Yu Jung-soo type oil painting sunscreen cosmetic

Abstract

The present invention provides a water-in-oil emulsion sunscreen cosmetic that has a good texture without a powdery feel, prevents atmospheric harmful substances from adhering well to the coating film, and also has an excellent UV protection effect. A water-in-oil emulsion sunscreen cosmetic containing the following ingredients (A1), (A2), (B) and (C), wherein (D) the content of non-volatile silicone oil is 0 mass% or more and 5 mass% or less. (A1) Hydrophobically treated particulate titanium oxide 5 mass% or more (A2) Hydrophobically treated fine zinc oxide 10 mass% or more (B) Divalent polyol (C) Non-volatile hydrocarbon oil 2 mass% or more and 14 mass% or less

Description

Technology Field

[0001] The present invention relates to a water-in-oil emulsion sunscreen cosmetic. Background Technology

[0002] Typically, sunscreen cosmetics contain UV absorbers or UV scattering agents such as titanium oxide and zinc oxide. However, since there is a demand for cosmetics that are more skin-friendly, research has been conducted to reduce the content of organic UV absorbers. As such, for example, a UV-blocking cosmetic containing a suspension of ultrafine zinc oxide of a specific particle size dispersed in a silicone-based oil is known (Patent Document 1). Prior art literature

[0003] Japanese Published Patent Application No. 2000-191490 means of solving the problem

[0004] The present invention provides a water-in-oil emulsion sunscreen cosmetic containing the following components (A1), (A2), (B) and (C), wherein the content of (D) non-volatile silicone oil is 0 mass% or more and 5 mass% or less.

[0005] (A1) Hydrophobically treated particulate titanium oxide 5 mass% or more

[0006] (A2) Hydrophobically treated fine zinc oxide 10 mass% or more

[0007] (B) Divalent polyol

[0008] (C) Non-volatile hydrocarbon oil 2 mass% or more and 14 mass% or less Brief explanation of the drawing

[0009] Figure 1 is a schematic diagram showing a method for evaluating the effect of inhibiting the attachment of hazardous substances in the atmosphere. Specific details for implementing the invention

[0010] Upon review by the inventors, it was found that the UV-blocking cosmetic composition described in Patent Document 1 has excellent dispersibility within the formulation, but the coating film tends to become uneven after application to the skin and subsequent drying, and as a result, the UV protection effect may be insufficient.

[0011] In addition, since skin damage caused by hazardous air pollutants can be a cause of atopic dermatitis, recently, there has been a demand not only to suppress damage caused by ultraviolet rays but also to suppress skin damage caused by hazardous air pollutants. Through the inventors' investigation, it was found that when non-volatile silicone oil is used in a low content or not at all, it becomes difficult for hazardous air pollutants to adhere to the coating film of the cosmetic product; however, it was found that in this case, another problem arises in that the sensation of use during application feels like powder.

[0012] The present invention relates to providing a water-in-oil emulsion sunscreen cosmetic that has a good texture without a powdery feel, prevents atmospheric harmful substances from adhering well to the coating film, and also has an excellent UV protection effect.

[0013] The inventors have discovered that a water-in-oil emulsion sunscreen cosmetic composition, which contains a high content of hydrophobically treated fine particulate titanium oxide and a high content of hydrophobically treated fine particulate zinc oxide, a divalent polyol, a non-volatile hydrocarbon oil content of 2 mass% or more and 14 mass% or less, and a non-volatile silicone oil content of 0 mass% or more and 5 mass% or less, has a good texture without a powdery feel, prevents harmful atmospheric substances from adhering well to the coating film, and also has an excellent UV protection effect, thereby completing the present invention.

[0014] The water-in-oil emulsion sunscreen cosmetic of the present invention has a good texture without a powdery feel, prevents atmospheric harmful substances from adhering well to the coating film, and also has an excellent UV protection effect.

[0015] <Components (A1), (A2)>

[0016] The water-in-oil emulsion sunscreen cosmetic of the present invention contains (A1) hydrophobically treated particulate titanium oxide and (A2) hydrophobically treated particulate zinc oxide. In addition, trace elements with a valence of +2 or higher may be included in the particulate titanium oxide and particulate zinc oxide, and metals such as iron, zirconium, calcium, manganese, magnesium, and yttrium may be included in the particulate titanium oxide and particulate zinc oxide either alone or in combination of two or more types.

[0017] The shape of the above “hydrophobically treated titanium oxide” and “hydrophobically treated zinc oxide” is not particularly limited, and examples include spherical, plate-like, rod-like, spindle-like, needle-like, irregular shapes, etc.

[0018] In addition, the average primary particle size d of the above "hydrophobically treated titanium oxide microparticles" and "hydrophobically treated zinc oxide microparticles" A From the perspective of improving the UV protection effect, 1 nm or more is preferable, 5 nm or more is more preferable, 100 nm or less is preferable, and 80 nm or less is more preferable. Furthermore, from the perspective of improving the effect of inhibiting the attachment of hazardous atmospheric substances, 1 nm or more is preferable, 7 nm or more is more preferable, 200 nm or less is preferable, 80 nm or less is more preferable, and 50 nm or less is even more preferable. Average primary particle diameter d A The specific range is preferably 1 nm or more and 200 nm or less, more preferably 5 nm or more and 200 nm or less, even more preferably 5 nm or more and 100 nm or less, even more preferably 7 nm or more and 100 nm or less, even more preferably 7 nm or more and 80 nm or less, and particularly preferably 7 nm or more and 50 nm or less, in terms of improving the UV protection effect and the effect of inhibiting adhesion of hazardous substances in the atmosphere.

[0019] Average primary particle size d in this specification A It can be obtained from observation images obtained by a transmission electron microscope (TEM). Specifically, it is obtained by observing with a TEM at a magnification of 50,000x, measuring the maximum short diameter of 300 primary particles in the observation image, and calculating the number average value. Here, the maximum short diameter refers to the short diameter having the maximum length among the short diameters orthogonal to the major diameter when the "hydrophobically treated titanium oxide particulates" or "hydrophobically treated zinc oxide particulates" have a shape other than a plate. Also, when the "hydrophobically treated titanium oxide particulates" or "hydrophobically treated zinc oxide particulates" are plate-shaped, it is obtained by measuring the thickness of 300 primary particles in the observation image observed under the same conditions as above and calculating the number average value.

[0020] Components (A1) and (A2) are particulate titanium oxide and particulate zinc oxide that have been hydrophobized. Through hydrophobization treatment, the dispersibility of particulate titanium oxide and particulate zinc oxide is improved, and the effect of inhibiting the attachment of hazardous atmospheric substances is also enhanced.

[0021] Examples of hydrophobization treatments include silicon treatment; alkylalkoxysilane treatment; fatty acid treatment; treatment with fluorine-containing compounds such as perfluoroalkyl phosphate esters, perfluoroalcohols, and perfluoroalkylalkoxysilanes; amino acid treatment such as N-acylglutamic acid; and alkyl phosphate ester treatment.

[0022] Among these, fatty acid treatment is preferred from the perspective of increasing the dispersibility of ingredient (A1) in the cosmetic and improving the UV protection effect. Also, silicone treatment and alkylalkoxysilane treatment are preferred from the perspective of increasing the dispersibility of ingredient (A2) and improving the UV protection effect.

[0023] As surface treatment agents used for fatty acid treatment, examples include straight-chain or branched-chain fatty acids with 12 to 22 carbon atoms or salts thereof. Among these, from the perspective of increasing the dispersibility of ingredients (A1) and (A2) in the cosmetic product and improving the effect of inhibiting adhesion of harmful atmospheric substances, straight-chain or branched-chain fatty acids or salts thereof with 14 to 22 carbon atoms are preferred, straight-chain or branched-chain fatty acids or salts thereof with 16 to 20 carbon atoms are more preferred, and stearic acid, aluminum stearate, isostearic acid, and aluminum isostearate are even more preferred.

