Water-in-oil type sunscreen cosmetic

Abstract

To provide a water-in-oil type sunscreen cosmetic having a function for protecting ultraviolet rays and excellent in handleability in a production process and stability of a product after production.SOLUTION: (A) at least one compound which is pasty at 25 °C and has a viscosity at 60 °C of more than 30 MPa·s and 1,000 MPa·s or less, (B) at least one compound having a hydroxystearic acid group and an oxyalkylene group, (C) an organic ultraviolet absorber, (D) water, and (E) at least one solid oil having a melting point of 60 °C or more. The ingredient (C) is one or more organic UV absorbers selected from (C1) an oil-soluble organic UV absorber and (C2) a water-soluble organic UV absorber, and the content of the ingredient (E) is 2.5 to 20% by mass based on the total amount of the cosmetic.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to water-in-oil sunscreen cosmetics, for example, water-in-oil solid makeup cosmetics, water-in-oil makeup cosmetics, water-in-oil solid sunscreen cosmetics, water-in-oil sunscreen cosmetics, and other water-in-oil cosmetics having sunscreen effects. [Background technology]

[0002] Conventionally, water-in-oil emulsion cosmetics containing volatile silicone oils or silicone-based emulsifiers have been developed to reduce the sensation of application of oil-based cosmetics (stickiness, heavy spreadability) and the sensation of application after application (stickiness, filmy feel).

[0003] Patent Document 1 discloses a water-in-oil emulsion makeup cosmetic that contains a UVA absorber, a UVB absorber, a photoresponsive capsule, an ester oil that is liquid at 20°C, and water.

[0004] Patent Document 2 discloses a sunscreen composition containing a surfactant, water, an oil, a water-soluble ultraviolet absorber and / or an oil-soluble ultraviolet absorber.

[0005] Patent Document 3 describes a cosmetic or dermatological composition containing trans-resveratrol, an organic screening system.

[0006] The cosmetics and compositions described in Patent Documents 1 to 3 may contain silicone compounds to achieve a non-sticky feel when used, such as good spreadability, and to improve the dispersibility of powder components. However, in recent years, silicone compounds have become a problem due to their lack of biodegradability, leading to their accumulation over long-term use. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Japanese Patent Application Laid-Open No. 2016-84330 [Patent Document 2] Japanese Patent Application Laid-Open No. 2011-178769 [Patent Document 3] Special Publication No. 2016-503788 Summary of the Invention [Problem to be solved by the invention]

[0008] The present invention aims to provide a water-in-oil sunscreen cosmetic that is substantially silicone-free, has a function of protecting against ultraviolet rays, and is easy to handle during the production process and has excellent product stability after production. [Means for solving the problem]

[0009] The present invention relates to a composition comprising: (A) at least one compound (hereinafter referred to as "component (A)") that is pasty at 25°C and has a viscosity at 60°C of more than 30 mPa·s and not more than 1,000 mPa·s; (B) at least one compound having a hydroxystearic acid group and an oxyalkylene group (hereinafter referred to as "component (B)"); (C) an organic ultraviolet absorber (hereinafter referred to as "component (C)"); (D) water (hereinafter referred to as "component (D)"), and (E) contains at least one solid oil (hereinafter referred to as "component (E)") having a melting point of 60°C or higher, Component (C) is one or more organic ultraviolet absorbers selected from (C1) an oil-soluble organic ultraviolet absorber (hereinafter referred to as component (C1)) and (C2) a water-soluble organic ultraviolet absorber (hereinafter referred to as component (C2)), The present invention provides a water-in-oil sunscreen cosmetic, in which the content of component (E) is 2.5 to 20 mass % of the total amount of the cosmetic. [Effects of the Invention]

[0010] The water-in-oil sunscreen cosmetic of the present invention is substantially silicone-free and yet can improve ultraviolet absorption. It also has good handleability during the production process and excellent product stability after production. DETAILED DESCRIPTION OF THE INVENTION

[0011] <Water-in-oil sunscreen cosmetics> The water-in-oil sunscreen cosmetic of the present invention (hereinafter referred to as "the cosmetic of the present invention") can be composed of an oil phase containing the above-mentioned components (A), (B), (C1), (E), and optionally (F) a low-viscosity liquid oil having a viscosity of 40 mPa s or less at 25°C (hereinafter referred to as "component (F)"), an aqueous phase containing the above-mentioned components (C2) and (D), and optionally, if necessary, a powder phase containing (G) cellulose (hereinafter referred to as "component (G)"), as well as other cosmetic ingredients. Note that either component (C1) or component (C2) may be used alone, or both may be used.

