tris[4-(2-ethylhexyloxycarbonyl)anilino]-1,3,5-triazine and 2,4-bis-[{4-(2-ethylhexyloxy)-2-hydroxy}-phenyl]-6-(4-methoxyphenyl)-1,3,5-triazine.

[0024] Examples of the benzophenone-based oil-soluble ultraviolet absorber include 2,4-dihydroxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'4,4'-tetrahydroxybenzophenone, 4-(2-β-pyranosylsilyloxy)propoxy-2-hydroxybenzophenone, and 2-hydroxy-4-n-octyloxybenzophenone.

[0025] Examples of the hydantoin-based oil-soluble ultraviolet absorber include 2-ethylhexyl dimethoxybenzylidene dioxoimidazolidine propionate.

[0026] Examples of other oil-soluble ultraviolet absorbers include octocrylene, cinoxate, phenylbenzimidazole sulfonic acid, 1-(3,4-dimethoxyphenyl)-4,4-dimethyl-1,3-pentanedione, 3-(4-methylbenzylidene)camphor, and methylenebisbenzotriazolyltetramethylbutylphenol.

[0027] In addition, the oil-soluble ultraviolet absorber can be roughly divided into an oil-soluble ultraviolet absorber that is solid at 25°C under 1 atmosphere and an oil-soluble ultraviolet absorber that is liquid at 25°C under 1 atmosphere. In the present invention, it is preferred to use at least an oil-soluble ultraviolet absorber that is liquid at 25°C under 1 atmosphere as the oil-soluble ultraviolet absorber. In this case, the oil-soluble ultraviolet absorber that is liquid at 25°C under 1 atmosphere and the oil-soluble ultraviolet absorber that is solid at 25°C under 1 atmosphere can also be used in combination.

[0028] In addition, for example, the above-mentioned diethylaminohydroxybenzoyl hexyl benzoate, 2,4,6-tris[4-(2-ethylhexyloxycarbonyl)anilino]-1,3,5-triazine, 2,4-bis-[{4-(2-ethylhexyloxy)-2-hydroxy}-phenyl]-6-(4-methoxyphenyl)-1,3,5-triazine, etc. are oil-soluble ultraviolet absorbers that are solid at 25°C under one atmospheric pressure. In addition, the above-mentioned 2-ethylhexyl p-methoxycinnamate, isopropyl p-methoxycinnamate, 2-ethoxyethyl p-methoxycinnamate, etc. are oil-soluble ultraviolet absorbers that are liquid at 25°C under one atmospheric pressure.

[0029] The oil-soluble ultraviolet absorber may be used alone or in combination of two or more.

[0030] The content of the oil-soluble ultraviolet absorber is preferably 5% by mass or more, more preferably 7.5% by mass or more, further more preferably 10% by mass or more, and particularly preferably 12.5% ​​by mass or more in terms of ultraviolet protection effect and coating uniformity in the skin external preparation of the present invention; in addition, from the perspective of coating uniformity and lack of strong oily feeling and pressure, it is preferably 30% by mass or less, more preferably 25% by mass or less, further preferably 20% by mass or less, and particularly preferably 17.5% by mass or less in the skin external preparation of the present invention. As a specific range, it is preferably 5% by mass or more and 30% by mass or less, more preferably 7.5% by mass or more and 25% by mass or less, further preferably 10% by mass or more and 20% by mass or less, and particularly preferably 12.5% ​​by mass or more and 17.5% by mass or less in the skin external preparation of the present invention. When the content of the oil-soluble ultraviolet absorber is 7.5% by mass or more, coating uniformity and ultraviolet protection effect can be improved particularly, and when the content of the oil-soluble ultraviolet absorber is 25% by mass or less, coating uniformity can be improved particularly.

[0031] When the skin external preparation of the present invention is an aerosol type skin external preparation, the content of the oil-soluble ultraviolet absorber refers to the ratio when the stock solution is 100% by mass. The same applies to the other components below.

[0032] <Component (B)>

[0033] The external preparation for skin of the present invention contains (B) an oil gelling agent.

[0034] Examples of the oil gelling agent include one or more selected from the group consisting of sugar fatty acid ester oil gelling agents, glycerol fatty acid ester oil gelling agents, amino acid derivative oil gelling agents, and benzylidene sorbitol oil gelling agents. Among these, sugar fatty acid ester oil gelling agents, glycerol fatty acid ester oil gelling agents, and amino acid derivative oil gelling agents are preferred from the viewpoints of coating uniformity, UV protection effect, difficulty in dripping during coating, and lack of strong oily or oppressive feeling, and sugar fatty acid ester oil gelling agents are more preferred.

[0035] The fatty acid residue in the sugar fatty acid ester oil gelling agent or glycerol fatty acid ester oil gelling agent is preferably a linear or branched saturated fatty acid residue. The fatty acid residue preferably has 8 to 24 carbon atoms, more preferably 12 to 22 carbon atoms, and particularly preferably 14 to 20 carbon atoms.

[0036] Examples of sugar fatty acid ester oil gelling agents include dextrin myristate, dextrin palmitate, dextrin stearate, dextrin (palmitic acid / 2-ethylhexanoate), dextrin (palmitic acid / hexyldecanoate), etc.; sucrose fatty acid ester oil gelling agents such as sucrose palmitate and sucrose stearate; inulin fatty acid ester oil gelling agents such as inulin stearate; fructooligosaccharide fatty acid ester oil gelling agents such as fructooligosaccharide stearate and fructooligosaccharide 2-ethylhexanoate, etc.; and the like.

[0037] Examples of the glyceryl fatty acid ester oil gelling agent include (behenic acid / eicosanedioic acid) glyceryl, tri(behenic acid / isostearic acid / eicosanedioic acid) glyceryl, and polyglyceryl-10 (behenic acid / eicosanedioic acid) ester.

[0038] Examples of the amino acid derivative oil gelling agent include dibutyl lauroyl glutamine and dibutyl ethylhexanoyl glutamine.

[0039] Examples of the benzylidene sorbitol-based oil gelling agent include monobenzylidene sorbitol and dibenzylidene sorbitol.

[0040] Among the above-mentioned oil gelling agents, dextrin fatty acid ester oil gelling agents are preferred from the viewpoints of coating uniformity, UV protection effect, less dripping during coating, and no strong oily or oppressive feeling, and dextrin palmitate is particularly preferred.

[0041] The oil gelling agent can use a commercial product, or a synthetic product synthesized according to a common method. As a commercial product of dextrin myristate, Rheopearl MKL2 (manufactured by Chiba Flour Milling Co., Ltd.) can be cited. As a commercial product of dextrin palmitate, Rheopearl KL2 and Rheopearl TL2 (manufactured by Chiba Flour Milling Co., Ltd.) can be cited. As a commercial product of dextrin (palmitic acid / 2-ethylhexanoic acid) ester, Rheopearl TT2 (manufactured by Chiba Flour Milling Co., Ltd.) can be cited. As a commercial product of dextrin (palmitic acid / hexyldecanoic acid) ester, Rheopearl WX (manufactured by Chiba Flour Milling Co., Ltd.) can be cited. As a commercial product of inulin stearate, Rheopearl ISL2 and Rheopearl ISK2 (manufactured by Chiba Flour Milling Co., Ltd.) can be cited. As a commercial product of dibutyl ethylhexanoyl glutamine, amino acid gelling agent EB-21 (manufactured by Ajinomoto Co., Ltd.) can be cited.

[0042] The oil gelling agent may be used alone or in combination of two or more.

[0043] The content of the oil gelling agent in the skin external preparation of the present invention is 0.5 mass % or more and 20 mass % or less. By setting the content of the oil gelling agent to 0.5 mass % or more, dripping is less likely to occur during application, and the application uniformity of the components remaining on the skin after application can be improved, and an excellent ultraviolet protection effect can also be obtained. In addition, by setting the content of the oil gelling agent to 20 mass % or less, the oily feeling and the pressure feeling are reduced.

[0044] The content of the oil gelling agent is preferably 1% by mass or more, more preferably 1.5% by mass or more, further preferably 2% by mass or more, and particularly preferably 2.5% by mass or more, in terms of coating uniformity, UV protection effect, and difficulty in dripping during coating, in the skin external preparation of the present invention; in addition, from the perspective of no strong oily feeling and oppressive feeling and ease of manufacture, it is preferably 15% by mass or less, more preferably 10% by mass or less, further preferably 7.5% by mass or less, and particularly preferably 5% by mass or less in the skin external preparation of the present invention. As a specific range, in the skin external preparation of the present invention, it is preferably 1% by mass or more and 15% by mass or less, more preferably 1.5% by mass or more and 10% by mass or less, further preferably 2% by mass or more and 7.5% by mass or less, and particularly preferably 2.5% by mass or more and 5% by mass or less.

[0045] In addition, the content mass ratio of component (B) to component (A) [(B) / (A)] is preferably 0.01 or more, more preferably 0.05 or more, further preferably 0.1 or more, and particularly preferably 0.15 or more from the viewpoints of coating uniformity, UV protection effect, and difficulty in dripping during coating; and is preferably 1.5 or less, more preferably 1 or less, further preferably 0.6 or less, and particularly preferably 0.3 or less from the viewpoints of coating uniformity, UV protection effect, and no strong oily feeling or pressure feeling. As a specific range, it is preferably 0.01 or more and 1.5 or less, more preferably 0.05 or more and 1 or less, further preferably 0.1 or more and 0.6 or less, and particularly preferably 0.15 or more and 0.3 or less.

[0046] <Ingredient (C)>

[0047] The external skin preparation of the present invention contains (C) a non-aqueous volatile component.