[0024] Various silicone oils such as dimethylpolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, methylcyclopolysiloxane, dodecamethylcyclohexasiloxane, tetradecamethylhexasiloxane, dimethylsiloxane / methyl(polyoxyethylene)siloxane / methyl(polyoxypropylene)siloxane copolymer, dimethylsiloxane / methyl(polyoxyethylene)siloxane copolymer, dimethylsiloxane / methyl(polyoxypropylene)siloxane copolymer, dimethylsiloxane / methylcetyloxysiloxane copolymer, dimethylsiloxane / methylstearoxysiloxane copolymer, and alkyl acrylate / dimethicone copolymer can be used as surface treatment agents for silicone treatment. Among these, methylhydrogenpolysiloxane and dimethylpolysiloxane are preferred from the perspective of increasing the dispersibility of ingredients (A1) and (A2) in cosmetics and improving the effect of inhibiting the attachment of hazardous atmospheric substances.

[0025] As a surface treatment agent used for alkylalkoxysilane treatment, alkylalkoxysilane having a straight or branched alkyl group having 6 to 20 carbon atoms is preferred, and octyltriethoxysilane and octyltrimethoxysilane are more preferred, in order to increase the dispersibility of components (A1) and (A2) in the cosmetic product and to improve the effect of inhibiting adhesion of hazardous atmospheric substances.

[0026] Commercially available hydrophobically treated particulate titanium oxide (A1) products include the MT-100 series, JR series, and MPY series manufactured by Teika Co., Ltd., the STR-100 series manufactured by Sakai Chemical Industry Co., Ltd., and the TTO55 series, TTO51 series, and MPT series manufactured by Ishihara Sangyo Co., Ltd. Commercially available hydrophobically treated particulate zinc oxide (A2) products include the MZ-500 series and MZ-300 series manufactured by Teika Co., Ltd., and the FINEX-50 series, FINEX-30 series, and FINEX-25 series manufactured by Sakai Chemical Industry Co., Ltd.

[0027] The aforementioned surface treatment agent may be used as a single type or in combination of two or more types.

[0028] The amount of the surface treatment agent is preferably 0.1 mass% or more with respect to the total mass of component (A1) or the total mass of component (A2), with respect to increasing the dispersibility of component (A1) and component (A2) in the cosmetic product, and improving the UV protection effect and the effect of inhibiting adhesion of harmful atmospheric substances. It is also preferably 40 mass% or less, more preferably 30 mass% or less.

[0029] In addition, the above throughput refers to the amount when the sum of fine titanium oxide or fine zinc oxide and the surface treatment agent is 100 mass%. Also, the above average primary particle size d A , the content or mass ratio in the cosmetic composition described below, and the average primary particle size d including the surface treatment agent A , refers to the content and the ratio of the mass of the contents.

[0030] The content of hydrophobically treated fine titanium oxide particles is 5 mass% or more in the water-in-oil emulsion sunscreen cosmetic of the present invention. By making the content of hydrophobically treated fine titanium oxide particles 5 mass% or more, the UV protection effect is improved, so that a high UV protection effect can be obtained even when the content of UV absorbers is low or when UV absorbers are not used.

[0031] The content of hydrophobically treated fine titanium oxide particles is preferably 6 mass% or more, more preferably 7 mass% or more, and even more preferably 8 mass% or more in the water-in-oil emulsion sunscreen cosmetic of the present invention from the perspective of UV protection effect, etc., and is also preferably 25 mass% or less, more preferably 20 mass% or less, and even more preferably 15 mass% or less in the water-in-oil emulsion sunscreen cosmetic of the present invention from the perspective of no powdery feel, no white residue, and smoothness upon application. Specifically, in the water-in-oil emulsion sunscreen cosmetic of the present invention, 6 mass% or more and 25 mass% or less is preferred, 7 mass% or more and 20 mass% or less is more preferred, and 8 mass% or more and 15 mass% or less is even more preferred. Furthermore, when the content of hydrophobically treated fine titanium oxide particles is 8 mass% or more, the UV protection effect is particularly improved.

[0032] The content of hydrophobically treated fine particulate zinc oxide is 10 mass% or more in the water-in-oil emulsion sunscreen cosmetic of the present invention. By making the content of hydrophobically treated fine particulate zinc oxide 10 mass% or more, the UV protection effect is improved, so that a high UV protection effect can be obtained even when the content of UV absorbers is low or when UV absorbers are not used.

[0033] The content of hydrophobically treated fine particulate zinc oxide is preferably 12 mass% or more, more preferably 13 mass% or more, even more preferably 15 mass% or more, and particularly preferably 17 mass% or more in the water-in-oil emulsion sunscreen cosmetic of the present invention from the perspective of UV protection effect, etc., and is also preferably 35 mass% or less, more preferably 30 mass% or less, and even more preferably 25 mass% or less in the water-in-oil emulsion sunscreen cosmetic of the present invention from the perspective of no powdery feel, no white flaking, and smoothness upon application. As for specific ranges, in the water-in-oil emulsion sunscreen cosmetic of the present invention, 12 mass% or more and 35 mass% or less is preferred, 13 mass% or more and 30 mass% or less is more preferred, 15 mass% or more and 25 mass% or less is even more preferred, and 17 mass% or more and 25 mass% or less is particularly preferred. In addition, when the content of hydrophobically treated fine zinc oxide particles is 17 mass% or more, the UV protection effect is particularly improved.

[0034] The water-in-oil emulsion sunscreen cosmetic of the present invention may contain an ultraviolet scattering agent other than ingredients (A1) and (A2) as ingredient (A3). Examples of such ultraviolet scattering agents include hydrophobically treated microparticle cerium oxide, hydrophobically treated microparticle iron oxide, hydrophobically treated microparticle chromium oxide, etc. The hydrophobically treated agent in ingredient (A3) may be the same as the hydrophobically treated agent described in ingredients (A1) and (A2). Furthermore, these ultraviolet scattering agents may be used as a single type or in combination of two or more types.

[0035] As for the content of component (A3), in the water-in-oil emulsion sunscreen cosmetic of the present invention, 0 mass% or more and 5 mass% or less is preferred, 0 mass% or more and 2.5 mass% or less is more preferred, 0 mass% or more and 1 mass% or less is even more preferred, 0 mass% or more and 0.5 mass% or less is even more preferred, and 0 mass% is particularly preferred.

[0036] <Component (B)>

[0037] The water-in-oil emulsion sunscreen cosmetic of the present invention contains (B) a divalent polyol. In addition, "divalent polyol" means an alcohol having two hydroxyl groups within the same molecule. By including a divalent polyol, the coating film after drying becomes more uniform and has excellent UV protection effects.

[0038] Examples of divalent polyols include alkylene glycols such as ethylene glycol, propylene glycol, and 1,3-butylene glycol; dialkylene glycols such as diethylene glycol and dipropylene glycol; and polyalkylene glycols such as polyethylene glycol and polypropylene glycol. Among these, alkylene glycols and dialkylene glycols are preferred, dialkylene glycols are more preferred, and dipropylene glycols are particularly preferred, from the perspective of uniformity of the coating film after drying, UV protection effect, and lack of powderiness.

[0039] In addition, the number of carbon atoms in the divalent polyol is preferably 1 or more and 12 or less, more preferably 2 or more and 10 or less, even more preferably 2 or more and 8 or less, and particularly preferably 4 or more and 8 or less.

[0040] The divalent polyol may be a commercially available product or one obtained by synthesis according to conventional methods. Examples of commercially available 1,3-butylene glycol include 1,3-butylene glycol-P (manufactured by KH Neochem Co., Ltd.). Examples of commercially available dipropylene glycol include DPG-RF (manufactured by ADEKA Co., Ltd.).

[0041] In addition, divalent polyols may be used alone or in combination of two or more types.