[0012] The compound of component (A) used in the cosmetic of the present invention is used, for example, for the purpose of improving emulsion stability and powder dispersibility. Component (A) is in a paste state at 25°C. The viscosity of the paste-like compound at 60°C is preferably greater than 30 mPa·s and less than 1,000 mPa·s, and more preferably greater than 100 mPa·s and less than 500 mPa·s. The viscosity here is measured using a rheometer at 60°C and a shear rate of 10 (1 / s).

[0013] From the viewpoint of emulsion stability and powder dispersibility, the compound of component (A) can be, for example, one or more selected from hydrogenated castor oil isostearate, dipentaerythrityl hexahydroxystearate, dipentaerythrityl hexa(hydroxystearate / stearate / rosinate), dipentaerythrityl tri-polyhydroxystearate, bis-diglyceryl polyacyladipate-2, phytosteryl macadamiate, phytosteryl / isostearyl / cetyl / stearyl / behenyl dimer dilinoleate, di(octyldodecyl / phytosteryl / behenyl) lauroyl glutamate, and dimer dilinoleyl bis(behenyl / isostearyl / phytosteryl) dimer dilinoleate.

[0014] From the viewpoints of usability and stability over time, component (A) is particularly preferably one or more selected from hydrogenated castor oil isostearate, dipentaerythrityl hexahydroxystearate, dipentaerythrityl hexa(hydroxystearate / stearic acid / rosin acid), dipentaerythrityl tri-polyhydroxystearate, and bis-diglyceryl polyacyladipate-2.

[0015] Furthermore, from the viewpoint of dispersibility of the powder phase, etc., the cosmetic of the present invention preferably uses, for example, a combination of hydrogenated castor oil isostearate and bis-diglyceryl polyacyladipate-2 as component (A). When hydrogenated castor oil isostearate and bis-diglyceryl polyacyladipate-2 are used in combination as component (A), the mass ratio of the content of hydrogenated castor oil isostearate to the content of bis-diglyceryl polyacyladipate-2 [hydrogenated castor oil isostearate / bis-diglyceryl polyacyladipate-2] is preferably 1 or more, and more preferably 2 or more.

[0016] The content of component (A) is preferably 1.5 to 15 mass %, more preferably 4 to 13 mass %, of the total amount of the cosmetic of the present invention.

[0017] The compound of component (B) used in the cosmetic of the present invention is a compound having a hydroxystearic acid group and an oxyalkylene group, and is used, for example, as an emulsifier. The hydroxystearic acid group is the hydrophobic portion of the compound of component (B) of the present invention, and refers to a group formed by removing one hydrogen atom from the carbonyl group constituting, for example, polyhydroxystearic acid or a fatty acid obtained by saponifying hydrogenated castor oil.

[0018] The oxyalkylene group refers to, for example, an oxyalkylene group derived from one or more polyhydric alcohols selected from ethylene glycol, propylene glycol, butanediol, polyethylene glycol, and polypropylene glycol, or an oxyalkylene group in which two or more alkylene groups are linked by an ether bond. From the viewpoint of makeup durability, an oxyethylene group derived from polyethylene glycol is preferred. From the viewpoint of makeup durability, the average number of moles of oxyethylene groups added in component (B) is preferably in the range of 5 to 100, more preferably 20 to 40. In particular, when the hydroxystearic acid groups in the compound of component (B) are derived from fatty acids obtained by saponifying hydrogenated castor oil, the average number of moles of oxyethylene groups added in component (B) is more preferably 5 to 20.

[0019] Component (B) is preferably a compound in which the hydroxystearic acid group is derived from polyhydroxystearic acid or from a fatty acid obtained by saponifying hydrogenated castor oil.

[0020] When component (B) is a compound having a hydroxystearic acid group (polyhydroxystearic acid group) derived from polyhydroxystearic acid (hereinafter referred to as "component (B1)"), for example, dipolyhydroxystearate PEG-30, which is composed of a diester of two or more polyhydroxystearic acids and polyethylene glycol, is preferred, and examples thereof include the product name "CITHROL DPHS" (manufactured by CRODA).

[0021] In the case where component (B) is a compound having hydroxystearic acid (a hydroxystearic acid group derived from hydrogenated castor oil) derived from a fatty acid obtained by saponifying hydrogenated castor oil (hereinafter referred to as "component (B2)"), for example, it is preferably one or more selected from PEG-5 hydrogenated castor oil, PEG-10 hydrogenated castor oil, PEG-20 hydrogenated castor oil, PEG-30 hydrogenated castor oil, PEG-40 hydrogenated castor oil, PEG-50 hydrogenated castor oil, PEG-60 hydrogenated castor oil, PEG-70 hydrogenated castor oil, PEG-80 hydrogenated castor oil, PEG-90 hydrogenated castor oil, and PEG-100 hydrogenated castor oil, which are composed of esters of hydrogenated castor oil and polyethylene glycol, and more preferably one or more selected from PEG-5 hydrogenated castor oil and PEG-10 hydrogenated castor oil from the viewpoint of cosmetic durability, and HCO-5" and "NIKKOL HCO-10" (manufactured by Nikko Chemicals Co., Ltd.).