[0048] The non-aqueous volatile components refer to components other than water in the volatile components. In this specification, "volatile components" refer to components that are volatile at 25°C under 1 atmosphere, and components that are not volatile at 25°C under 1 atmosphere are referred to as "non-volatile components".

[0049] As the non-aqueous volatile component, for example, one or more selected from (C-1) volatile silicone oil, (C-2) lower alcohol and (C-3) volatile liquid oils other than volatile silicone oil can be cited. As the skin external preparation of the present invention, from the viewpoints of the feeling of use (no strong oily feeling or pressure feeling), the uniformity of application of the components remaining on the skin after application, and the sprayability when used as a spray, it is preferred to contain at least component (C-1) as component (C) and at least component (C-2) as component (C), and more preferably contain components (C-1) and (C-2). In addition, when component (C-1) is contained, the feeling of use (no strong oily feeling or pressure feeling) can be improved. In addition, when component (C-2) is contained, the feeling of use (no strong oily feeling or pressure feeling) and the sprayability when used as a spray can be improved. In particular, when component (C-2) is contained, even when a spray containing a high content of an oil gelling agent is prepared, good sprayability and quick-drying properties can be obtained.

[0050] (Component (C-1))

[0051] The volatile silicone oil may be any volatile silicone oil that is liquid at 25°C under 1 atmosphere, and examples thereof include decamethylcyclopentasiloxane, octamethylcyclotetrasiloxane, dodecamethylcyclohexasiloxane, methyltrimethicone, decamethyltetrasiloxane, octamethyltrisiloxane, ethyltrisiloxane, and volatile dimethylpolysiloxane. These may be used alone or in combination of two or more. The kinematic viscosity of the volatile dimethylpolysiloxane at 25°C is preferably 0.5 mm 2 / s or more and 2mm 2 / s or less, more preferably 0.65 mm 2 / s or more and 2mm 2 / s or less.

[0052] Commercially available products of decamethylcyclopentasiloxane include TFS405 (manufactured by Momentive Performance Materials Japan LLC), SH245, DC345 (manufactured by Dow Corning Toray Co., Ltd.), and KF-995 (manufactured by Shin-Etsu Chemical Co., Ltd.). Commercially available products of methyl trimethylsiloxane include Silicone TMF-1.5 (manufactured by Shin-Etsu Chemical Co., Ltd.). Commercially available products of decamethyltetrasiloxane include KF-96L-1.5CS (manufactured by Shin-Etsu Chemical Co., Ltd.). Commercially available products of ethyl trisiloxane include SILSOFTETS (manufactured by Momentive Performance Materials Japan LLC). Commercially available products of dimethylpolysiloxane include KF-96L-2CS (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0053] (Component (C-2))

[0054] The lower alcohol is preferably a linear or branched monohydric alcohol having 1 to 6 carbon atoms, and more preferably a linear or branched saturated monohydric alcohol having 1 to 6 carbon atoms. The lower alcohol preferably has 1 to 4 carbon atoms, and more preferably 2 to 3 carbon atoms.

[0055] As the lower alcohol, for example, ethanol, n-propanol, isopropanol, butanol, etc. can be listed, among which only one can be used alone, or two or more can be used in combination. Among these, from the viewpoint of ejection property when used as a spray, ethanol and isopropanol are preferred, and ethanol is more preferred.

[0056] (Component (C-3))

[0057] Examples of the volatile liquid oil agent other than the volatile silicone oil include volatile hydrocarbon oils.

[0058] The volatile hydrocarbon oil may be any volatile hydrocarbon oil having a flash point of 35°C or higher and 100°C or lower and being liquid at 25°C under 1 atmosphere, and examples thereof include paraffin-based volatile hydrocarbon oils such as n-decane, n-undecane, and n-dodecane; and isoparaffin-based volatile hydrocarbon oils such as isodecane, isododecane, and light isoparaffins. Among these, one type may be used alone, or two or more types may be used in combination.

[0059] The non-aqueous volatile component may be used alone or in combination of two or more.

[0060] The content of the non-aqueous volatile component in the skin external preparation of the present invention is 50% by mass or more. When the content of the non-aqueous volatile component is 50% by mass or more, dripping is less likely to occur during application.

[0061] The content of the non-aqueous volatile component is preferably 52% by mass or more, more preferably 55% by mass or more, further preferably 60% by mass or more, and particularly preferably 62% by mass or more in the skin external preparation of the present invention from the viewpoints of coating uniformity, ultraviolet protection effect, and formulation stability; in addition, from the viewpoints of ultraviolet protection effect, etc., it is preferably 90% by mass or less, more preferably 85% by mass or less, further preferably 80% by mass or less, and particularly preferably 75% by mass or less in the skin external preparation of the present invention. As a specific range, it is preferably 52% by mass or more and 90% by mass or less, more preferably 55% by mass or more and 85% by mass or less, further preferably 60% by mass or more and 80% by mass or less, and particularly preferably 62% by mass or more and 75% by mass or less in the skin external preparation of the present invention.

[0062] When a volatile silicone oil is used as component (C), the content of the volatile silicone oil is preferably 0.5% by mass or more, more preferably 1% by mass or more, further preferably 2% by mass or more, and particularly preferably 4% by mass or more, from the viewpoints of ultraviolet protection effect, coating uniformity, and feeling of use (suppression of stickiness or oiliness from non-volatile oils). In addition, from the viewpoints of clarity, compatibility with non-volatile oils, coating uniformity, ultraviolet protection effect, and formulation stability, the content of the volatile silicone oil 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 in the skin preparation of the present invention. As a specific range, in the skin preparation of the present invention, it is preferably 0.5% by mass or more and 30% by mass or less, more preferably 1% by mass or more and 25% by mass or less, further preferably 2% by mass or more and 20% by mass or less, and particularly preferably 4% by mass or more and 15% by mass or less.

[0063] When a lower alcohol is used as component (C), the content of the lower alcohol is preferably 40% by mass or more, more preferably 45% by mass or more, and further preferably 50% by mass or more in the skin external preparation of the present invention from the viewpoints of no strong oily feeling or pressure feeling, sprayability when made into a spray, etc.; in addition, from the viewpoints of ultraviolet protection effect, formulation stability, etc., it is preferably 95% by mass or less, more preferably 90% by mass or less, and further preferably 80% by mass or less in the skin external preparation of the present invention. As a specific range, it is preferably 40% by mass or more and 95% by mass or less, more preferably 45% by mass or more and 90% by mass or less, and further preferably 50% by mass or more and 80% by mass or less in the skin external preparation of the present invention.

[0064] In addition, the content mass ratio of component (A) to component (C) [(A) / (C)] is preferably 0.01 or more, more preferably 0.05 or more, further preferably 0.1 or more, and particularly preferably 0.15 or more from the viewpoints of ultraviolet protection effect and coating uniformity; in addition, it is preferably 1.5 or less, more preferably 1 or less, and further preferably 0.5 or less from the viewpoint of coating uniformity. As a specific range, it is preferably 0.01 or more and 1.5 or less, more preferably 0.05 or more and 1 or less, further preferably 0.1 or more and 0.5 or less, and particularly preferably 0.15 or more and 0.5 or less.

[0065] In addition, the total content mass ratio of components (A) and (B) to component (C) [((A) + (B)) / (C)] is preferably 0.02 or more, more preferably 0.05 or more, further preferably 0.1 or more, and particularly preferably 0.23 or more from the viewpoints of coating uniformity, no strong oily feeling or pressure, not easy to drip during coating, and ultraviolet protection effect; in addition, from the same viewpoint as above, it is preferably 3 or less, more preferably 0.8 or less, further preferably 0.6 or less, and particularly preferably 0.3 or less. As a specific range, it is preferably 0.02 or more and 3 or less, more preferably 0.05 or more and 0.8 or less, further preferably 0.1 or more and 0.6 or less, and particularly preferably 0.23 or more and 0.3 or less.

[0066] The content mass ratio of component (C-2) to component (C-1) [(C-2) / (C-1)] is preferably 0.5 or more, more preferably 1 or more, further preferably 3 or more, and particularly preferably 6 or more. From the viewpoint of ultraviolet protection effect, coating uniformity, etc., it is preferably 600 or less, more preferably 100 or less, further preferably 25 or less, and particularly preferably 9 or less. As a specific range, it is preferably 0.5 or more and 600 or less, more preferably 1 or more and 100 or less, further preferably 3 or more and 25 or less, and particularly preferably 6 or more and 9 or less.

[0067] As the skin external preparation of the present invention, in addition to components (A) to (C), it is preferred to further contain one or more selected from (D) a non-volatile liquid oil agent (but excluding component (A)) and (E) a film-forming agent, more preferably containing components (A) to (D), and particularly preferably containing components (A) to (E). In addition, when component (D) is further contained in addition to components (A) to (C), the formulation stability, coating uniformity, etc. can be improved. In addition, when component (E) is further contained in addition to components (A) to (C), the ultraviolet protection effect, coating uniformity, water resistance, friction resistance, etc. can be improved.

[0068] <Ingredient (D)>

[0069] The nonvolatile liquid oil agent may be any nonvolatile oil agent other than component (A) that is liquid at 25° C. under 1 atmosphere, and examples thereof include nonvolatile hydrocarbon oils such as liquid isoparaffin, heavy liquid isoparaffin, and squalane, and nonvolatile silicone oils such as nonvolatile dimethylpolysiloxane and nonvolatile methylphenylpolysiloxane, in addition to nonvolatile ester oils. Among these, nonvolatile ester oils are preferred from the viewpoints of compatibility, coating uniformity, ultraviolet protection effect, and the like.

[0070] Examples of the nonvolatile ester oil include nonvolatile fatty acid ester oils and nonvolatile aromatic carboxylic acid ester oils. Examples of the nonvolatile aromatic carboxylic acid ester oil include alkyl (C12-15) benzoate.