[0042] The content of the divalent polyol is preferably 1 mass% or more, more preferably 3 mass% or more, even more preferably 4 mass% or more, and particularly preferably 4.5 mass% or more in the water-in-oil emulsion sunscreen cosmetic of the present invention, in terms of uniformity of the coating film after drying, UV protection effect, and lack of powderiness; additionally, in terms of non-stickiness and emulsion stability, it is preferably 14 mass% or less, more preferably 12 mass% or less, even more preferably 10 mass% or less, and particularly preferably 8 mass% or less in the water-in-oil emulsion sunscreen cosmetic of the present invention. As for specific ranges, in the water-in-oil emulsion sunscreen cosmetic of the present invention, 1 mass% or more and 14 mass% or less is preferred, 3 mass% or more and 12 mass% or less is more preferred, 4 mass% or more and 10 mass% or less is even more preferred, and 4.5 mass% or more and 8 mass% or less is particularly preferred. In addition, when the content of divalent polyol is 1 mass% or more, the uniformity of the coating film after drying, the UV protection effect, and the absence of powderiness are particularly improved.

[0043] In addition, the mass ratio of component (B) to the sum of components (A1) and (A2) [(B) / ((A1) + (A2))] is preferably 0.05 or higher, more preferably 0.1 or higher, and even more preferably 0.125 or higher from the perspective of uniformity of the coating film after drying, UV protection effect, reduction of powderiness during application, and improvement of smooth texture, and is also preferably 0.75 or lower, more preferably 0.5 or lower, and even more preferably 0.4 or lower from the perspective of non-stickiness. Specifically, the range is preferably 0.05 or higher and 0.75 or lower, more preferably 0.1 or higher and 0.5 or lower, and even more preferably 0.125 or higher and 0.4 or lower.

[0044] <Component (C)>

[0045] The water-in-oil emulsion sunscreen cosmetic of the present invention contains (C) a non-volatile hydrocarbon oil.

[0046] The non-volatile hydrocarbon oil may be a liquid hydrocarbon oil that does not exhibit volatility at 25°C under 1 atmosphere. The flash point of the non-volatile hydrocarbon oil at 25°C under 1 atmosphere is preferably 100°C or higher. Among the non-volatile hydrocarbon oils at 25°C under 1 atmosphere, it is preferable that the viscosity be 300 mPa·s or lower at 25°C, more preferably 150 mPa·s or lower, and even more preferably 100 mPa·s or lower, from the perspective of having no powdery feel, no stickiness, and good spreadability. Examples include liquid paraffin, liquid isoparaffin, squalane, etc., and one of these may be used alone or two or more may be used in combination.

[0047] In addition, the viscosity of component (C) is measured using a Type B viscometer TVB-10 (manufactured by Toki Sangyo Co., Ltd.) under conditions of rotor 2, 25°C, and 30 rpm.

[0048] Commercially available liquid isoparaffins include Perlim EX and Perlim 6 (both manufactured by Nichiyu Co., Ltd.). Commercially available squalanes include Nichol Squalane (manufactured by Nippon Surfactant Co., Ltd.).

[0049] The content of non-volatile hydrocarbon oil is 2 mass% or more and 14 mass% or less in the water-in-oil emulsion sunscreen cosmetic of the present invention. By setting the content of non-volatile hydrocarbon oil to this range, the powdery texture is improved, and a smooth texture with less roughness is obtained.

[0050] The content of non-volatile hydrocarbon oil is preferably 4 mass% or more, more preferably 5 mass% or more, and even more preferably 6 mass% or more in the oil-in-water emulsion sunscreen cosmetic of the present invention, from the perspective of reducing the powdery sensation upon application and improving the smooth texture upon application; additionally, in the perspective of the absence of an oily sensation, the content of non-volatile hydrocarbon oil is preferably 14 mass% or less, more preferably 13 mass% or less, and even more preferably 12 mass% or less in the oil-in-water emulsion sunscreen cosmetic of the present invention. As for specific ranges, in the oil-in-water emulsion sunscreen cosmetic of the present invention, 4 mass% or more and 14 mass% or less is preferred, 4 mass% or more and 13 mass% or less is more preferred, 5 mass% or more and 13 mass% or less is even more preferred, and 6 mass% or more and 12 mass% or less is particularly preferred. Furthermore, when the content of non-volatile hydrocarbon oil is 6 mass% or more, the absence of a powdery sensation is particularly improved.

[0051] In addition, the mass ratio of component (C) to the sum of components (A1) and (A2) [(C) / ((A1) + (A2))] is preferably 0.05 or higher, more preferably 0.1 or higher, even more preferably 0.2 or higher, and particularly preferably 0.3 or higher, from the perspective of reducing powderiness upon application, suppressing roughness, improving smoothness upon application, and moisturizing sensation after application; and in addition, it is preferably 1.5 or lower, more preferably 1 or lower, even more preferably 0.75 or lower, and particularly preferably 0.39 or lower, from the perspective of UV protection effect and inhibition of adhesion of harmful atmospheric substances. Specifically, the range is preferably 0.05 or higher and 1.5 or lower, more preferably 0.1 or higher and 1 or lower, even more preferably 0.2 or higher and 0.75 or lower, and particularly preferably 0.3 or higher and 0.39 or lower.

[0052] <Component (D)>

[0053] The non-volatile silicone oil may be a liquid silicone oil that does not exhibit volatility at 25°C under 1 atmosphere.

[0054] Examples of non-volatile silicone oils include non-volatile chain-type polysiloxanes such as dimethylpolysiloxane, methylphenylpolysiloxane, and methylhydrogenpolysiloxane; and non-volatile cyclic polysiloxanes such as tetramethyltetrahydrogenpolysiloxane. Additionally, one of these may be used alone, or two or more may be used in combination. Among these, dimethylpolysiloxane and methylphenylpolysiloxane are preferred.

[0055] The kinematic viscosity of the non-volatile silicone oil at 25°C is preferably 300 mm² / s or less, more preferably 150 mm² / s or less, even more preferably 100 mm² / s or less, particularly preferably 50 mm² / s or less, and also preferably 3 mm² / s or more, in terms of the duration of moisturizing sensation and skin smoothness, non-stickiness, and good spreadability.

[0056] Commercially available dimethylpolysiloxane products include KF-96L-6CS and KF-96A-10CS (both manufactured by Shin-Etsu Chemical Co., Ltd.). Commercially available methylphenylpolysiloxane products include SH556Fluid (manufactured by Toray Dow).

[0057] The water-in-oil emulsion sunscreen cosmetic of the present invention may or may not include non-volatile silicone oil, and the content of non-volatile silicone oil is 0 mass% or more and 5 mass% or less in the water-in-oil emulsion sunscreen cosmetic of the present invention. By making the content of non-volatile silicone oil 0 mass% or more and 5 mass% or less, the effect of inhibiting the attachment of hazardous substances to the atmosphere is improved.

[0058] The content of non-volatile silicone oil is preferably 0.1 mass% or more, more preferably 0.5 mass% or more, in the oil-in-water emulsion sunscreen cosmetic of the present invention, from the perspective of the effect of inhibiting stickiness or the persistence of skin smoothness; additionally, in the perspective of the effect of inhibiting adhesion of hazardous airborne substances and the absence of an oily sensation, it is preferably 4 mass% or less, more preferably 3 mass% or less, in the oil-in-water emulsion sunscreen cosmetic of the present invention. As for specific ranges, in the oil-in-water emulsion sunscreen cosmetic of the present invention, 0 mass% or more and 4 mass% or less is preferred, 0 mass% or more and 3 mass% or less is more preferred, 0.1 mass% or more and 3 mass% or less is even more preferred, and 0.5 mass% or more and 3 mass% or less is particularly preferred. Furthermore, when the content of non-volatile silicone oil is 4 mass% or less or 3 mass% or less, the effect of inhibiting adhesion of hazardous airborne substances is particularly improved.

[0059] In addition, the mass ratio of component (D) to the sum of components (A1) and (A2) [(D) / ((A1) + (A2))] is preferably 0 or more, more preferably 0.005 or more, even more preferably 0.01 or more, and particularly preferably 0.025 or more from the perspective of anti-stickiness effect and persistence of skin smoothness, and is also preferably 0.5 or less, more preferably 0.25 or less, even more preferably 0.2 or less, even more preferably 0.15 or less, even more preferably 0.1 or less, and particularly preferably 0.06 or less from the perspective of UV protection effect, inhibition of adhesion of harmful atmospheric substances, and lack of oiliness. As for the specific range, 0 or more and 0.5 or less is preferred, 0.005 or more and 0.25 or less is more preferred, 0.01 or more and 0.15 or less is even more preferred, and 0.025 or more and 0.1 or less is particularly preferred.