[0022] Component (B) is preferably one or more selected from component (B1) and component (B2), and component (B1) and component (B2) may be used in combination. From the viewpoint of makeup durability, component (B1) is more preferred.

[0023] When component (B1) and component (B2) are used in combination as component (B), the (B1) / (B2) (mass ratio) is preferably in the range of 0.3 to 5, more preferably 0.5 to 3.

[0024] The content of component (B) is preferably 0.5 to 10 mass %, more preferably 1 to 8 mass %, and even more preferably 1.5 to 6 mass %, of the total amount of the cosmetic of the present invention.

[0025] Component (C) used in the cosmetic of the present invention is an organic ultraviolet absorber, and is used, for example, for the purpose of protecting against ultraviolet rays. Component (C) used in the cosmetic of the present invention may be either component (C1) or component (C2), or a combination of both.

[0026] Examples of component (C1) include oxybenzone-3, t-butyl methoxydibenzoylmethane, ethylhexyl methoxycinnamate, octocrylene, ethylhexyl salicylate, homosalate, ethylhexyl dimethyl PABA, ethylhexyl triazone, bisethylhexyloxyphenol methoxyphenyl triazine, diethylamino hydroxybenzoyl hexyl benzoate, and drometrizole trisiloxane.

[0027] Examples of the component (C2) include terephthalylidene dicamphorsulfonic acid, phenylbenzimidazole sulfonic acid, oxybenzone-4, and ferulic acid.

[0028] When component (C) contains component (C1) and component (C2), the mass ratio (C1) / (C2) of component (C1) to component (C2) is preferably 0.05 to 30, more preferably 0.2 to 15, and even more preferably 1 to 6.

[0029] The content of component (C) is preferably 2 to 30 mass %, more preferably 3 to 25 mass %, of the total amount of the cosmetic of the present invention.

[0030] Component (D) used in the cosmetic of the present invention is water, preferably purified water from a hygienic standpoint. The content of component (D) is preferably 5 to 70 mass %, more preferably 20 to 55 mass %, of the total amount of the cosmetic of the present invention.

[0031] Furthermore, the mass ratio (B) / (D) of the content of component (B) to the content of component (D) in the cosmetic preparation may be in the range of 0.01 to 0.5, preferably in the range of 0.02 to 0.4, more preferably in the range of 0.07 to 0.3, and even more preferably in the range of 0.1 to 0.3. Within this range, the product can be easily handled during the manufacturing process, and the product will have excellent feel during use and stability over time.

[0032] Component (E) used in the cosmetic of the present invention is a solid oil having a melting point of 60°C or higher, and the cosmetic of the present invention is used for the purpose of improving, for example, moldability and stability over time.

[0033] Component (E) is preferably one or more selected from, for example, plant-derived wax esters and hydrocarbon waxes. Specifically, one or more solid waxes selected from sunflower seed wax, synthetic wax, beeswax, candelilla wax, candelilla wax esters, candelilla wax hydrocarbons, carnauba wax, rice bran wax, microcrystalline wax, polyethylene, (ethylene / propylene) copolymer, solid paraffin, Japan wax, ozokerite, ceresin, and hydrogenated hardened oils can be used.

[0034] From the viewpoints of usability and stability over time, component (E) is preferably one or more selected from sunflower seed wax, synthetic wax, beeswax, candelilla wax, carnauba wax, rice bran wax, microcrystalline wax, and (ethylene / propylene) copolymers.

[0035] Synthetic waxes are hydrocarbon waxes obtained by the Fischer-Tropsch process or ethylene polymerization process, and are listed in the "List of Cosmetic Ingredient Labeling Names" compiled by the Japan Cosmetic Industry Association.

[0036] The content of component (E) is 2.5 to 20 mass %, preferably 8 to 15 mass %, of the total amount of the cosmetic of the present invention.

[0037] The cosmetic of the present invention can use, as component (F), a low-viscosity liquid oil having a viscosity of 40 mPa·s or less at 25°C. Component (F) is preferably a low-viscosity liquid oil having a viscosity of 15 mPa·s or less. For example, the viscosity may be measured by measuring the kinematic viscosity and then converting it. While there are no particular limitations on the method used to measure kinematic viscosity, suitable methods include ISO 23581:2020 "Petroleum and related products -- Determination of kinematic viscosity -- Method using a Stabinger viscometer" and ISO 12185:1996 "Crude oil and petroleum products -- Determination of density -- Oscillating U-tube method."