[0071] The fatty acid residue in the nonvolatile fatty acid ester oil is preferably a linear or branched saturated fatty acid residue. The number of carbon atoms in the fatty acid residue is preferably 8 to 24, more preferably 12 to 22, and particularly preferably 14 to 20 from the viewpoints of compatibility, coating uniformity, ultraviolet protection effect, etc.

[0072] As the nonvolatile fatty acid ester oil, nonvolatile monohydric alcohol fatty acid ester oil and nonvolatile polyhydric alcohol fatty acid ester oil can be cited. Among these, nonvolatile monohydric alcohol fatty acid ester oil is preferred from the viewpoints of compatibility, coating uniformity, ultraviolet protection effect, etc. In addition, nonvolatile monohydric alcohol fatty acid ester oil is a nonvolatile ester oil of fatty acid and monohydric alcohol. As the monohydric alcohol residue in the ester oil, from the viewpoints of compatibility, coating uniformity, ultraviolet protection effect, etc., it is preferably a linear or branched monohydric alcohol residue with 3 to 20 carbon atoms, more preferably a linear or branched monohydric alcohol residue with 3 to 14 carbon atoms, and particularly preferably a linear or branched monohydric alcohol residue with 3 to 8 carbon atoms.

[0073] Examples of the nonvolatile monohydric alcohol fatty acid ester oil include cetyl 2-ethylhexanoate, isononyl isononanoate, isotridecyl isononanoate, isopropyl myristate, isopropyl palmitate, 2-ethylhexyl palmitate, 2-ethylhexyl stearate, and stearyl stearate.

[0074] Examples of the nonvolatile polyol fatty acid ester oil include fatty acid triglycerides such as tri(caprylic acid / capric acid)glyceryl and tri(2-ethylhexanoic acid)glyceryl; and ester oils of fatty acids and neopentyl glycol such as neopentyl glycol dicaprate and neopentyl glycol diethylhexanoate.

[0075] As commercial products of liquid isoparaffins, PARLEAM 6 (manufactured by NOF Corporation) and the like can be cited. As commercial products of non-volatile dimethylpolysiloxanes, KF-96A-10CS (manufactured by Shin-Etsu Chemical Co., Ltd.) and the like can be cited. As commercial products of isopropyl palmitate, EXCEPARL IPP (manufactured by Kao Corporation) and the like can be cited. As commercial products of alkyl benzoate (C12-15), FINSOLV TN (manufactured by Innospec Active Chemicals) and the like can be cited. As commercial products of neopentyl glycol dicaprate, ESTEMOL N-01 (manufactured by Nisshin OilliO Group Ltd.) and the like can be cited.

[0076] In the present invention, by using a volatile silicone oil as component (C) and using the above-mentioned nonvolatile ester oil, the volatile silicone oil and the oil-soluble ultraviolet absorber are not separated but easily miscible, which is preferred from the viewpoint of achieving both excellent feeling in use and excellent coating uniformity and excellent ultraviolet protection effect.

[0077] The nonvolatile liquid oil of component (D) may be used alone or in combination of two or more.

[0078] The content of the nonvolatile liquid oil of component (D) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and further preferably 1% by mass or more in the skin external preparation of the present invention from the viewpoints of compatibility, coating uniformity, ultraviolet protection effect, storage stability, etc.; in addition, from the viewpoints of coating uniformity, ultraviolet protection effect, etc., it is preferably 35% by mass or less, more preferably 25% by mass or less, further preferably 20% by mass or less, and particularly preferably 10% by mass or less in the skin external preparation of the present invention. As a specific range, it is preferably 0.1% by mass or more and 35% by mass or less, more preferably 0.5% by mass or more and 25% by mass or less, further preferably 1% by mass or more and 20% by mass or less, and particularly preferably 1% by mass or more and 10% by mass or less in the skin external preparation of the present invention.

[0079] In addition, the content mass ratio of component (B) to the total of components (A) and (D) [(B) / ((A)+(D))] is preferably 0.01 or more, more preferably 0.05 or more, and further preferably 0.1 or more from the viewpoints of coating uniformity, ultraviolet protection effect, etc.; in addition, from the same viewpoints as above, it is preferably 1 or less, more preferably 0.5 or less, further preferably 0.25 or less, and particularly preferably 0.18 or less. As a specific range, it is preferably 0.01 or more and 1 or less, more preferably 0.05 or more and 0.5 or less, further preferably 0.1 or more and 0.25 or less, and particularly preferably 0.1 or more and 0.18 or less.

[0080] <Ingredient (E)>

[0081] Examples of the film-forming agent include silicone film-forming agents and (meth)acrylic film-forming agents, and silicone film-forming agents are preferred from the viewpoints of ultraviolet protection effect, water resistance, abrasion resistance, etc. In addition, oil-soluble film-forming agents are preferred.

[0082] In this specification, the so-called silicone film-forming agent refers to a film-forming agent having a silicone segment in the molecule, and the position of the silicone segment in the molecule is arbitrary, for example, it can be the main chain or side chain of the polymer. In addition, the silicone segment can be a chain structure or a branched structure. As the silicone segment of the branched structure, a dendritic siloxane segment, a silsesquioxane segment, and a silicone segment of a network molecular structure can be listed.

[0083] Examples of the silicone film-forming agent include poly(N-acylalkyleneimine)-modified silicones such as oxazoline-modified silicones; amino-modified silicones such as amino-terminated dimethylpolysiloxane (amodimethicone), aminoethylaminopropyl dimethylpolysiloxane, and aminopropyl dimethylpolysiloxane; fluorine-modified silicones; trimethylsiloxysilicic acid; (trimethylsiloxysilicic acid / dimethiconol) cross-linked polymers; (acrylate / trimethylsiloxane methacrylate) copolymers. (meth)acrylic polymers having a branch-type siloxane structure in the side chain such as polymethylsilsesquioxane, polypropylsilsesquioxane, etc.; (meth)acrylic-silicone graft copolymers such as (acrylate / dimethylpolysiloxane) copolymer, (acrylate / ethylhexyl acrylate / polydimethylsiloxane methacrylate) copolymer, (acrylate / stearyl acrylate / polydimethylsiloxane methacrylate) copolymer, (acrylate / behenyl acrylate / polydimethylsiloxane methacrylate) copolymer, etc. Among these, only one kind may be used alone, or two or more kinds may be used in combination.

[0084] Among these, from the viewpoints of water resistance, ease of production, etc., poly(N-acylalkyleneimine)-modified silicone and trimethylsiloxysilicic acid are preferred, and poly(N-acylalkyleneimine)-modified silicone or a combination of poly(N-acylalkyleneimine)-modified silicone and trimethylsiloxysilicic acid is more preferred.

[0085] (Poly(N-acylalkyleneimine) modified silicone)

[0086] The poly(N-acylalkyleneimine)-modified silicone is an organopolysiloxane in which a poly(N-acylalkyleneimine) segment composed of a repeating unit represented by the following general formula (1) is bonded to at least two silicon atoms of an organopolysiloxane segment constituting the main chain via a cationic divalent linking group. Preferably, the organopolysiloxane has a number average molecular weight of 500 to 4000 and a weight average molecular weight of 10000 to 200000 (hereinafter, the organopolysiloxane is also referred to as organopolysiloxane (OX)).

[0087]

[0088] [In formula (1), R 41 represents a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, an aralkyl group or an aryl group, and t represents 2 or 3.]

[0089] Here, the organopolysiloxane (OX) will be described in detail.

[0090] At least two poly(N-acylalkyleneimine) segments are bonded to any silicon atom constituting the organopolysiloxane segment via a cationic divalent linking group. Preferably, the poly(N-acylalkyleneimine) segments are bonded to one or more silicon atoms excluding both ends of the organopolysiloxane segment via a cationic divalent linking group, and more preferably, the poly(N-acylalkyleneimine) segments are bonded to two or more silicon atoms excluding both ends via a cationic divalent linking group.

[0091] The cationic divalent linking group functions as a linking group of the poly(N-acylalkyleneimine) segment.

[0092] Examples of the cationic divalent linking group include an alkylene group containing a cationic group, preferably an alkylene group containing 2 to 20 carbon atoms and containing 1 to 3 cationic groups, and more preferably an alkylene group containing 1 to 3 cationic groups of one or more selected from a primary amino group, a secondary amino group, a tertiary amino group and a quaternary ammonium group and containing 1 to 3 carbon atoms.

[0093] Among such cationic divalent linking groups, a group represented by any one of the following formulae (A1) to (A9) is preferred, a group represented by any one of the formulae (A1) to (A4) is more preferred, and a group represented by the formulae (A1) or (A2) is particularly preferred.

[0094] In addition, in the formula, An - It represents the counter ion of the quaternary ammonium salt, and examples thereof include halide ions (e.g., chloride ions, iodide ions), sulfate ions, phosphate ions, acetate ions, lactate ions, p-toluenesulfonate ions, perchlorate ions, and monoalkyl nitrate ions (e.g., methylsulfate ions, ethylsulfate ions).

[0095]

[0096] In the N-acylalkyleneimine unit constituting the poly(N-acylalkyleneimine) segment, in the general formula (1), R 41 The number of carbon atoms of the alkyl group is 1 to 22, preferably 1 to 14, more preferably 1 to 6, and particularly preferably 1 to 3. The alkyl group may be linear or branched, and examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, pentyl, and hexyl.

[0097] As R 41 The aralkyl group represented by is preferably an aralkyl group having 7 to 15 carbon atoms, and examples thereof include benzyl, phenethyl, trityl, naphthylmethyl, anthracenemethyl and the like.

[0098] As R 41The aryl group represented by is preferably an aryl group having 6 to 14 carbon atoms, and examples thereof include phenyl, tolyl, xylyl, naphthyl, biphenylyl, anthracenyl, and phenanthryl.