[0060] In addition, the mass ratio of component (D) to component (C) [(D) / (C)] is preferably 0 or more, more preferably 0.05 or more, even more preferably 0.075 or more, and particularly preferably 0.1 or more, from the perspective of suppressing roughness of the skin, reducing powderiness, and improving the persistence of smoothness of the skin; and in addition, it is preferably 1 or less, more preferably 0.75 or less, even more preferably 0.5 or less, and particularly preferably 0.2 or less, from the perspective of reducing powderiness, improving smooth texture, and improving the effect of inhibiting adhesion of harmful atmospheric substances. As for specific ranges, 0 or more and 1 or less is preferred, 0.05 or more and 0.75 or less is more preferred, 0.075 or more and 0.5 or less is even more preferred, and 0.1 or more and 0.2 or less is particularly preferred.

[0061] <Component (E)>

[0062] (E) The water content is preferably 1 mass% or more, more preferably 3 mass% or more, and even more preferably 5 mass% or more in the oil-in-water emulsion sunscreen cosmetic of the present invention in terms of emulsion stability, lack of oiliness, etc., and is also preferably 25 mass% or less, more preferably 20 mass% or less, even more preferably 17.5 mass% or less, and particularly preferably 15 mass% or less in the oil-in-water emulsion sunscreen cosmetic of the present invention in terms of water resistance, good spreadability, lack of stickiness, etc. As for the specific range, in the oil-in-water emulsion sunscreen cosmetic of the present invention, 1 mass% or more and 25 mass% or less is preferred, 1 mass% or more and 20 mass% or less is more preferred, 3 mass% or more and 17.5 mass% or less is even more preferred, and 5 mass% or more and 15 mass% or less is particularly preferred.

[0063] In the water-in-oil emulsion sunscreen cosmetic of the present invention, in terms of the effect of inhibiting adhesion of hazardous atmospheric substances, emulsion stability, dispersion stability, etc., in addition to each of the above components, it is preferable to contain one or more selected from (F) a non-volatile oil other than components (C) and (D), (G) a volatile oil, (H) a surfactant, (I) a powder other than components (A1) to (A3), and (J) an oily thickener; and the composition contains components (A1), (A2), (B), (C), (E), and (F), with a content of component (D) of 0 mass% or more and 5 mass% or less, the composition contains components (A1), (A2), (B), (C), (E), and (G), with a content of component (D) of 0 mass% or more and 5 mass% or less, or the composition contains components (A1), (A2), (B), (C), (E), and (J), with a content of component (D) of 0 It is more preferable that the mass% is 5 mass% or more and 5 mass% or less, and it is even more preferable that the content of component (D) is 0 mass% or more and 5 mass% or less, and it is particularly preferable that the content of component (D) is 0 mass% or more and 5 mass% or less, and it is especially preferable that the content of component (D) is 0 mass% or more and 5 mass% or less.

[0064] <Ingredient (F)>

[0065] Non-volatile oil other than components (C) and (D) means a liquid oil that does not exhibit volatility at 25°C under 1 atmosphere, excluding components (C) and (D) and a liquid ultraviolet absorber at 25°C under 1 atmosphere.

[0066] As for the nonvolatile oil other than components (C) and (D), nonvolatile ester oils are preferred. Examples include nonvolatile fatty acid ester oils such as 2-ethylhexanoate, isononyl isononanate, isotridecyl isononanate, isopropyl myristate, isopropyl palmitate, 2-ethylhexyl palmitate, 2-ethylhexyl stearate, stearyl stearate; alkyl benzoate (C12-15), etc. In addition, as nonvolatile fatty acid ester oils, fatty acid triglycerides such as tri(caprylic acid / capric acid)glyceryl and tri(2-ethylhexanoate)glyceryl; esters of fatty acids and neopentyl glycol such as neopentyl glycol dicapricate and neopentyl glycol diethylhexanoate; and other polyhydric alcohol fatty acid ester oils may be used.

[0067] Among these, non-volatile fatty acid ester oils are preferred in terms of the effect of inhibiting adhesion of harmful atmospheric substances and good skin compatibility, non-volatile polyalcohol fatty acid ester oils are more preferred, and fatty acid triglycerides and esters of fatty acids and neopentyl glycol are particularly preferred.

[0068] Examples of commercially available isopropyl palmitate include ExePul IPP (manufactured by Kao Co., Ltd.). Examples of commercially available alkyl benzoate (C12-15) include FINSOLV TN (manufactured by Innospec Active Chemicals Co., Ltd.). Examples of commercially available tri(2-ethylhexanoate)glyceryl include ExePul TGO (manufactured by Kao Co., Ltd.). Examples of commercially available neopentyl glycol dicapricate include Estemol N-01 (manufactured by Nissin Oilio Group Co., Ltd.). Examples of commercially available neopentyl glycol diethylhexanoate include Cosmol 525 (manufactured by Nissin Oilio Group Co., Ltd.).

[0069] In addition, nonvolatile oils other than components (C) and (D) may be used as a single type or in combination of two or more types.

[0070] When a nonvolatile ester oil is used as a nonvolatile oil other than components (C) and (D), the content of the nonvolatile ester oil is preferably 0.5 mass% or more and 15 mass% or less in the water-in-oil emulsion sunscreen cosmetic of the present invention, more preferably 1 mass% or more and 10 mass% or less, and particularly preferably 3 mass% or more and 7.5 mass% or less. By setting the content of the nonvolatile ester oil to this range, the effect of inhibiting the attachment of hazardous atmospheric substances becomes even more excellent.

[0071] <Component (G)>

[0072] Volatile oil may be any liquid oil that exhibits volatility at 25°C under 1 atmosphere. Examples of volatile oils include volatile silicone oil and volatile hydrocarbon oil. The flash point of the volatile hydrocarbon oil is preferably 100°C or lower, and more preferably 35°C or higher and 100°C or lower.

[0073] Examples of volatile silicone oils include volatile cyclic silicone oils such as octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane; and straight-chain or branched volatile silicone oils such as octamethyltrisiloxane, methyltrimethicone, ethyltrisiloxane, decamethyltetrasiloxane, and volatile dimethylpolysiloxane.

[0074] The kinematic viscosity of the volatile dimethylpolysiloxane at 25°C is preferably 0.5 mm² / s or more and 2 mm² / s or less, and more preferably 0.65 mm² / s or more and 2 mm² / s or less.

[0075] Examples of volatile hydrocarbon oils include, for instance, paraffinic volatile hydrocarbon oils such as n-decane, n-undecane, and n-dodecane; and isoparaffinic volatile hydrocarbon oils such as isodecane, isododecane, and light liquid isoparaffin.

[0076] Commercially available decamethylcyclopentasiloxane products include TSF405A (manufactured by Momentive Performance Materials Japan), SH245, DC345 (manufactured by Toray Dow Corning), and KF-995 (manufactured by Shin-Etsu Chemical Co., Ltd.). Commercially available methyltrimethicone products include Silicon TMF-1.5 (manufactured by Shin-Etsu Chemical Co., Ltd.). Commercially available ethyltrisiloxane products include SILSOFTETS (manufactured by Momentive Performance Materials Japan). Commercially available decamethyltetrasiloxane products include KF-96L-1.5CS (manufactured by Shin-Etsu Chemical Co., Ltd.). Commercially available volatile dimethylpolysiloxane products include KF-96L-2CS (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0077] In addition, commercially available hard liquid isoparaffins include Pearlim 4 (manufactured by Nichiyu Co., Ltd.).

[0078] In addition, volatile oils may be used as a single type or in combination of two or more types.

[0079] Regarding the volatile oil content, in terms of good spreadability and lack of oiliness, among other things, in the water-in-oil emulsion sunscreen cosmetic of the present invention, 0 mass% or more and 50 mass% or less is preferred, 5 mass% or more and 40 mass% or less is more preferred, and 10 mass% or more and 35 mass% or less is particularly preferred.