[0038] Examples of component (F) include hexyl laurate, isoamyl laurate, isopropyl myristate, isocetyl myristate, octyldodecyl myristate, isopropyl palmitate, ethylhexyl palmitate, isocetyl stearate, ethyl isostearate, isopropyl isostearate, hexyldecyl isostearate, isostearyl isostearate, ethylhexyl isononanoate, isobutyl isostearate, cetyl ethylhexanoate, isostearyl neopentanoate, isononyl isononanoate, isodecyl isononanoate, isotridecyl isononanoate, and isononanoic acid. One or more selected from tricyclodecane methyl hydroxybenzoate, jojoba oil, neopentyl glycol diethylhexanoate, neopentyl glycol dicaprate, neopentyl glycol diisononanoate, isostearyl neopentanoate, bisethoxydiglycol succinate, diethoxyethyl succinate, diethylhexyl succinate, tritridecyl trimellitate, caprylic / capric triglyceride, triethylhexanoin, mineral oil, squalane, dodecane, isododecane, tetradecane, hexadecane, isohexadecane, and hydrogenated polyisobutene can be used.

[0039] As component (F), from the viewpoints of feel in use (lightness of spread) and stability over time (hardness), for example, one or more selected from ethylhexyl palmitate, triethylhexanoin, tri(caprylic / capric acid)glyceryl, dodecane, isododecane, and isohexadecane are preferred.

[0040] Furthermore, from the viewpoint of feel during use (lightness of spread), a combination of ethylhexyl palmitate and triethylhexanoin is more preferred as component (F).

[0041] Furthermore, from the viewpoint of feel in use (lightness of spreading) and stability over time (hardness), a more preferred component (F) is, for example, a combination of triethylhexanoin and one or more selected from dodecane, isododecane, and isohexadecane.

[0042] The content of component (F) may be 10 to 50% by mass, preferably 15 to 45% by mass, and more preferably 17 to 40% by mass, based on the total amount of the cosmetic of the present invention.

[0043] In the cosmetic of the present invention, the total content of components (A), (C1), (E), and (F), excluding component (B), is preferably 23 to 70% by mass, more preferably 30 to 50% by mass. Within this range, stable emulsification is possible, and a satisfactory feel in use (freshness, light spreadability) can be obtained.

[0044] The cosmetic preparation of the present invention may further optionally contain cellulose as component (G).

[0045] As component (G), for example, spherical cellulose is preferred, and the average particle size of the spherical cellulose is preferably in the range of 1 to 150 μm, more preferably in the range of 5 to 50 μm.

[0046] The average particle size of spherical cellulose can be determined by determining the particle size distribution using a laser diffraction particle size distribution analyzer "SALD-2100 (manufactured by Shimadzu Corporation)" and using the value of the particle size at 50% of the cumulative volume.

[0047] As the spherical cellulose, cellulose itself can be used, or a cellulose derivative such as acetyl cellulose can also be used. For example, "GE-800" (manufactured by Toshoku Pigment Co., Ltd., average particle size 5 to 8 μm) can be used.

[0048] Hydrophobic spherical cellulose can also be used, which has been surface-treated with a hydrophobic treatment agent as needed. Examples of hydrophobic treatment agents that can be used as needed include metal soaps such as zinc stearate and magnesium stearate, and amino acids such as disodium stearoyl glutamate. Silicone-treated spherical cellulose, which has been surface-treated with a silicone compound, is not included in component (G).

[0049] The content of component (G) is preferably 0.3 to 10% by mass, more preferably 0.7 to 3% by mass, based on the total amount of the cosmetic of the present invention.

[0050] The cosmetic of the present invention comprises 100% by mass of the total of components (A), (B), (C), (D), (E), (F), and, if necessary, (G), as well as the remainder including other cosmetic components.

[0051] The "remaining components, including other cosmetic ingredients" are ingredients that are not involved in the manifestation of the effects of the invention, but are used to form the water-in-oil sunscreen cosmetic and to manifest the functions of the cosmetic (for example, the coloring effect of the colorant).

[0052] In the cosmetic of the present invention, the mass ratio (A) / (B) of the content of component (A) to the content of component (B) is preferably in the range of 0.3 to 10, more preferably in the range of 0.5 to 5, and even more preferably in the range of 0.6 to 3.