[0099] Among these, R 41 , preferably a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms, more preferably a linear or branched alkyl group having 1 to 3 carbon atoms.

[0100] In formula (1), t represents 2 or 3, and preferably 2.

[0101] The mass ratio (a / b) of the organopolysiloxane segment (a) and the poly(N-acylalkyleneimine) segment (b) constituting the main chain is preferably 40 / 60 to 98 / 2, more preferably 45 / 55 to 82 / 18, further preferably 60 / 40 to 80 / 20, further preferably 65 / 35 to 80 / 20, further preferably 68 / 32 to 80 / 20, and particularly preferably 70 / 30 to 79 / 21.

[0102] In this specification, the mass ratio (a / b) refers to the mass ratio of 5 mass % of the organopolysiloxane (OX) dissolved in deuterated chloroform and measured by nuclear magnetic resonance ( 1 The value determined by H-NMR) analysis is the integrated ratio of the alkyl group or phenyl group in the organopolysiloxane segment to the methylene group in the poly(N-acylalkyleneimine) segment.

[0103] In the organopolysiloxane (OX), the weight average molecular weight (hereinafter also referred to as "MWg") of the organopolysiloxane segment between adjacent poly(N-acylalkyleneimine) segments is preferably 1,000 to 40,000, more preferably 1,500 to 30,000, and particularly preferably 1,750 to 5,000.

[0104] In the present specification, the "organopolysiloxane segment between adjacent poly(N-acylalkyleneimine) segments" refers to the portion surrounded by a dotted line between two points from the bonding point (bonding point A) of the poly(N-acylalkyleneimine) segment to the organopolysiloxane segment to the bonding point (bonding point B) of the adjacent poly(N-acylalkyleneimine) segment, as shown in the following formula (2), and consisting of one R 42 SiO unit, 1 R 43 and y+1 (R 42 )2SiO units. In addition, the so-called "poly (N-acyl alkylene imine) segment" refers to the above R 43 Bonded-Z 11 -R 44 .

[0105]

[0106] [In formula (2), R 42 Each independently represents an alkyl group having 1 to 22 carbon atoms or a phenyl group, and R 43 represents a cationic divalent linking group, -Z 11 -R 44 represents a poly(N-acylalkyleneimine) segment, R 44 represents a residue of a polymerization initiator or a hydrogen atom, and y represents a positive number. 42 , R 43 , R 44 Can be the same or different.]

[0107] MWg is the molecular weight of the portion surrounded by the dotted line in the above formula (2), and can be understood as the mass (g / mol) of the organopolysiloxane segment per 1 mol of the poly(N-acylalkyleneimine) segment. In addition, if the functional group of the modified organopolysiloxane of the raw material compound is 100% replaced by the poly(N-acylalkyleneimine), it is consistent with the functional group equivalent (g / mol) of the modified organopolysiloxane.

[0108] The molecular weight of the poly(N-acylalkyleneimine) segment can be calculated from the molecular weight and polymerization degree of the N-acylalkyleneimine unit, or can be measured by gel permeation chromatography (GPC). In this specification, it refers to the number average molecular weight (hereinafter also referred to as MNox) in terms of polystyrene measured by GPC under the measurement conditions described below. MNox is preferably 800 to 3500, and more preferably 1000 to 3000.

[0109] In addition, MWg can be determined from the following formula (I) using the content (mass %) of the organopolysiloxane segment constituting the main chain (hereinafter also referred to as Csi).

[0110] MWg=Csi×MNox / (100-Csi)(I)

[0111] The weight average molecular weight (hereinafter also referred to as MWsi) of the organopolysiloxane segment constituting the main chain is preferably 15,000 to 160,000, more preferably 20,000 to 150,000, and particularly preferably 25,000 to 100,000.

[0112] Since the organopolysiloxane segment constituting the main chain has a common skeleton with the modified organopolysiloxane of the raw material compound, MWsi is substantially the same as the weight average molecular weight of the modified organopolysiloxane of the raw material compound. In addition, the weight average molecular weight of the modified organopolysiloxane of the raw material compound is a weight average molecular weight in terms of polystyrene measured by GPC performed under the following measurement conditions.

[0113] (Measurement Conditions for Weight Average Molecular Weight of Modified Organopolysiloxane)

[0114] Column: Super HZ4000+Super HZ2000 (manufactured by Tosoh Corporation)

[0115] Eluent: 1 mM triethylamine / THF

[0116] Flow rate: 0.35mL / min

[0117] Column temperature: 40°C

[0118] Detector: UV

[0119] Sample: 50 μL

[0120] The weight average molecular weight (hereinafter also referred to as MWt) of the organopolysiloxane (OX) is preferably 10,000 to 500,000, more preferably 12,000 to 200,000, further preferably 25,000 to 160,000, and particularly preferably 35,000 to 150,000. MWt refers to a value in terms of polystyrene measured by GPC under the following measurement conditions.

[0121] (Measurement conditions of MNox and MWt)

[0122] Column: Two K-804L (manufactured by Tosoh Corporation) connected in series

[0123] Eluent: 1 mM dimethyldodecylamine / chloroform

[0124] Flow rate: 1.0mL / min

[0125] Column temperature: 40°C

[0126] Detector: RI

[0127] Sample: 50 μL

[0128] When the poly(N-acylalkyleneimine) segment is a poly(N-propionylethyleneimine) segment, the mass ratio (a / b) is calculated as 1 H-NMR measurement can be performed, for example, under the following conditions.

[0129] ( 1 H-NMR measurement conditions)

[0130] A solution prepared by dissolving 0.5 g of a polymer sample in 2 g of a measuring solvent (deuterated chloroform) was prepared by 1 The measurement was performed by H-NMR (400 MHz, manufactured by Varian). Then, the ratio of silicone to poly(N-acylalkyleneimine) was calculated from each integrated value.

[0131] PULSE SEQUENCE

[0132] Relaxation: 30 seconds Pulse: 45 degrees Accumulation times: 8 times

[0133] Confirm the peak near 0ppm: methyl group of polydimethylsiloxane

[0134] Around 3.4 ppm: methylene part of ethyleneimine.

[0135] The organopolysiloxane (OX) may be a synthetic product synthesized by the method described in Japanese Patent Application Publication No. 2008-143820, Japanese Patent Application Publication No. 2009-24114, Japanese Patent Application Publication No. 2015-67603, Japanese Patent Application Publication No. 2016-204336, etc. For example, the organopolysiloxane (OX) may be produced by reacting an organopolysiloxane modified with a functional group for deriving the above-mentioned cationic divalent linking group with a terminally reactive poly (N-acylalkylene imine) obtained by ring-opening polymerization of a cyclic imino ether corresponding to the repeating unit represented by the general formula (1).

[0136] Specific examples of the poly(N-acylalkyleneimine)-modified silicone include poly(N-formylethyleneimine)-modified silicone, poly(N-acetylethyleneimine)-modified silicone, poly(N-propionylethyleneimine)-modified silicone, poly(N-octanoylethyleneimine)-modified silicone, poly(N-dodecanoylethyleneimine)-modified silicone, poly(N-formylpropyleneimine)-modified silicone, poly(N-acetylpropyleneimine)-modified silicone, poly(N-propionylpropyleneimine)-modified silicone, poly(N-octanoylpropyleneimine)-modified silicone, and poly(N-dodecanoylpropyleneimine)-modified silicone.

[0137] The film-forming agent may be used alone or in combination of two or more.

[0138] The content of the film-forming agent is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, further preferably 0.75% by mass or more, and particularly preferably 1% by mass or more in the skin external preparation of the present invention from the viewpoints of ultraviolet protection effect, water resistance, friction resistance, etc.; in addition, from the viewpoints of ejection properties when used as a spray (in addition, the spray includes a mist preparation), in the skin external preparation of the present invention, it is preferably 10% by mass or less, more preferably 7.5% by mass or less, further preferably 5% by mass or less, and particularly preferably 4% by mass or less. As a specific range, in the skin external preparation of the present invention, it is preferably 0.1% by mass or more and 10% by mass or less, more preferably 0.5% by mass or more and 7.5% by mass or less, further preferably 0.75% by mass or more and 5% by mass or less, and particularly preferably 1% by mass or more and 4% by mass or less.

[0139] The skin external preparation of the present invention may contain, in addition to the above-mentioned components, ultraviolet scattering agents, powders other than ultraviolet scattering agents (organic powders, inorganic powders, organic-inorganic composite powders), surfactants, water, water-soluble ultraviolet absorbers, fragrances, animal and plant extracts, cooling agents, preservatives, anti-inflammatory agents, emollients, pH adjusters, chelating agents, antioxidants, colorants, etc. In addition, among these, only one type may be used alone, or two or more types may be used in combination.

[0140] The content of the ultraviolet scattering agent is preferably 0% by mass or more and 2.5% by mass or less, more preferably 0% by mass or more and 1% by mass or less, further preferably 0% by mass or more and 0.5% by mass or less, and particularly preferably 0% by mass in the skin external preparation of the present invention from the viewpoints of coating uniformity, non-whitening, use feeling (no roughness), etc. The skin external preparation of the present invention can obtain an excellent ultraviolet protection effect even when the ultraviolet scattering agent is contained in such a content.

[0141] The content of the surfactant in the skin external preparation of the present invention is preferably 0 mass % to 2.5 mass %, more preferably 0 mass % to 1 mass %, further preferably 0 mass % to 0.5 mass %, particularly preferably 0 mass %.

[0142] The water content in the skin external preparation of the present invention is preferably from 0 mass % to 10 mass %, more preferably from 0 mass % to 5 mass %, further preferably from 0 mass % to 0.5 mass %, and particularly preferably 0 mass %, from the viewpoints of water resistance, uniformity of application of components remaining on the skin after application, and stability of the formulation.