[0080] <Component (H)>

[0081] For the surfactant, known surfactants such as anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants may be used, but nonionic surfactants are preferred from the perspective of water resistance and ease of formulation, and nonionic surfactants with an HLB of 8 or lower (preferably HLB 1 to 7, more preferably HLB 2 to 6, particularly preferably HLB 3 to 5) are more preferred. In addition, the surfactant is preferably in a liquid state at 25°C.

[0082] Here, HLB is an indicator representing the hydrophilic-lipophilic balance and is defined by the following equation by Oda, Teramura, et al.

[0083] HLB = (ΣInorganic Value / ΣOrganic Value) × 10

[0084] Examples of nonionic surfactants include polyhydric alcohol fatty acid ester type surfactants, polyoxyethylene fatty acid ester type surfactants, polyether-modified silicone type surfactants, and polyoxyethylene alkyl ether type surfactants. Among these, polyhydric alcohol fatty acid ester type surfactants and polyether-modified silicone type surfactants are preferred.

[0085] Examples of polyhydric alcohol fatty acid ester type surfactants include glycerin fatty acid ester type surfactants, sorbitan fatty acid ester type surfactants, diglycerin fatty acid ester type surfactants, polyglycerin fatty acid ester type surfactants, propylene glycol fatty acid ester type surfactants, etc. Among these, sorbitan fatty acid ester type surfactants are preferred, and sorbitan mono fatty acid ester type surfactants are particularly preferred. Specifically, examples include sorbitan monostearate, sorbitan monoisostearate, and sorbitan monooleate.

[0086] As polyether-modified silicone-type surfactants, polyoxyethylene-methylpolysiloxane copolymers and poly(oxyethylene-oxypropylene)methylpolysiloxane copolymers are preferred. Specifically, examples include PEG-3 dimethicone, PEG-9 dimethicone, PEG-10 dimethicone, etc.

[0087] In addition, surfactants may be used as a single type or in combination of two or more types.

[0088] Regarding the content of the surfactant, in terms of improving powder dispersibility, emulsion stability, and the absence of stickiness, in the water-in-oil emulsion sunscreen cosmetic of the present invention, 0.2 mass% or more and 10 mass% or less is preferred, 0.5 mass% or more and 8 mass% or less is more preferred, and 1 mass% or more and 5 mass% or less is particularly preferred.

[0089] <Component (I)>

[0090] Powders other than components (A1) to (A3) may include, for example, hydrophobically treated talc, cellulose particles, porous silica, cross-linked (meth)acrylic acid ester-based resin particles, silicone resin particles, etc. In addition, only one of these may be used alone, or two or more may be used in combination.

[0091] Regarding the content of powder other than ingredients (A1) to (A3), in the oil-in-water emulsion sunscreen cosmetic of the present invention, from the perspective of no powdery feeling, persistence of skin smoothness, and no stickiness, 0.2 mass% or more and 10 mass% or less is preferred, 0.5 mass% or more and 8 mass% or less is more preferred, and 1 mass% or more and 5 mass% or less is particularly preferred.

[0092] <Component (J)>

[0093] Examples of oily thickeners include, for instance, glycofatty acid ester-based oily thickeners such as inulin fatty acid esters and dextrin fatty acid esters, as well as isostearic acid polyglyceryl, (behenic acid / eicosanic acid)glyceryl, organic modified clay minerals, etc. In addition, one of these may be used alone, or two or more may be used in combination.

[0094] Among these, a glycofatty acid ester-based oily thickener is preferred in terms of the absence of an oily sensation or the persistence of skin smoothness. As for the fatty acid residues in the glycofatty acid ester-based oily thickener, straight-chain or branched-chain saturated fatty acid residues are preferred. In addition, the number of carbon atoms in the fatty acid residues is preferably 8 to 24, more preferably 12 to 22, and particularly preferably 14 to 20.

[0095] As for the glycofatty acid ester-based oily thickener, dextrin fatty acid esters are preferred. Specifically, examples include dextrin myristate, dextrin palmitate, dextrin stearate, (palmitic acid / 2-ethylhexanoic acid)dextrin, (palmitic acid / hexyldecanoic acid)dextrin, etc.

[0096] Regarding the content of the oil-based thickener, in terms of the absence of an oily sensation, the absence of stickiness, and the persistence of skin smoothness, in the water-in-oil emulsion sunscreen cosmetic of the present invention, 0.05 mass% or more and 5 mass% or less is preferred, 0.1 mass% or more and 4 mass% or less is more preferred, and 0.2 mass% or more and 3 mass% or less is particularly preferred.

[0097] The water-in-oil emulsion sunscreen cosmetic of the present invention may include, in addition to each of the above components, a film-forming agent such as trimethylsiloxysilicic acid; a polyol other than component (B); a lower alcohol; a wax; a preservative; a fragrance; a pH adjuster; a moisturizer; a texture enhancer; a sebum absorbent; a viscosity adjuster; vitamins such as tocopherol; terpenes such as carotene, etc. Furthermore, only one of these may be used alone, or two or more may be used in combination.

[0098] As for the content of the film-forming agent, in the water-in-oil emulsion sunscreen cosmetic of the present invention, 0 mass% or more and 0.075 mass% or less is preferred, 0 mass% or more and 0.01 mass% or less is more preferred, and 0 mass% is particularly preferred.

[0099] Examples of formulations of the water-in-oil emulsion sunscreen cosmetic of the present invention include non-solid forms such as liquid, cream, paste, and gel.

[0100] In addition, the water-in-oil emulsion sunscreen cosmetic of the present invention can be applied to the skin (preferably the skin excluding the scalp, more preferably the face, body, hands and feet, etc.) and used as a sunscreen. In addition, the method of use is not particularly limited, but it is preferable to apply it with hands or an application device.

[0101] The water-in-oil emulsion sunscreen cosmetic of the present invention can be manufactured according to a conventional method.

[0102] Furthermore, the water-in-oil emulsion sunscreen cosmetic of the present invention has a pleasant texture without a powdery feel, prevents atmospheric harmful substances from adhering well to the coating film, and also possesses an excellent UV protection effect. The inventors deduce that the reason such an excellent UV protection effect is exhibited is that the coating film after drying tends to become uniform, and the UV protection effect is obtained evenly.

[0103] In addition, the water-in-oil emulsion sunscreen cosmetic of the present invention can obtain a high UV protection effect even when the content of the UV absorber is low or when the UV absorber is not used. As for the content of the UV absorber, in the water-in-oil emulsion sunscreen cosmetic of the present invention, 0 mass% or more and 5 mass% or less is preferred, 0 mass% or more and 2.5 mass% or less is more preferred, 0 mass% or more and 1 mass% or less is even more preferred, 0 mass% or more and 0.5 mass% or less is even more preferred, and 0 mass% is particularly preferred.

[0104] With respect to the embodiments described above, the present invention further discloses the following cosmetic compositions, etc.

[0105] <1> A water-in-oil emulsion sunscreen cosmetic containing the following ingredients (A1), (A2), (B) and (C), wherein (D) the content of non-volatile silicone oil is 0 mass% or more and 5 mass% or less.

[0106] (A1) Hydrophobically treated particulate titanium oxide 5 mass% or more

[0107] (A2) Hydrophobically treated fine zinc oxide 10 mass% or more

[0108] (B) Divalent polyol

[0109] (C) Non-volatile hydrocarbon oil 2 mass% or more and 14 mass% or less

[0110] <2> Average primary particle size d of components (A1) and (A2) A A water-in-oil emulsion sunscreen cosmetic described in <1>, preferably 1 nm or more, more preferably 5 nm or more, and also preferably 100 nm or less, more preferably 80 nm or less.

[0111] <3> Average primary particle size d of components (A1) and (A2) A A water-in-oil emulsion sunscreen cosmetic described in <1>, preferably 1 nm or more, more preferably 7 nm or more, and also preferably 200 nm or less, more preferably 80 nm or less, and even more preferably 50 nm or less.