[0053] <Other ingredients> The cosmetic of the present invention may contain the following cosmetic ingredients as other cosmetic ingredients. higher alcohols such as behenyl alcohol and octyldodecanol; Polysaccharide fatty acid esters such as dextrin palmitate; Polyglycerol fatty acid esters such as polyglyceryl-10 stearate; antioxidants such as d-δ tocopherol; Rosin pentaerythrityl ester, neopentyl glycol diisooctanoate, glycerin triisooctanoate, propylene glycol monolaurate, polyglyceryl-10 pentaisostearate, etc.; Solvents include ethanol, isopropanol, polyhydric alcohols, water-soluble polymers, bentonite, polyoxyethylene sorbitan monostearate, sorbitan sesquiisostearate, ethyl acetate, butyl acetate, and butanol; Moisturizing agents include glycerin, propylene glycol, sorbitol, polyethylene glycol, dipropylene glycol, 1,3-butylene glycol, pentylene glycol, diglycerin, mannitol, POE methylglycoside, biopolymers, sucrose, etc.; emollient ingredients such as cetyl ethylhexanoate; Quince seeds, pectin, cellulose derivatives, xanthan gum, sodium alginate, soybean gin, carboxyvinyl polymer; Sorbitan Monooleate, Glycerin Triisooctanoate, Octyl Methoxycinnamate, POE Sorbitan Monooleate, Isostearic Acid, Stearic Acid, Acetyl Tributyl Citrate, Trimethylpentanediyl Dibenzoate, Stearalkonium Bentonite; Thickeners, preservatives, emulsifiers, stabilizers, plasticizers; Anionic surfactants, cationic surfactants, nonionic surfactants, zwitterionic surfactants, protein-based surfactants; Medicinal ingredients, Vitamin C dipalmitate, vitamins, amino acids, whitening agents, disinfectants; Extender pigments such as talc, kaolin, mica, sericite, alumina, silica, glass flakes, calcium carbonate, magnesium carbonate, silicic anhydride, barium sulfate, and pearl pigments; pH adjuster, potassium hydroxide, sodium hydroxide, triethanolamine, magnesium stearate, zinc stearate, metal ion sequestering agent, citric acid, sodium citrate, lactic acid, sodium lactate, Antioxidants, fragrances, preservatives, chelating agents, antioxidants, dispersants, browning inhibitors, buffers, anti-precipitation ingredients, organically modified clay minerals, usability modifiers; As a powder phase, metal oxides such as red iron oxide (iron oxide), yellow iron oxide, black iron oxide, titanium oxide, chromium oxide, etc.; (HDI / trimethylolhexyl lactone) crosspolymer; Luminous powders such as bismuth oxychloride, titanium mica, iron oxide coated mica, titanium iron oxide mica, titanium mica treated with organic pigments, aluminum powder, and pearl pigments. In addition, in the cosmetic of the present invention, the raw materials for producing the other components described above do not contain silicone, and among the other powder components described above, powder components treated with silicone are not used.

[0054] The cosmetic of the present invention is substantially free of silicone compounds (with the exception of drometrizole trisiloxane). "Substantially free of silicone compounds (with the exception of drometrizole trisiloxane)" means that no silicone compounds other than drometrizole trisiloxane have been intentionally added to the cosmetic of the present invention. However, since the possibility of trace amounts of silicone compounds being mixed in during the manufacturing process of the cosmetic components containing the above-mentioned components (A) to (G) and optional components cannot be ruled out, and since the possibility of trace amounts of silicone compounds being contained as blended ingredients cannot be ruled out in some cases, the cosmetic of the present invention also includes those containing preferably 0.01% by mass or less, more preferably 0.001% by mass or less of silicone compounds (in terms of silicon content).

[0055] The content of silicone compounds can be measured by known methods. For example, the silicon content in silicone compounds can be measured based on the description in "Quantitative Method for Dimethylpolysiloxane in Foods by Atomic Absorption Spectroscopy" (Nishijima Motohiro et al., Food Hygiene Journal, Vol. 16, No. 2, pp. 110-115) or "Analysis of Silicone Oil in Sewage by Atomic Absorption Spectroscopy" (Tsuchiya Yuichi et al., Analytical Chemistry, Vol. 27 (1978), No. 6, pp. 343-346).

[0056] The water-in-oil sunscreen cosmetic of the present invention can be produced, for example, by a production method including the following first to fourth steps. First step: A step of melting and kneading an oil phase containing component (A), component (B), component (C1), component (E), and component (F), and, if necessary, adding a powder phase containing optional component (G) to disperse or knead the oil phase. Second step: melt-kneading an aqueous phase containing component (C2) and component (D); A third step: a step of adding the kneaded material obtained in the second step to the dispersion or kneaded material obtained in the first step and emulsifying the mixture; Step 4: A step of degassing the emulsion obtained in step 3 as necessary, and then filling or molding it into a container.

[0057] In the first step, component (A) and oil phase components including component (B), component (C1), component (E), and component (F) are heated to 80 to 90°C and melted using a paddle mixer or the like to obtain a kneaded product. Furthermore, a powder phase including optional component (G) and any powdery cosmetic component is added to the molten kneaded product as needed, and the mixture is uniformly mixed using a triple roller or the like to obtain a molten dispersion or kneaded product in which the powder phase is dispersed in the oil phase.