[0143] The form of the skin preparation of the present invention is not particularly limited, and may be, for example, a transparent liquid, emulsion, paste, cream, gel, milk, spray (aerosol type, non-aerosol type), foaming agent (aerosol type, non-aerosol type), etc., and may also be a sheet preparation in which the skin preparation of the present invention is used as a permeating liquid to be permeated into a sheet substrate. In addition, when the skin preparation is an aerosol type, the container of the skin preparation is usually a pressure-resistant container, and when the skin preparation is in other forms, as a container, for example, a can container, a bottle container, a squeeze container, a pump dispensing container, a pump spray container, a trigger spray container, etc. can be listed. In addition, the skin preparation of the present invention has good sprayability even when it is a spray as described above containing an oil gelling agent.

[0144] Among the above, as the form of the skin external preparation of the present invention, from the viewpoints of coating uniformity, ultraviolet protection effect, usability, etc., it is preferably a spray, and more preferably an aerosol spray-type skin external preparation; non-aerosol spray-type skin external preparations such as pump spray type and trigger spray type are particularly preferably aerosol spray-type skin external preparations.

[0145] In addition, as the skin external preparation of the present invention (in the case of an aerosol-type skin external preparation, it is a concentrate), emulsified skin external preparations (oil-in-water skin external preparations, water-in-oil skin external preparations), multi-layer separation type skin external preparations, and oily skin external preparations can be listed. From the viewpoint of achieving both excellent water resistance and excellent coating uniformity and excellent ultraviolet protection effect, oily skin external preparations are preferred.

[0146] In addition, in this specification, an oily skin external preparation refers to a skin external preparation in which the oil-soluble ultraviolet absorber and the components other than the oil-soluble ultraviolet absorber are soluble in each other. For example, when the oil-soluble ultraviolet absorber and the components other than the oil-soluble ultraviolet absorber are soluble in each other and are in a transparent liquid state, even if the components other than oil such as ethanol are contained, they are included in the oily skin external preparation.

[0147] The skin external preparation of the present invention (in the case of an aerosol type skin external preparation, a stock solution) is preferably in a liquid state. In addition, the viscosity at 25°C is preferably 0 mPa·s or more, more preferably 2.5 mPa·s or more, from the viewpoint of sprayability, etc.; and in addition, from the viewpoint of sprayability, etc., it is preferably 20,000 mPa·s or less, more preferably 10,000 mPa·s or less.

[0148] Moreover, when the skin external preparation of the present invention is an aerosol spray-type skin external preparation, the viscosity of the stock solution at 25°C is preferably 0 mPa·s or more, more preferably 5 mPa·s or more, and further preferably 10 mPa·s or more, from the viewpoint of sprayability, etc., and is preferably 10,000 mPa·s or less, more preferably 2500 mPa·s or less, further preferably 1500 mPa·s or less, and particularly preferably less than 500 mPa·s, from the viewpoint of sprayability, etc.

[0149] In addition, when the skin topical preparation of the present invention is a non-aerosol spray-type skin topical preparation, the viscosity of the skin topical preparation at 25°C is preferably 0 mPa·s or more, more preferably 2.5 mPa·s or more, from the viewpoint of sprayability, etc. as described above, and is more preferably 10 mPa·s or less, particularly preferably 5 mPa·s or less, from the viewpoint of sprayability, etc.

[0150] In addition, when the skin external preparation of the present invention is a skin external preparation filled in a pump dispensing container, the viscosity of the skin external preparation at 25°C is preferably 5,000 mPa·s or more, particularly preferably 5,500 mPa·s or more, from the viewpoint of sprayability, etc., and is preferably 20,000 mPa·s or less, more preferably 15,000 mPa·s or less, from the same viewpoint.

[0151] In addition, when the skin external preparation of the present invention is an emulsion or the like filled in a pouring container, the viscosity of the skin external preparation at 25°C is preferably 0 mPa·s or more, more preferably 5 mPa·s or more, from the viewpoint of usability, etc., and is preferably 10,000 mPa·s or less, more preferably 5,000 mPa·s or less, from the viewpoint of sprayability, feeling of use, etc.

[0152] The viscosity at 25° C. can be measured using a Brookfield viscometer (B-type viscometer), and specifically, can be measured according to the method described in Examples.

[0153] In addition, in the skin external preparation of the present invention (the stock solution in the case of an aerosol type skin external preparation), the viscosity at 25°C when all volatile components (when not containing water, (C) non-aqueous volatile components) are volatilized is preferably 10,000 mPa·s or more, more preferably 100,000 mPa·s or more, further preferably 200,000 mPa·s or more, and particularly preferably 300,000 mPa·s or more from the viewpoint of ultraviolet protection effect, etc. The upper limit of the viscosity is not particularly limited, and may be, for example, 20,000,000 mPa·s.

[0154] The viscosity at 25° C. when all volatile components are released may be measured using a Brookfield viscometer (B-type viscometer) after all volatile components ((C) non-aqueous volatile components when no water is contained) are volatilized. Alternatively, the viscosity may be measured by the method described in the Examples.

[0155] Here, as a specific form of the aerosol type external preparation for skin, the following aerosol type external preparation for skin (α) can be mentioned.

[0156] (α) An aerosol-type external skin preparation comprising a stock solution containing the following components (A), (B) and (C) (and, if necessary, component (D) and / or component (E) or other components) and a propellant in a pressure-resistant container. The stock solution is the total composition of the content solution excluding the propellant.

[0157] (A) Oil-soluble UV absorber;

[0158] (B) an oil gelling agent, which is 0.5% by mass or more and 20% by mass or less in the stock solution;

[0159] (C) The non-aqueous volatile component accounts for 50% by mass or more in the stock solution.

[0160] The aerosol type external skin preparation (α) may be either an aerosol spray type or an aerosol foam type, and is preferably an aerosol spray type external skin preparation.

[0161] Examples of the propellant include liquefied petroleum gas (LPG), dimethyl ether (DME), carbon dioxide, nitrogen, and mixtures thereof. Alternatively, chlorofluorocarbon substitutes such as HFC-152a may be used.

[0162] In addition, the mass ratio of the stock solution to the propellant (stock solution / propellant) is preferably 10 / 90 or more, more preferably 20 / 80 or more, particularly preferably 30 / 70 or more, and preferably 99 / 1 or less, more preferably 85 / 15 or less, and particularly preferably 75 / 25 or less. As a specific range, it is preferably 10 / 90 or more and 99 / 1 or less, more preferably 20 / 80 or more and 85 / 15 or less, and particularly preferably 30 / 70 or more and 75 / 25 or less. In addition, it is preferred to adjust the amount of the propellant in a manner that is 0.12 MPa or more and 0.45 MPa or less at a temperature of 25°C.

[0163] The skin external preparation of the present invention is useful as a sunscreen. The skin external preparation of the present invention can be applied to the skin (preferably skin other than the scalp, more preferably face, body, hands and feet, etc.) by a method depending on the type of the dosage form and used as a sunscreen.

[0164] The skin external preparation of the present invention can be manufactured by a conventional method. In the case of an aerosol type skin external preparation, for example, components (A), (B) and (C) (as required, component (D) and / or component (E) or other components) are mixed and dissolved or dispersed to prepare a stock solution, and the obtained stock solution is filled into a pressure-resistant container together with a propellant.

[0165] Regarding the above-mentioned embodiment, the present invention further discloses the following external skin preparations and the like.

[0166] <1> A skin external preparation comprising the following components (A), (B) and (C),

[0167] (A) Oil-soluble UV absorber;

[0168] (B) 0.5 mass % or more and 20 mass % or less of an oil gelling agent;

[0169] (C) Non-aqueous volatile components: 50% by mass or more.

[0170] <2> like <1> The skin external preparation, wherein component (A) is preferably selected from benzoic acid oil-soluble ultraviolet absorbers, anthranilic acid oil-soluble ultraviolet absorbers, salicylic acid oil-soluble ultraviolet absorbers, cinnamic acid oil-soluble ultraviolet absorbers, benzoylmethane oil-soluble ultraviolet absorbers, triazine oil-soluble ultraviolet absorbers, benzophenone oil-soluble ultraviolet absorbers, and hydantoin oil-soluble ultraviolet absorbers. One or more kinds of ultraviolet absorbers selected from benzoic acid oil-soluble ultraviolet absorbers, cinnamic acid oil-soluble ultraviolet absorbers and triazine oil-soluble ultraviolet absorbers are more preferred, and further preferably selected from p-aminobenzoic acid, glyceryl p-aminobenzoic acid, ethyl dihydroxypropyl p-aminobenzoic acid, octyl dimethyl p-aminobenzoic acid, p- One or more of dimethylaminobenzoic acid amyl ester, diethylaminohydroxybenzoylbenzoic acid hexyl ester, p-methoxycinnamic acid 2-ethylhexyl ester, di-p-methoxycinnamic acid mono-2-ethylhexanoin, methyl 2,5-diisopropylcinnamate, methyl trimethoxycinnamate bis(trimethylsiloxy)silylisoamyl ester, p-methoxycinnamic acid isopropyl, a mixture of p-methoxycinnamic acid isopropyl ester and diisopropyl cinnamate, p-methoxycinnamic acid 2-ethoxyethyl ester, p-methoxycinnamic acid diethanolamine salt, 2,4,6-tris[4-(2-ethylhexyloxycarbonyl)anilino]-1,3,5-triazine, and 2,4-bis-[{4-(2-ethylhexyloxy)-2-hydroxy}-phenyl]-6-(4-methoxyphenyl)-1,3,5-triazine.