[0112] <4> Average primary particle size d of components (A1) and (A2) A A water-in-oil emulsion sunscreen cosmetic described in <1>, preferably 1 nm or more and 200 nm or less, more preferably 5 nm or more and 200 nm or less, even more preferably 5 nm or more and 100 nm or less, even more preferably 7 nm or more and 100 nm or less, even more preferably 7 nm or more and 80 nm or less, particularly preferably 7 nm or more and 50 nm or less.

[0113] <5> A water-in-oil emulsion sunscreen cosmetic described in any one of <1> to <4>, wherein the hydrophobization treatment of component (A1) is preferably selected from silicone treatment, alkylalkoxysilane treatment, fatty acid treatment, fluorine-containing compound treatment, amino acid treatment, and alkyl phosphate ester treatment, and more preferably fatty acid treatment.

[0114] <6> A water-in-oil emulsion sunscreen cosmetic described in any one of <1> to <5>, wherein the hydrophobization treatment of component (A2) is preferably selected from silicone treatment, alkylalkoxysilane treatment, fatty acid treatment, fluorine-containing compound treatment, amino acid treatment, and alkyl phosphate ester treatment, and more preferably selected from silicone treatment and alkylalkoxysilane treatment.

[0115] <7> A water-in-oil emulsion sunscreen cosmetic described in any one of <1> to <6>, wherein the content of component (A1) is preferably 6 mass% or more, more preferably 7 mass% or more, and even more preferably 8 mass% or more in the water-in-oil emulsion sunscreen cosmetic, and furthermore preferably 25 mass% or less, more preferably 20 mass% or less, and even more preferably 15 mass% or less in the water-in-oil emulsion sunscreen cosmetic.

[0116] <8> A water-in-oil emulsion sunscreen cosmetic described in any one of <1> to <6>, wherein the content of ingredient (A1) is preferably 6 mass% or more and 25 mass% or less, more preferably 7 mass% or more and 20 mass% or less, and even more preferably 8 mass% or more and 15 mass% or less.

[0117] <9> A water-in-oil emulsion sunscreen cosmetic described in any one of <1> to <8>, wherein the content of component (A2) is preferably 12 mass% or more, more preferably 13 mass% or more, even more preferably 15 mass% or more, particularly preferably 17 mass% or more, and furthermore, preferably 35 mass% or less, more preferably 30 mass% or less, even more preferably 25 mass% or less.

[0118] <10> A water-in-oil emulsion sunscreen cosmetic described in any one of <1> to <8>, wherein the content of ingredient (A2) is preferably 12 mass% or more and 35 mass% or less, more preferably 13 mass% or more and 30 mass% or less, even more preferably 15 mass% or more and 25 mass% or less, and particularly preferably 17 mass% or more and 25 mass% or less.

[0119] <11> A water-in-oil emulsion sunscreen cosmetic described in any one of <1> to <10>, wherein component (B) is preferably one or more selected from alkylene glycol, dialkylene glycol and polyalkylene glycol, more preferably one or more selected from alkylene glycol and dialkylene glycol, even more preferably dialkylene glycol, and particularly preferably dipropylene glycol.

[0120] <12> A water-in-oil emulsion sunscreen cosmetic described in any one of <1> to <11>, wherein the carbon number of component (B) is preferably 1 or more and 12 or less, more preferably 2 or more and 10 or less, even more preferably 2 or more and 8 or less, and particularly preferably 4 or more and 8 or less.

[0121] <13> A water-in-oil emulsion sunscreen cosmetic described in any one of <1> to <12>, wherein the content of component (B) is preferably 1 mass% or more, more preferably 3 mass% or more, even more preferably 4 mass% or more, particularly preferably 4.5 mass% or more, and furthermore, preferably 14 mass% or less, more preferably 12 mass% or less, even more preferably 10 mass% or less, and particularly preferably 8 mass% or less.

[0122] <14> A water-in-oil emulsion sunscreen cosmetic described in any one of <1> to <12>, wherein the content of component (B) is preferably 1 mass% or more and 14 mass% or less, more preferably 3 mass% or more and 12 mass% or less, even more preferably 4 mass% or more and 10 mass% or less, and particularly preferably 4.5 mass% or more and 8 mass% or less.

[0123] <15> A water-in-oil emulsion sunscreen cosmetic described in any one of <1> to <14>, wherein the mass ratio of component (B) to the sum of components (A1) and (A2) [(B) / ((A1) + (A2))] is preferably 0.05 or more, more preferably 0.1 or more, even more preferably 0.125 or more, and also preferably 0.75 or less, more preferably 0.5 or less, and even more preferably 0.4 or less.

[0124] <16> A water-in-oil emulsion sunscreen cosmetic described in any one of <1> to <14>, wherein the mass ratio of component (B) to the sum of components (A1) and (A2) [(B) / ((A1) + (A2))] is preferably 0.05 or more and 0.75 or less, more preferably 0.1 or more and 0.5 or less, and even more preferably 0.125 or more and 0.4 or less.

[0125] <17> A water-in-oil emulsion sunscreen cosmetic described in any one of <1> to <16>, wherein the flash point of component (C) is preferably 100°C or higher.

[0126] <18> A water-in-oil emulsion sunscreen cosmetic described in any one of <1> to <17>, wherein the viscosity of component (C) at 25°C is preferably 300 mPa·s or less, more preferably 150 mPa·s or less, and even more preferably 100 mPa·s or less.

[0127] <19> A water-in-oil emulsion sunscreen cosmetic described in any one of <1> to <18>, wherein component (C) is preferably one or more selected from liquid paraffin, liquid isoparaffin, and squalane.

[0128] <20> A water-in-oil emulsion sunscreen cosmetic described in any one of <1> to <19>, wherein the content of component (C) is preferably 4 mass% or more, more preferably 5 mass% or more, and even more preferably 6 mass% or more in the water-in-oil emulsion sunscreen cosmetic, and furthermore preferably 14 mass% or less, more preferably 13 mass% or less, and even more preferably 12 mass% or less in the water-in-oil emulsion sunscreen cosmetic.

[0129] <21> A water-in-oil emulsion sunscreen cosmetic described in any one of <1> to <19>, wherein the content of component (C) is preferably 4 mass% or more and 14 mass% or less, more preferably 4 mass% or more and 13 mass% or less, even more preferably 5 mass% or more and 13 mass% or less, and particularly preferably 6 mass% or more and 12 mass% or less.

[0130] <22> A water-in-oil emulsion sunscreen cosmetic described in any one of <1> to <21>, wherein the mass ratio of component (C) to the sum of components (A1) and (A2) [(C) / ((A1) + (A2))] is preferably 0.05 or more, more preferably 0.1 or more, even more preferably 0.2 or more, particularly preferably 0.3 or more, and also preferably 1.5 or less, more preferably 1 or less, even more preferably 0.75 or less, and particularly preferably 0.39 or less.

[0131] <23> A water-in-oil emulsion sunscreen cosmetic described in any one of <1> to <21>, wherein the mass ratio of component (C) to the sum of components (A1) and (A2) [(C) / ((A1) + (A2))] is preferably 0.05 or more and 1.5 or less, more preferably 0.1 or more and 1 or less, even more preferably 0.2 or more and 0.75 or less, and particularly preferably 0.3 or more and 0.39 or less.

[0132] <24> A water-in-oil emulsion sunscreen cosmetic described in any one of <1> to <23>, wherein component (D) is preferably one or more nonvolatile silicone oils selected from nonvolatile chain-type polysiloxanes and nonvolatile cyclic polysiloxanes, more preferably one or more nonvolatile silicone oils selected from dimethylpolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, and tetramethyltetrahydrogenpolysiloxane, and particularly preferably one or more nonvolatile silicone oils selected from dimethylpolysiloxane and methylphenylpolysiloxane.

[0133] <25> A water-in-oil emulsion sunscreen cosmetic described in any one of <1> to <24>, wherein the kinematic viscosity of component (D) at 25°C is preferably 300 mm² / s or less, more preferably 150 mm² / s or less, even more preferably 100 mm² / s or less, particularly preferably 50 mm² / s or less, and also preferably 3 mm² / s or more.