[0058] The oil phase may contain, in addition to component (A), component (B), component (C1), component (E), and component (F), any cosmetic component (oil phase) in liquid, gel, or solid form.

[0059] In the second step, the aqueous phase components including the components (C2) and (D) are heated to 80 to 90°C and melted using a paddle mixer or the like.

[0060] In the third step, the kneaded product obtained in the second step is added to the dispersion or kneaded product obtained in the first step while heated to 80 to 90°C, and the mixture is dispersed using a homogenizer or the like to obtain a water-in-oil sunscreen cosmetic composition. Optional ingredients may be added in this step.

[0061] In the fourth step, the composition obtained in the third step is heated to 80 to 100°C and degassed while stirring using a vacuum degasser, and then filled into a container or molded to obtain the water-in-oil sunscreen cosmetic of the present invention. For example, the degassed composition is filled into a lipstick mold, and the resulting stick-shaped solid is cooled and solidified, and then placed in a lipstick container.

[0062] Because the cosmetic of the present invention is substantially free of silicone compounds, it does not undergo phase separation even when cooled during the production process, for example, during or immediately after step 1, during or immediately after step 2, or during or immediately after step 3. In particular, it is easy to re-emulsify even when cooled during or immediately after step 3, in which water, component (D), is added.

[0063] In the cosmetic of the present invention, the content of the powder phase consisting of component (G) and other components such as legal colorants and extender pigments in the cosmetic is preferably 1 to 30 mass %, more preferably 3 to 20 mass %, in the cosmetic in the above-mentioned manufacturing method, although this will vary depending on the type of cosmetic. The remainder is made up of an oil phase containing components (A), (B), (C1), (E), and (F) and an aqueous phase containing components (C2) and (D). [Example]

[0064] <Ingredients used> Component (A) Hydrogenated castor oil isostearate: Product name: "Castride MIS-P" (paste at 25°C), manufactured by National Mimatsu Co., Ltd. Bis-diglyceryl polyacyladipate-2: Product name: Softisan 649 (paste at 25°C), manufactured by IOI Oleo GmbH Ingredient (B) PEG-30 dipolyhydroxystearate: Product name: CITHROL DPHS, manufactured by CRODA PEG-20 hydrogenated castor oil: Product name "NIKKOL HCO-20", manufactured by Nikko Chemicals Co., Ltd.

[0065] Component (C1) Ethylhexyl methoxycinnamate: Product name: Parsol MCX, manufactured by DSM K.K. Octocrylene: Product name: Parsol 340, manufactured by DSM Co., Ltd. Dimethyl PABA ethylhexyl: Product name "Escarol 507", manufactured by Ashland Ethylhexyl triazone: Product name: Parsol EHT, manufactured by DSM K.K. Bis-ethylhexyloxyphenol methoxyphenyl triazine: Product name: Parsol Shield, manufactured by DSM K.K. Diethylaminohydroxybenzoyl hexyl benzoate: Product name: Parsol DHHB, manufactured by DSM K.K. Drometrizole trisiloxane: Product name "Sun-Shel DMTS", manufactured by Serasoo Component (C2) Terephthalidene dicamphorsulfonic acid: Product name "Sun-Shel TDSA", manufactured by Serasoo Phenylbenzimidazole sulfonic acid: Product name: Parsol HS, manufactured by DSM K.K.

[0066] Ingredient (E) Synthetic wax: Product name: PERFORMA SW-88 Synthetic Wax, manufactured by NuCera Solutions Beeswax: Product name: "Beeswax", manufactured by Miki Chemical Industry Co., Ltd. Sunflower seed wax: Product name: "Refined Sunflower Wax", manufactured by Yokoseki Oil & Fat Industries Co., Ltd. Ingredient (F) Triethylhexanoin: Product name "Triphat S-308", manufactured by Nippon Surfactant Industries Co., Ltd. Ethylhexyl palmitate: Product name "IOP", manufactured by Nikko Chemicals Co., Ltd. Dodecane: Product name "PARAFOL 12-97", manufactured by SASOL Germany GmbH Ingredients (G) Cellulose (spherical): "GE-800", Toshiki Pigment Co., Ltd.

[0067] Comparison component (C') Methylenebisbenzotriazolyltetramethylbutylphenol (neither water-soluble nor fat-soluble, used by dispersing in water): Product name "Tinosorb M", manufactured by BASF Japan Ltd.