[0171] <3> like <1> The above-mentioned external preparation for skin preferably contains, as component (A), at least an oil-soluble ultraviolet absorber which is liquid at 25° C. under 1 atmospheric pressure.

[0172] <4> like <1> ~ <3> The skin external preparation described in any one of the above, wherein the content of component (A) in the skin external preparation is preferably 5 mass % or more, more preferably 7.5 mass % or more, further preferably 10 mass % or more, particularly preferably 12.5 mass % or more; further, in the skin external preparation, it is preferably 30 mass % or less, more preferably 25 mass % or less, further preferably 20 mass % or less, particularly preferably 17.5 mass % or less.

[0173] <5> like <1> ~ <3> The skin external preparation described in any one of the above, wherein the content of component (A) in the skin external preparation is preferably from 5 mass % to 30 mass %, more preferably from 7.5 mass % to 25 mass %, further preferably from 10 mass % to 20 mass %, particularly preferably from 12.5 mass % to 17.5 mass %.

[0174] <6> like <1> ~ <5> The skin external preparation described in any one of the preceding claims, wherein component (B) is preferably one or more selected from sugar fatty acid ester oil gelling agents, glycerol fatty acid ester oil gelling agents, amino acid derivative oil gelling agents and benzylidene sorbitol oil gelling agents, more preferably one or more selected from sugar fatty acid ester oil gelling agents, glycerol fatty acid ester oil gelling agents and amino acid derivative oil gelling agents, and further preferably a sugar fatty acid ester oil gelling agent.

[0175] <7> like <6> The skin external preparation, wherein the sugar fatty acid ester oil gelling agent is preferably one or more selected from dextrin fatty acid ester oil gelling agents, sucrose fatty acid ester oil gelling agents, inulin fatty acid ester oil gelling agents and fructooligosaccharide fatty acid ester oil gelling agents, more preferably one or more selected from dextrin myristate, dextrin palmitate, dextrin stearate, dextrin (palmitic acid / 2-ethylhexanoate), dextrin (palmitic acid / hexyldecanoate), sucrose palmitate, sucrose stearate, inulin stearate, fructooligosaccharide stearate and fructooligosaccharide 2-ethylhexanoate, particularly preferably dextrin palmitate.

[0176] <8> like <6> or <7> In the skin external preparation, the amino acid derivative oil gelling agent is at least one selected from dibutyl lauroyl glutamine and dibutyl ethylhexanoyl glutamine.

[0177] <9> like <1> ~ <8> The skin external preparation described in any one of the above, wherein the content of component (B) in the skin external preparation is preferably 1% by mass or more, more preferably 1.5% by mass or more, further preferably 2% by mass or more, and particularly preferably 2.5% by mass or more; further, in the skin external preparation, it is preferably 15% by mass or less, more preferably 10% by mass or less, further preferably 7.5% by mass or less, and particularly preferably 5% by mass or less.

[0178] <10> like <1> ~ <8> The skin external preparation described in any one of the above, wherein the content of component (B) in the skin external preparation is preferably from 1 mass % to 15 mass %, more preferably from 1.5 mass % to 10 mass %, further preferably from 2 mass % to 7.5 mass %, particularly preferably from 2.5 mass % to 5 mass %.

[0179] <11> like <1> ~ <10> The skin external preparation described in any one of the preceding claims, wherein the content mass ratio of component (B) to component (A) [(B) / (A)] is preferably 0.01 or more, more preferably 0.05 or more, further preferably 0.1 or more, and particularly preferably 0.15 or more; and is preferably 1.5 or less, more preferably 1 or less, further preferably 0.6 or less, and particularly preferably 0.3 or less.

[0180] <12> like <1> ~ <10> The skin external preparation described in any one of the preceding claims, wherein the content mass ratio of component (B) to component (A) [(B) / (A)] is preferably from 0.01 to 1.5, more preferably from 0.05 to 1, further preferably from 0.1 to 0.6, and particularly preferably from 0.15 to 0.3.

[0181] <13> like <1> ~ <12> In any one of the skin external preparations, component (C) is preferably one or more selected from (C-1) volatile silicone oils, (C-2) lower alcohols, and (C-3) volatile liquid oils other than volatile silicone oils.

[0182] <14> like <1> ~ <13> The skin external preparation described in any one of the above-mentioned preparations preferably contains at least (C-1) a volatile silicone oil as the component (C), and more preferably contains (C-1) a volatile silicone oil and (C-2) a lower alcohol as the component (C).

[0183] <15> like <1> ~ <14> The skin external preparation described in any one of the above, wherein the content of component (C) in the skin external preparation is preferably 52 mass % or more, more preferably 55 mass % or more, further more preferably 60 mass % or more, particularly preferably 62 mass % or more; further, in the skin external preparation, it is preferably 90 mass % or less, more preferably 85 mass % or less, further preferably 80 mass % or less, particularly preferably 75 mass % or less.

[0184] <16> like <1> ~ <14> The skin external preparation described in any one of the above, wherein the content of component (C) in the skin external preparation is preferably from 0.5 mass % to 30 mass %, more preferably from 1 mass % to 25 mass %, further preferably from 2 mass % to 20 mass %, particularly preferably from 4 mass % to 15 mass %.

[0185] <17> like <1> ~ <16> The skin external preparation described in any one of the preceding claims, wherein the content of the (C-2) lower alcohol in the skin external preparation is preferably 40% by mass or more, more preferably 45% by mass or more, and further preferably 50% by mass or more; and in the skin external preparation, is preferably 95% by mass or less, more preferably 90% by mass or less, and further preferably 80% by mass or less.

[0186] <18> like <1> ~ <17> The skin external preparation described in any one of the preceding claims, wherein the content mass ratio of component (A) to component (C) [(A) / (C)] is preferably 0.01 or more, more preferably 0.05 or more, further preferably 0.1 or more, and particularly preferably 0.15 or more; and is preferably 1.5 or less, more preferably 1 or less, and further preferably 0.5 or less.

[0187] <19> like <1> ~ <17> The skin external preparation described in any one of the preceding claims, wherein the content mass ratio of component (A) to component (C) [(A) / (C)] is preferably from 0.01 to 1.5, more preferably from 0.05 to 1, further preferably from 0.1 to 0.5, and particularly preferably from 0.15 to 0.5.

[0188] <20> like <1> ~ <19> The skin external preparation described in any one of the preceding claims, wherein the mass ratio of the total content of components (A) and (B) to component (C) [((A)+(B)) / (C)] is preferably 0.02 or more, more preferably 0.05 or more, further preferably 0.1 or more, and particularly preferably 0.23 or more; and is preferably 3 or less, more preferably 0.8 or less, further preferably 0.6 or less, and particularly preferably 0.3 or less.

[0189] <21> like <1> ~ <19> The skin external preparation described in any one of the preceding claims, wherein the content mass ratio of the total of components (A) and (B) to component (C) [((A)+(B)) / (C)] is preferably from 0.02 to 3, more preferably from 0.05 to 0.8, further preferably from 0.1 to 0.6, and particularly preferably from 0.23 to 0.3.

[0190] <22> like <13> or <14> The skin external preparation described above, wherein the content mass ratio of component (C-2) to component (C-1) [(C-2) / (C-1)] is preferably 0.5 or more, more preferably 1 or more, further preferably 3 or more, and particularly preferably 6 or more; in addition, it is preferably 600 or less, more preferably 100 or less, further preferably 25 or less, and particularly preferably 9 or less.

[0191] <23> like <1> ~ <22> The skin external preparation described in any one of the above, wherein it is preferred that it further contains one or more selected from (D) a non-volatile liquid oil agent (excluding component (A)) and (E) a film-forming agent, more preferably contains components (A) to (D), and even more preferably contains components (A) to (E).

[0192] <24> like <23> The skin external preparation, wherein component (D) is preferably one or more selected from non-volatile ester oils, non-volatile hydrocarbon oils and non-volatile silicone oils, more preferably non-volatile ester oils, further preferably one or more selected from non-volatile fatty acid ester oils and non-volatile aromatic carboxylic acid ester oils, further preferably one or more selected from non-volatile monohydric alcohol fatty acid ester oils, non-volatile polyhydric alcohol fatty acid ester oils and non-volatile aromatic carboxylic acid ester oils, further preferably one or more selected from non-volatile monohydric alcohol fatty acid ester oils and non-volatile aromatic carboxylic acid ester oils, particularly preferably one or more selected from cetyl 2-ethylhexanoate, isononyl isononanoate, isotridecyl isononanoate, isopropyl myristate, isopropyl palmitate, 2-ethylhexyl palmitate, 2-ethylhexyl stearate, stearyl stearate, and alkyl (C12-15) benzoate.

[0193] <25> like <23> or <24> The skin external preparation, wherein the content of component (D) in the skin external preparation is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, further preferably 1% by mass or more; further, in the skin external preparation, it is preferably 35% by mass or less, more preferably 25% by mass or less, further preferably 20% by mass or less, particularly preferably 10% by mass or less.

[0194] <26> like <23> or <24> The skin external preparation, wherein the content of component (D) in the skin external preparation is preferably from 0.1 mass % to 35 mass %, more preferably from 0.5 mass % to 25 mass %, further preferably from 1 mass % to 20 mass %, particularly preferably from 1 mass % to 10 mass %.

[0195] <27> like <23> ~ <26> The skin external preparation described in any one of the preceding claims, wherein the mass ratio of the content of component (B) relative to the total of components (A) and (D) [(B) / ((A)+(D))] is preferably not less than 0.01, more preferably not less than 0.05, and further preferably not less than 0.1; and is preferably not more than 1, more preferably not more than 0.5, further preferably not more than 0.25, and particularly preferably not more than 0.18.