[0134] <26> A water-in-oil emulsion sunscreen cosmetic described in any one of <1> to <25>, wherein the content of component (D) is preferably 0.1 mass% or more, more preferably 0.5 mass% or more, in the water-in-oil emulsion sunscreen cosmetic, and preferably 4 mass% or less, more preferably 3 mass% or less, in the water-in-oil emulsion sunscreen cosmetic.

[0135] <27> A water-in-oil emulsion sunscreen cosmetic described in any one of <1> to <25>, wherein the content of component (D) is preferably 0 mass% or more and 4 mass% or less, more preferably 0 mass% or more and 3 mass% or less, even more preferably 0.1 mass% or more and 3 mass% or less, and particularly preferably 0.5 mass% or more and 3 mass% or less.

[0136] <28> A water-in-oil emulsion sunscreen cosmetic described in any one of <1> to <27>, wherein the mass ratio of component (D) to the sum of components (A1) and (A2) [(D) / ((A1) + (A2))] is preferably 0 or more, more preferably 0.005 or more, even more preferably 0.01 or more, particularly preferably 0.025 or more, and also preferably 0.5 or less, more preferably 0.25 or less, even more preferably 0.2 or less, even more preferably 0.15 or less, even more preferably 0.1 or less, and particularly preferably 0.06 or less.

[0137] <29> A water-in-oil emulsion sunscreen cosmetic described in any one of <1> to <27>, wherein the mass ratio of component (D) to the sum of components (A1) and (A2) [(D) / ((A1) + (A2))] is preferably 0 or more and 0.5 or less, more preferably 0.005 or more and 0.25 or less, even more preferably 0.01 or more and 0.15 or less, and particularly preferably 0.025 or more and 0.1 or less.

[0138] <30> A water-in-oil emulsion sunscreen cosmetic described in any one of <1> to <29>, wherein the mass ratio [(D) / (C)] of component (D) to component (C) is preferably 0 or more, more preferably 0.05 or more, even more preferably 0.075 or more, particularly preferably 0.1 or more, and also preferably 1 or less, more preferably 0.75 or less, even more preferably 0.5 or less, and particularly preferably 0.2 or less.

[0139] <31> A water-in-oil emulsion sunscreen cosmetic described in any one of <1> to <29>, wherein the mass ratio of component (D) to component (C) [(D) / (C)] is preferably 0 or more and 1 or less, more preferably 0.05 or more and 0.75 or less, even more preferably 0.075 or more and 0.5 or less, and particularly preferably 0.1 or more and 0.2 or less.

[0140] <32> (E) A water-in-oil emulsion sunscreen cosmetic described in any one of <1> to <31>, wherein the water content is preferably 1 mass% or more, more preferably 3 mass% or more, even more preferably 5 mass% or more, and also preferably 25 mass% or less, more preferably 20 mass% or less, even more preferably 17.5 mass% or less, particularly preferably 15 mass% or less.

[0141] <33> (E) A water-in-oil emulsion sunscreen cosmetic described in any one of <1> to <31>, wherein the water content is preferably 1 mass% or more and 25 mass% or less, more preferably 1 mass% or more and 20 mass% or less, even more preferably 3 mass% or more and 17.5 mass% or less, and particularly preferably 5 mass% or more and 15 mass% or less.

[0142] <34> Preferably, it further contains one or more selected from (F) a non-volatile oil other than components (C) and (D), (G) a volatile oil, (H) a surfactant, (I) a powder other than components (A1) to (A3), and (J) an oily thickener; more preferably, it contains components (A1), (A2), (B), (C), (E), and (F), with a content of component (D) of 0 mass% or more and 5 mass% or less; it contains components (A1), (A2), (B), (C), (E), and (G), with a content of component (D) of 0 mass% or more and 5 mass% or less; or it contains components (A1), (A2), (B), (C), (E), and (J), with a content of component (D) of 0 mass% or more and 5 mass% or less; and even more preferably, components (A1), (A2), (B), (C), and A water-in-oil emulsion sunscreen cosmetic described in any one of <1> to <33>, containing (E) to (G) and having a content of component (D) of 0 mass% or more and 5 mass% or less, and particularly preferably containing components (A1), (A2), (B), (C) and (E) to (J) and having a content of component (D) of 0 mass% or more and 5 mass% or less.

[0143] <35> A water-in-oil emulsion sunscreen cosmetic described in any one of <1> to <34>, wherein the formulation is preferably in the form of an emulsion, cream, paste, or gel.

[0144] <36> A water-in-oil emulsion sunscreen cosmetic described in any one of <1> to <35>, wherein the content of a UV absorber is preferably 0 mass% or more and 5 mass% or less, more preferably 0 mass% or more and 2.5 mass% or less, even more preferably 0 mass% or more and 1 mass% or less, even more preferably 0 mass% or more and 0.5 mass% or less, and particularly preferably 0 mass%.

[0145] Examples

[0146] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. In addition, in the present examples, various measurements and evaluations were performed by the following methods.

[0147] (Measurement and Evaluation Methods)

[0148] (1) UV protection effect (SPF value)

[0149] Each cosmetic was uniformly applied to a PMMA plate to a concentration of 2 mg / cm² and dried in a cool, dark place for 15 minutes. After drying, the transmittance (%) of the absorption spectrum (wavelength 350 nm) at 9 points—the sum of the midpoint on the square PMMA plate, each vertex, and the midpoint of the side connecting each vertex—was measured using an SPF analyzer (SPF 290S plus, manufactured by Optometricus USA, Inc.), and the average value of the transmittance at the 9 points was calculated. The SPF value was calculated from this average transmittance value (%) and evaluated according to the following criteria.

[0150] (Evaluation criteria for UV protection effectiveness)

[0151] AA: SPF 75 or higher

[0152] A: SPF 67 or higher but less than 75

[0153] B: SPF 60 or higher, but less than 67

[0154] C: SPF less than 60

[0155] (2) Effect of inhibiting the attachment of hazardous substances to the air

[0156] Each cosmetic was applied to white artificial leather (product name "Laforet S2923", manufactured by Okamoto Shinwa Co., Ltd.) as a substitute for skin, such that the application amount of ingredients (A1) and (A2) was 0.12 mg / cm², and left to dry overnight at room temperature.

[0157] The surface of artificial leather coated with each of the above cosmetic products was exposed to a blowing environment of hazardous atmospheric substances for evaluation, and the color difference ΔE before and after exposure was measured using a colorimeter by the following method.

[0158] [Measurement of Color Difference ΔE]

[0159] L1 of the artificial leather surface before exposure, using a colorimeter (product name "CM-2002", manufactured by Konica Minolta). * , a1 * , b1 * The value was measured.

[0160] Separately, a blower (product name "Silky Wind 9ZF002RH02", size: 129 × 106 × 83 mm, manufactured by Rhythm Watch Industry Co.) and a mesh screen (Test sieves JIS Z 8801, frame dimensions: φ100 × 45H, mesh size: 106 μm, manufactured by Tokyo Screen Co.) were fixed inside a glove bag (part number "3-118-01", manufactured by As One Co.). The installation height of the mesh screen was set to 17 cm.

[0161] Next, an artificial leather (5 cm × 4 cm) coated with the cosmetic of the test sample was attached to a support so that the height of the bottom of the artificial leather was 11 cm. The distance between the coated surface of the artificial leather attached to the support and the blower was set to 15 cm, and as shown in Fig. 1, the coated surface of the artificial leather was installed perpendicular to the blower's blowing direction so that the center height of the blower blade and the center height of the artificial leather were the same.

[0162] The temperature inside the glove bag was set to 25°C and the relative humidity to 57%RH, and using a clogging removal brush (product name “JNB-5”, brush diameter 53 μm, manufactured by Tokyo Screen Co., Ltd.), 50 mg of graphite powder (product name “J-CPB”, average particle size: 5.5 μm, manufactured by Nippon Graphite Industry Co., Ltd.) was classified as an atmospheric hazardous substance for evaluation, and the surface of the artificial leather coated with each cosmetic was exposed to the air blowing environment of the atmospheric hazardous substance for evaluation by dropping it from a mesh for 1 minute in front of the blower opening of a blower with the blower scale set to 1.