[0068] The water-in-oil sunscreen cosmetics of the Examples and Comparative Examples were prepared by the following method. An oil phase containing components (A), (B), (C1) (if present), (E), and (F) shown in Table 1 was melt-kneaded at 90 to 100°C using a paddle mixer (first step). The powder phase containing component (G) was added to the melted oil phase, and the mixture was kneaded three times using a triple roller to obtain a kneaded mixture (Step 2). The kneaded mixture was then heated to around 90°C, and mixed with component (C2) (if present) and (D) at 90-100°C, followed by further mixing with the optional components shown in the table to obtain water-in-oil sunscreen cosmetic compositions of the Examples and Comparative Examples (Step 3). The obtained cosmetic composition was defoamed while stirring using a vacuum defoamer, and then filled into a predetermined container to obtain a water-in-oil sunscreen cosmetic (Step 4). The cosmetic was evaluated for the following items, and the results are shown in Tables 1 and 2.

[0069] <Cosmetic evaluation method> ·Moldability The cosmetic compositions obtained in the Examples and Comparative Examples were melted at approximately 90°C, filled into a predetermined mold for stick-shaped cosmetic preparations (inner diameter 12 mm x length 44 mm, 4.0 g capacity), and solidified by leaving to stand at -20°C for 5 minutes. The solidified stick-shaped cosmetic preparation was placed in a predetermined container, and after leaving to stand at room temperature for 6 hours, the appearance of the cosmetic preparation was visually observed, and moldability was evaluated according to the following criteria.

[0070] ◯: It was confirmed that the cosmetic could be easily removed from the mold, could be loaded into a predetermined container, and had a uniform surface. △: The cosmetic could be removed from the mold and loaded into the specified container, but scratches caused by rubbing when removed from the mold were observed on the surface of the cosmetic. ×: Solidification was incomplete and the product could not be removed from the mold.

[0071] ·Dispersion stability when remelted ·Emulsion stability After the third step, the water-in-oil sunscreen cosmetic composition was allowed to stand at room temperature (approximately 25°C) for at least 6 hours to cool. After confirming that the cosmetic composition had completely solidified, the solidified cosmetic composition was re-melted at approximately 90°C while stirring (30 rpm) with a propeller mixer, and evaluated according to the following criteria.

[0072] ◯: No precipitates or aggregates were found, and the particles were uniformly dispersed. △: Some precipitates and aggregates were observed, and the dispersion was somewhat uneven. ×: Precipitation was observed.

[0073] · Stability of cosmetics over time (appearance) The cosmetic compositions obtained in the Examples and Comparative Examples were melted at approximately 90°C and filled into a predetermined mold for stick-shaped cosmetic preparations (inner diameter 12 mm x length 44 mm, 4.0 g capacity), and allowed to stand at -20°C for 5 minutes to solidify. The solidified stick-shaped cosmetic preparations were placed in a predetermined container and allowed to stand at room temperature for at least 6 hours. The cosmetic preparations were placed in a thermostatic chamber for cycle testing, and the chamber was set to 0°C and allowed to stand for 12 hours. The chamber was then set to 40°C and allowed to stand for 12 hours. This cycle test was carried out over one month (approximately 30 cycles), with one cycle per day. The appearance of the cosmetic preparations after the test was visually observed and evaluated according to the following criteria.

[0074] ○: No change △: There is a change, but it is not enough to affect the product quality. ×: Changes occurred (oil droplets seeping out onto the surface, wax crystals precipitation, partial melting of the surface, scratches due to rubbing against the container, etc.) -: No rating

[0075] · Stability of cosmetics over time (hardness) The cosmetic compositions obtained in the Examples and Comparative Examples were melted at approximately 90°C and filled into a predetermined mold for stick-shaped cosmetic compositions (inner diameter 12 mm x length 44 mm, 4.0 g capacity), and allowed to stand at -20°C for 5 minutes to solidify. The solidified stick-shaped cosmetic compositions were placed in a predetermined container and allowed to stand at room temperature for at least 6 hours. The hardness of the cosmetic composition after 6 hours was recorded as the "initial value." The cosmetic compositions were placed in a thermostatic chamber for cycle testing, set to 0°C and allowed to stand for 12 hours, then set to 40°C and allowed to stand for 12 hours. This cycle test was carried out over one month (approximately 30 cycles), with one cycle per day. After the test, the hardness of the cosmetic compositions was measured and evaluated according to the following criteria. In this evaluation, the stress (g) exerted when a 3 mm diameter probe was inserted 5 mm into the center of the cosmetic composition was recorded as the hardness.