[0196] <28> like <23> ~ <26> The skin external preparation described in any one of the preceding claims, wherein the content mass ratio of component (B) to the total of components (A) and (D) [(B) / ((A)+(D))] is preferably from 0.01 to 1, more preferably from 0.05 to 0.5, further preferably from 0.1 to 0.25, and particularly preferably from 0.1 to 0.18.

[0197] <29> like <23> ~ <28> The skin external preparation according to any one of the preceding claims, wherein the component (E) is preferably at least one selected from silicone film-forming agents and (meth)acrylic film-forming agents, more preferably a silicone film-forming agent, further preferably at least one selected from poly(N-acylalkyleneimine)-modified silicone, amino-modified silicone, fluorine-modified silicone, trimethylsiloxysilicic acid, (trimethylsiloxysilicic acid / polydimethiconol) crosslinked polymer, (meth)acrylic polymer having a dendritic siloxane structure in a side chain, polyalkylsilsesquioxane, and (meth)acrylic acid-silicone graft copolymer, further preferably at least one selected from poly(N-acylalkyleneimine)-modified silicone and trimethylsiloxysilicic acid, and particularly preferably a poly(N-acylalkyleneimine)-modified silicone or a combination of a poly(N-acylalkyleneimine)-modified silicone and trimethylsiloxysilicic acid.

[0198] <30> like <29> The skin external preparation, wherein the poly(N-acylalkylene imine) modified silicone is one or more selected from poly(N-formylethyleneimine) modified silicone, poly(N-acetylethyleneimine) modified silicone, poly(N-propionylethyleneimine) modified silicone, poly(N-octanoylethyleneimine) modified silicone, poly(N-dodecanoylethyleneimine) modified silicone, poly(N-formylpropyleneimine) modified silicone, poly(N-acetylpropyleneimine) modified silicone, poly(N-propionylpropyleneimine) modified silicone, poly(N-octanoylpropyleneimine) modified silicone and poly(N-dodecanoylpropyleneimine) modified silicone.

[0199] <31> like <23> ~ <30> The skin external preparation described in any one of the above, wherein the content of component (E) in the skin external preparation is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, further preferably 0.75% by mass or more, and particularly preferably 1% by mass or more; further, in the skin external preparation, it is preferably 10% by mass or less, more preferably 7.5% by mass or less, further preferably 5% by mass or less, and particularly preferably 4% by mass or less.

[0200] <32> like <23> ~ <30> The skin external preparation described in any one of the preceding claims, wherein the content of component (E) in the skin external preparation is preferably from 0.1 mass % to 10 mass %, more preferably from 0.5 mass % to 7.5 mass %, further preferably from 0.75 mass % to 5 mass %, particularly preferably from 1 mass % to 4 mass %.

[0201] <33> like <1> ~ <32> The skin external preparation according to any one of the preceding claims, wherein the content of the ultraviolet scattering agent in the skin external preparation is preferably 0% by mass or more and 2.5% by mass or less, more preferably 0% by mass or more and 1% by mass or less, further preferably 0% by mass or more and 0.5% by mass or less, and particularly preferably 0% by mass.

[0202] <34> like <1> ~ <33> The skin external preparation described in any one of the preceding claims, wherein the content of the surfactant in the skin external preparation is preferably 0 mass % to 2.5 mass %, more preferably 0 mass % to 1 mass %, further preferably 0 mass % to 0.5 mass %, particularly preferably 0 mass %.

[0203] <35> like <1> ~ <34> The skin external preparation according to any one of the preceding claims, wherein the water content in the skin external preparation is preferably 0 mass % to 10 mass %, more preferably 0 mass % to 5 mass %, further preferably 0 mass % to 0.5 mass %, particularly preferably 0 mass %.

[0204] <36> like <1> ~ <35> The skin external preparation described in any one of the above is preferably a transparent liquid, emulsion, ointment, cream, gel, milk, spray or foaming agent, more preferably a spray, further preferably an aerosol spray-type skin external preparation or a non-aerosol spray-type skin external preparation, and particularly preferably an aerosol spray-type skin external preparation.

[0205] <37> like <1> ~ <36> The skin external preparation according to any one of the above aspects, wherein the skin external preparation (in the case of an aerosol-type skin external preparation, a stock solution) is preferably in a liquid form.

[0206] <38> like <1> ~ <37> The skin external preparation described in any one of the above, wherein the viscosity of the skin external preparation (the original solution in the case of an aerosol-type skin external preparation) at 25°C is preferably 0 mPa·s or more, more preferably 2.5 mPa·s or more, further preferably 5 mPa·s or more, and particularly preferably 10 mPa·s or more; in addition, it is preferably 20,000 mPa·s or less, more preferably 10,000 mPa·s or less, further preferably 2500 mPa·s or less, further preferably 1500 mPa·s or less, and particularly preferably less than 500 mPa·s.

[0207] <39> An aerosol-type skin external preparation, wherein a stock solution containing the following components (A), (B) and (C) (and, if necessary, component (D) and / or component (E) or other components) and a propellant are filled in a pressure-resistant container. The stock solution is the total composition of the content liquid excluding the propellant.

[0208] (A) Oil-soluble UV absorber;

[0209] (B) an oil gelling agent, which is 0.5% by mass or more and 20% by mass or less in the stock solution;

[0210] (C) The non-aqueous volatile component accounts for 50% by mass or more in the stock solution.

[0211] <40> like <39> The skin external preparation is preferably an aerosol spray type or an aerosol foam type, and more preferably an aerosol spray type.

[0212] <41> like <1> ~ <40> The skin external preparation according to any one of the above aspects is preferably a sunscreen agent.

[0213] Example

[0214] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.

[0215] [Examples 1 to 15 and Comparative Examples 1 to 4 Aerosol Spray Type Oily Skin External Preparations]

[0216] Aerosol spray type oily skin external preparations were prepared, and the following measurements and evaluations were performed. The results are shown in Tables 1 to 3.

[0217] (Manufacturing method)

[0218] The stock solution of the aerosol spray type oily skin external preparation was prepared by mixing the components uniformly using a homogenizer equipped with a paddle blade according to the formulations shown in Tables 1 to 3. The obtained stock solution and propellant (LPG) were filled into an aerosol pressure container at a pressure of 0.22 MPa (25° C.) and a mass ratio of stock solution:propellant = 40:60.

[0219] In addition, the skin external preparation filled in the following aerosol pressure-resistant container of specification 1 was used for the evaluation of the feeling of use, and the skin external preparation filled in the following aerosol pressure-resistant container of specification 2 was used for the evaluation of the difficulty in dripping.

[0220] Specification 1: Made in Japan precision valve, shaft: 04-5241, shell: 07-5166, pressure head: 20-1213-0146

[0221] Specification 2: Made by Mitani Valve, dosing valve: C16-HCP4B22(51)314HG8101(ALPS2)34(10), pressure head: P94W 05112D”3”

[0222] (Measurement method and evaluation method)

[0223] (1) Viscosity

[0224] The stock solution of each oily skin external preparation before filling the pressure-resistant container was filled in a glass bottle with a lid, and the viscosity at 25°C on the day after preparation was measured. The measurement was performed using a B-type viscometer (TVB-10) manufactured by Toki Sangyo Co., Ltd., and the viscosity was measured under the conditions of rotor No. 2, rotation speed: 60 rpm, and measurement time: 1 minute after stirring the glass bottle in advance, and the evaluation was performed based on the following criteria. In addition, the viscosity of the stock solution of the oily skin external preparation of Example 1 was 27 mPa·s, and the viscosity of the stock solution of the oily skin external preparation of Example 2 was 29 mPa·s.

[0225] (Evaluation criteria for viscosity)

[0226] ○: less than 500mPa·s

[0227] ╳: 500mPa·s or more

[0228] (2) Viscosity after volatile components evaporate

[0229] From the composition of the stock solution of each oily skin external preparation, a composition after removing the volatile components (component (C) in Examples 1 to 14 and Comparative Examples 1 to 4, component (C) and water in Example 15) (i.e., a composition equivalent to the components remaining on the skin after the spray is sprayed on the skin) was prepared, and the composition was filled in a glass bottle with a lid, and the viscosity at 25°C on the day after preparation was measured as the viscosity after the volatile components volatilized. The viscosity was measured using a B-type viscometer (TVB-10) manufactured by Toki Sangyo Co., Ltd. under the conditions of rotor: TC, rotation speed: 5 rpm, and measurement time: 1 minute, and the evaluation was performed based on the following criteria. In addition, the viscosity of the oily skin external preparation of Example 1 after the volatile components volatilized was 400,000 mPa·s, and the viscosity of the oily skin external preparation of Example 2 after the volatile components volatilized was 340,000 mPa·s.

[0230] (Evaluation criteria for viscosity after volatile components evaporate)

[0231] ○: 10,000 mPa·s or more

[0232] ╳: less than 10,000 mPa·s

[0233] (3) SPF

[0234] The original solution of each oily skin external preparation before filling the pressure-resistant container was measured at 1.3 g / cm 2 The skin was spread with a finger gloved in HelioPlates HD6 (manufactured by Labsphere) for 30 seconds, dried for 15 minutes, and then the SPF value was measured using an SPF analyzer (UV-2000S, manufactured by Labsphere) and evaluated based on the following criteria. The SPF value of the oily skin external preparation of Example 1 was 95.6, and the SPF value of the oily skin external preparation of Example 2 was 94.7.