[0163] Next, L2 of the artificial leather surface after exposure using the above colorimeter * , a2 * , b2 * The value was measured, and the color difference ΔE value was calculated from the following equation (I).

[0164] ΔE = [(L1 * ― L2 * ) 2 + (a1 * ― a2 * ) 2 + (b1 * ― b2 * ) 2 ] 0.5 (I)

[0165] The above operation was performed three times for each test sample, and the average value of the color difference ΔE of the artificial leather coated with the cosmetic of the test sample was denoted as ΔEt. In addition, the same operation as above was performed three times for artificial leather not coated with the cosmetic as a standard sample, and the average value of the color difference ΔE was denoted as ΔEs, and the adhesion inhibition rate was calculated from the following formula (II). The higher the adhesion inhibition rate, the better the adhesion inhibition effect of hazardous airborne substances.

[0166] Inhibition rate of attachment of hazardous air pollutants (%) = 100 × (ΔEs ― ΔEt) / ΔEs (II)

[0167] (Evaluation criteria for the effect of inhibiting the attachment of hazardous air pollutants)

[0168] AA: Attachment inhibition rate of 50% or more

[0169] A: Adhesion inhibition rate is 30% or more and less than 50%

[0170] B: Adhesion inhibition rate is 10% or more and less than 30%

[0171] C: Attachment inhibition rate less than 10%

[0172] (3) No powdery sensation when applied

[0173] 0.02 mL of each cosmetic product was applied to the inner side of the forearm of two panelists within a diameter of 3 cm. The absence of a powdery sensation upon application was scored according to the following criteria, and the average score of the two panelists was calculated. If the average score was greater than 3 points, the evaluation was AA; if the average score was greater than 2 points and 3 points or less, the evaluation was A; if the average score was greater than 1 point and 2 points or less, the evaluation was B; and if the average score was 1 point or less, the evaluation was C.

[0174] 4 points: I don't feel any powdery sensation at all.

[0175] 3 points: Does not feel powdery

[0176] 2 points: Cannot say either way

[0177] 1 point: Feels slightly powdery

[0178] 0 points: Strong powdery sensation

[0179] Examples 1 to 7 and Comparative Examples 1 to 6

[0180] The water-in-oil emulsion sunscreen cosmetic formulations of Examples 1 to 7 and Comparative Examples 1 to 6 were prepared by conventional methods according to the formulations shown in Tables 1 and 2, and the above measurements and evaluations were performed. The results are shown in Tables 1 and 2.

[0181]

[0182]

[0183] The symbols in the table represent the following:

[0184] *1 : MT-100TV (average primary particle size d A : 15 nm, manufactured by Teika Co.)

[0185] *2 : MZX-304R3M (average primary particle size d A : 35 nm, manufactured by Teika Co.)

[0186] *3 : MZX-304OTS (average primary particle size d A : 35 nm, manufactured by Teika Co.)

[0187] *4 : KF-96L-6CS (Manufactured by Shin-Etsu Chemical Co., Ltd.)

[0188] *5 : Pearlim EX (Manufactured by Nichiyu)

[0189] *6 : Nicole Squalane (Manufactured by Nippon Surfactant Co., Ltd.)

[0190] *7 : KF-6015 (Manufactured by Shin-Etsu Chemical Co., Ltd.)

[0191] *8 : KF-6017 (Manufactured by Shin-Etsu Chemical Co., Ltd.)

[0192] *9 : Leopard KL2 (Manufactured by Chiba Milling Co.)

[0193] *10 : SI-Talc JA-46R (Manufactured by Miyoshi Chemical Co.)

[0194] *11 : Cosmol 525 (Manufactured by Nissin Oilio Group)

[0195] *12 : Estemol N-01 (Manufactured by Nissin Oilio Group)

[0196] *13 : Pearlim 4 (Manufactured by Nichiyu Co.)

[0197] *14 : KF-96L-2CS (Manufactured by Shin-Etsu Chemical Co., Ltd.)

[0198] *15 : DPG-RF (Manufactured by ADEKA)

[0199] Example 8

[0200] The water-in-oil emulsion sunscreen cosmetic of Example 8 was prepared by a conventional method according to the formulation shown in Table 3, and the above measurements and evaluations were performed. The results are shown in Table 3. In addition, the water-in-oil emulsion sunscreen cosmetic of Example 8 has a good, matte finish.

[0201]

[0202] *16 in the table represents silicon TSF405A (manufactured by Momentive), and other symbols have the same meaning as above. Explanation of the symbols

[0203] 1 : Sample of the subject of evaluation 2 : Support 3 : Net 4: Air hazardous substances for evaluation 5 : Blower

Claims

Claim 1 A water-in-oil emulsion comprising the following components (A1), (A2), (B), and (C), wherein (D) the content of non-volatile silicone oil is 0.1 mass% or more and 4 mass% or less, the content of ultraviolet absorber is 0 mass%, the hydrophobization treatment of component (A1) is fatty acid treatment, the hydrophobization treatment of component (A2) is one or more selected from silicone treatment and alkylalkoxysilane treatment, component (B) is one or more selected from ethylene glycol, propylene glycol, 1,3-butylene glycol, diethylene glycol, dipropylene glycol, polyethylene glycol, and polypropylene glycol, component (C) is one or more selected from liquid paraffin, liquid isoparaffin, and squalane, and component (D) is one or more selected from dimethylpolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, and tetramethyltetrahydrogenpolysiloxane. Sunscreen cosmetic. (A1) Hydrophobically treated particulate titanium oxide 5 mass% or more and 25 mass% or less (A2) Hydrophobically treated particulate zinc oxide 10 mass% or more and 35 mass% or less (B) Divalent polyol (C) Non-volatile hydrocarbon oil 2 mass% or more and 14 mass% or less Claim 2 A water-in-oil emulsion sunscreen cosmetic according to claim 1, wherein the mass ratio of component (B) to the sum of components (A1) and (A2) [(B) / ((A1) + (A2))] is 0.05 or more and 0.75 or less. Claim 3 A water-in-oil emulsion sunscreen cosmetic according to claim 1, wherein the mass ratio of component (C) to the sum of components (A1) and (A2) [(C) / ((A1) + (A2))] is 0.05 or more and 0.93 or less. Claim 4 A water-in-oil emulsion sunscreen cosmetic according to claim 1, wherein the mass ratio of component (D) to the sum of components (A1) and (A2) [(D) / ((A1) + (A2))] is 0.005 or more and 0.2 or less. Claim 5 A water-in-oil emulsion sunscreen cosmetic according to claim 1, wherein the mass ratio of component (D) to the sum of components (A1) and (A2) [(D) / ((A1) + (A2))] is 0.005 or more and 0.1 or less. Claim 6 A water-in-oil emulsion sunscreen cosmetic according to claim 1, wherein the mass ratio of component (D) to component (C) [(D) / (C)] is 0.05 or more and 1 or less. Claim 7 A water-in-oil emulsion sunscreen cosmetic according to claim 1, wherein the mass ratio of component (D) to component (C) [(D) / (C)] is 0.05 or more and 0.2 or less. Claim 8 In claim 1, the average primary particle size d of components (A1) and (A2). A a. A water-in-oil emulsion sunscreen cosmetic having a thickness of 1 nm or more and 200 nm or less. Claim 9 delete Claim 10 delete Claim 11 A water-in-oil emulsion sunscreen cosmetic according to claim 1, wherein the content of component (B) is 1 mass% or more and 14 mass% or less in the water-in-oil emulsion sunscreen cosmetic. Claim 12 A water-in-oil emulsion sunscreen cosmetic according to claim 1, wherein the content of component (C) is 6 mass% or more and 12 mass% or less in the water-in-oil emulsion sunscreen cosmetic. Claim 13 A water-in-oil emulsion sunscreen cosmetic according to claim 1, wherein the content of the film-forming agent is 0 mass% or more and 0.075 mass% or less in the water-in-oil emulsion sunscreen cosmetic. Claim 14 delete Claim 15 delete

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