[0235] (SPF evaluation criteria)

[0236] 5: Very high (SPF90 or above)

[0237] 4: Quite high (SPF70 or above and less than 90)

[0238] 3: Slightly higher (SPF50 or higher and less than 70)

[0239] 2: Allowable limit (SPF20 or above and less than 50)

[0240] 1: Low (SPF less than 20)

[0241] (4) Uniformity

[0242] 0.03 g of the original solution of each oily skin external preparation before filling the pressure-resistant container was taken on a PMMA plate, and the coating state was observed by VISIA-CR (manufactured by Canfield Scientific) with a finger wearing a cot for 1 minute. The blue component was extracted from the obtained image (RGB), and the average reflection absorbance and standard deviation were calculated from the images before and after coating. The average reflection absorbance was divided by the standard deviation to calculate the deviation (CV value). The uniformity was evaluated based on the following criteria. In addition, the captured images of Example 7 and Comparative Example 1 are shown in Figure 1 .

[0243] (Evaluation criteria for uniformity)

[0244] AAA: CV value less than 0.06

[0245] AA: CV value 0.06 or more and less than 0.07

[0246] A: CV value 0.07 or more and less than 0.1

[0247] B: CV value 0.1 or more

[0248] (5) Whether there is a strong sense of oiliness (greasy feeling) or pressure

[0249] Regarding the feeling of use of each oily skin external preparation (the presence or absence of strong oiliness and oppression), 15 professional evaluators conducted sensory evaluation based on the following criteria. The average of the 15 ratings was used as the score of each oily skin external preparation (rounded off to the second decimal place). In addition, after spraying an appropriate amount on the inner side of the forearm, blend it with the hand and evaluate.

[0250] (Evaluation criteria for usability)

[0251] 5 points: No uncomfortable oiliness or pressure

[0252] 4 points: Not too uncomfortable oily or oppressive

[0253] 3 points: Slightly feel uncomfortable oiliness or pressure

[0254] 2 points: Feeling of uncomfortable oiliness or pressure, but within the acceptable limit

[0255] 1 point: A noticeable uncomfortable feeling of oiliness or oppression

[0256] (6) Difficulty of dripping

[0257] Each oily skin external preparation (a single push valve (Mitani Valve Co., Ltd.) was placed on a table, and a black pad was placed vertically on the table 6 cm away from the spray port of the oily skin external preparation. The oily skin external preparation was sprayed once on the surface of the black pad, and the surface of the black pad was visually observed for 10 seconds, and the ease of dripping was evaluated based on the following criteria.

[0258] (Evaluation criteria for the difficulty of dripping)

[0259] 3: No liquid dripping

[0260] 2: Slow dripping

[0261] 1: Obvious dripping [Table 1]

[0262]

[0263] [Table 2]

[0264]

[0265] [Table 3]

[0266]

[0267] The symbols in the table are as follows.

[0268] *1: Uvinul MC-80 (manufactured by BASF)

[0269] *2: Uvinul A plus (manufactured by BASF)

[0270] *3: Tinosorb S (manufactured by BASF)

[0271] *4: Uvinul T-150 (manufactured by BASF)

[0272] *5: Rheopearl KL2 (manufactured by Chiba Flour Milling Co., Ltd.)

[0273] *6: KF-96L-2cs (manufactured by Shin-Etsu Chemical Co., Ltd.)

[0274] *7: FINSOLV TN (manufactured by Innospec Active Chemicals)

[0275] *8: EXCEPARL IPP (manufactured by Kao Corporation)

[0276] *9: A synthetic product prepared according to the description of Synthesis Example 1 in Japanese Patent Application Laid-Open No. 2008-143820 (In addition, the values ​​in the table refer to the content of the active ingredient in the external preparation for skin.)

[0277] *10: KF-7312L (manufactured by Shin-Etsu Chemical Co., Ltd.) (The values ​​in the table refer to the content of the active ingredient in the skin external preparation.)

[0278] *11: Rheopearl ISL2 (manufactured by Chiba Flour Milling Co., Ltd.)

[0279] *12: Amino acid gelling agent EB-21 (manufactured by Ajinomoto Co., Ltd.)

[0280] *13: KF-96L-1.5cs (manufactured by Shin-Etsu Chemical Co., Ltd.)

Claims

1. A skin external preparation, wherein: Contains the following ingredients (A), (B), (C) and (D): (A) one or more oil-soluble ultraviolet absorbers selected from the group consisting of benzoic acid oil-soluble ultraviolet absorbers, cinnamic acid oil-soluble ultraviolet absorbers and triazine oil-soluble ultraviolet absorbers; (B) one or more oil gelling agents selected from the group consisting of sugar fatty acid ester oil gelling agents, glycerol fatty acid ester oil gelling agents, amino acid derivative oil gelling agents, and benzylidene sorbitol oil gelling agents, wherein the content of the oil gelling agents is 0.5% by mass or more and 20% by mass or less; (C) a non-aqueous volatile component having a content of 50% by mass or more; (D) a non-volatile liquid oil agent excluding component (A), the content of which is 0.1 mass % or more and 10 mass % or less, The composition comprises at least (C-2) a lower alcohol as a component (C), wherein the (C-2) lower alcohol is a linear or branched monohydric alcohol having 2 or 3 carbon atoms, and the content of the (C-2) lower alcohol in the skin external preparation is 40% by mass or more and 95% by mass or less, The skin external preparation does not include the liquid described in (1) below and the aerosol composition described in (2) below, (1) a liquid containing 5.0% by mass of a decamethylcyclopentasiloxane dispersion of methyl hydrogen-treated fine zinc oxide, 8.0% by mass of ethylhexyl methoxycinnamate, 1.0% by mass of tert-butyl methoxydibenzoylmethane, 25.0% by mass of a mixture of polyether-modified silicone and decamethylcyclopentasiloxane, 32.0% by mass of decamethylcyclopentasiloxane, 8.0% by mass of methyl polytrimethicone, 2.0% by mass of isononyl isononanoate, 13.0% by mass of polymethylsilsesquioxane spherical powder, 1.0% by mass of disteardimethylammonium hectorite, and 5.0% by mass of ethanol; (2) An aerosol composition comprising 15% by mass of the liquid described in (1) above and 85% by mass of LPG as a propellant.

2. The skin external preparation according to claim 1, wherein The content of the component (A) is 5% by mass or more and 30% by mass or less.

3. The external skin preparation according to claim 1 or 2, wherein The content of the component (A) is 10% by mass or more and 20% by mass or less.

4. The external skin preparation according to claim 1 or 2, wherein Component (B) is one or more selected from the group consisting of sugar fatty acid ester oil gelling agents, glycerin fatty acid ester oil gelling agents, and amino acid derivative oil gelling agents.

5. The external skin preparation according to claim 1 or 2, wherein Component (B) is a sugar fatty acid ester oil gelling agent.

6. The external skin preparation according to claim 5, wherein The sugar fatty acid ester oil gelling agent is one or more selected from dextrin myristate, dextrin palmitate, dextrin stearate, dextrin (palmitic acid / 2-ethylhexanoate), dextrin (palmitic acid / hexyldecanoate), sucrose palmitate, sucrose stearate, inulin stearate, fructooligosaccharide stearate and fructooligosaccharide 2-ethylhexanoate.

7. The external skin preparation according to claim 1 or 2, wherein The content of the component (B) is 0.5% by mass or more and 15% by mass or less.

8. The external skin preparation according to claim 1 or 2, wherein The content of the component (B) is 2.5% by mass or more and 5% by mass or less.

9. The external skin preparation according to claim 1 or 2, wherein The content mass ratio (B) / (A) of the component (B) to the component (A) is 0.01 or more and 1.5 or less.

10. The external skin preparation according to claim 1 or 2, wherein The content mass ratio (B) / (A) of the component (B) to the component (A) is 0.1 or more and 0.6 or less.

11. The external skin preparation according to claim 1 or 2, wherein The content mass ratio (A) / (C) of the component (A) to the component (C) is 0.01 or more and 1.5 or less.

12. The external skin preparation according to claim 1 or 2, wherein The content mass ratio (A) / (C) of the component (A) to the component (C) is 0.15 or more and 0.5 or less.

13. The external skin preparation according to claim 1 or 2, wherein The content mass ratio of the total of the components (A) and (B) to the component (C) ((A)+(B)) / (C) is 0.02 or more and 3 or less.

14. The external skin preparation according to claim 1 or 2, wherein The content mass ratio of the total of the components (A) and (B) to the component (C) ((A)+(B)) / (C) is 0.23 or more and 0.3 or less.

15. The external skin preparation according to claim 1, wherein Component (D) is a non-volatile ester oil.

16. The external skin preparation according to claim 1 or 2, wherein It contains at least (C-1) a volatile silicone oil as the component (C).

17. The external skin preparation according to claim 16, wherein The content of the component (C-1) is 0.5% by mass or more and 30% by mass or less in the external preparation for skin.

18. The external skin preparation according to claim 16, wherein The content of the component (C-1) is 4% by mass or more and 15% by mass or less in the external preparation for skin.

19. The external skin preparation according to claim 1, wherein The content of the lower alcohol (C-2) in the external preparation for skin is 50% by mass or more and 80% by mass or less.

20. The external skin preparation according to claim 1 or 2, wherein It further contains (E) a film-forming agent.

21. The external skin preparation according to claim 20, wherein Component (E) is one or more selected from silicone-based film-forming agents and (meth)acrylic-based film-forming agents.

22. The external skin preparation according to claim 20, wherein The content of the component (E) is 0.1% by mass or more and 10% by mass or less in the external preparation for skin.

23. The external skin preparation according to claim 1 or 2, wherein The content of the ultraviolet scattering agent in the external preparation for skin is 0 mass % or more and 2.5 mass % or less.

24. The external skin preparation according to claim 1 or 2, wherein The content of the surfactant in the external preparation for skin is 0 mass % or more and 2.5 mass % or less.

25. The external skin preparation according to claim 1 or 2, wherein The content of water in the external preparation for skin is 0 mass % or more and 10 mass % or less.

26. The external skin preparation according to claim 1 or 2, wherein The skin external preparation is an aerosol spray type or a non-aerosol spray type.

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