[0076] The hardness of the cosmetic composition was calculated by measuring the maximum stress from the time when the measuring needle described below came into contact with the surface of the cosmetic composition to the time when it penetrated 5 mm. Measuring device: Rheotex: SD-700II (Sun Scientific) Measurement conditions: 30°C Measurement speed: 60mm / min Measuring needle: 3mmφ

[0077] ○: The decrease in hardness from the initial value was less than 30%. △: The decrease in hardness from the initial value was 30% or more and less than 40%. ×: The hardness decreased by 40% or more from the initial value. -: No rating

[0078] · Stability of cosmetics over time (precipitation of UV absorbers) The cosmetic compositions obtained in the Examples and Comparative Examples were melted at approximately 90°C and filled into a predetermined mold for stick-shaped cosmetic compositions (inner diameter 12 mm x length 44 mm, 4.0 g capacity), and allowed to stand at -20°C for 5 minutes to solidify. The solidified stick-shaped cosmetic compositions were loaded into a predetermined container and stored at room temperature. After one month, each stick-shaped cosmetic composition was removed, cut approximately 10 mm from the tip with a utility knife, and the cut portion was placed on aluminum foil and spread by rubbing with a spatula. The spread cosmetic compositions were visually inspected and traced with a finger to check for the presence of foreign matter, and evaluated according to the following criteria.

[0079] ○: No foreign matter was found ×: Foreign matter was found -: No rating

[0080] UV absorption of cosmetics The skin of each subject was irradiated with ultraviolet light, both on bare skin and on skin on which the cosmetic compositions obtained in the Examples and Comparative Examples were applied. The MED (Minimal Erythema Dose) of the untreated area and the MED of the treated area were measured, and the SPF was calculated using the following formula (1). The MED is the minimum amount of ultraviolet light that first induces a slight, clearly demarcated erythema over at least two-thirds of the irradiated area 16 to 24 hours after irradiation. The ultraviolet absorption test for cosmetics was conducted in accordance with the "Japan Cosmetic Industry Association SPF Measurement Standards (2007 revised edition)" and evaluated according to the following criteria.

[0081] SPF = MED of applied area / MED of unapplied area (1)

[0082] ○: SPF 6 or higher ×: Less than SPF6 -: No rating

[0083] ·comprehensive evaluation The total score was calculated by giving 3 points for ◯, 1 point for △, and 0 points for × and -. A total of 12 points or more is a pass, but even one × is a fail.

[0084] [Table 1]

[0085] As is clear from Table 1, Examples 1 to 6, which contained all of the components (A) to (E), were good in moldability, dispersibility, stability over time, and UV absorbency. Comparing Example 1 and Comparative Example 1, both received an overall rating of 12 points, but Example 1 was superior in that it provided ultraviolet absorption and, furthermore, no foreign matter was found even after leaving it undisturbed for one month. Comparative Example 2, which contained methylenebisbenzotriazolyltetramethylbutylphenol, which has an ultraviolet absorbing effect but is neither water-soluble nor oil-soluble, failed to provide good ultraviolet absorbing properties, as well as poor dispersibility and long-term stability.

[0086] [Table 2]

[0087] As is clear from Table 2, Examples 7 to 11, in which the content of component (E) was 2.5 to 20 mass %, were all good in moldability, dispersibility, stability over time, and UV absorbency. Comparative Example 3, which did not contain component (E), and Comparative Examples 4 and 5, which contained less than 2.5% by mass of component (E), were poor in moldability, dispersibility, and stability over time, and were not in a state suitable for use as cosmetics.

[0088] Prescription example 1 A beauty stick (Formulation Example 1) was prepared as a water-in-oil sunscreen cosmetic containing components (A) to (E) of the present invention. Formulation Example 1 is shown in Table 3.

[0089] [Table 3] [Industrial Applicability]

[0090] The present invention can be used in water-in-oil sunscreen cosmetics such as stick-type makeup cosmetics, suncare cosmetics, skincare cosmetics, and haircare cosmetics.

Claims

1. (A) at least one compound that is pasty at 25°C and has a viscosity at 60°C of more than 30 mPa s and not more than 1,000 mPa s (hereinafter referred to as "component (A)"); (B) at least one compound having a hydroxystearic acid group and an oxyalkylene group (hereinafter referred to as "component (B)"); (C) an organic ultraviolet absorber (hereinafter referred to as “component (C)”), (D) water (hereinafter referred to as "component (D)"), and (E) at least one solid oil having a melting point of 60°C or higher (hereinafter referred to as "component (E)"), Component (C) is one or more organic ultraviolet absorbers selected from (C1) an oil-soluble organic ultraviolet absorber (hereinafter referred to as “component (C1)”) and (C2) a water-soluble organic ultraviolet absorber (hereinafter referred to as “component (C2)”), A water-in-oil sunscreen cosmetic, in which the content of component (E) is 2.5 to 20 mass % of the total amount of the cosmetic.

2. 2. The water-in-oil sunscreen cosmetic according to claim 1, which is substantially free of silicone compounds.

3. 2. The water-in-oil sunscreen cosmetic according to claim 1, wherein component (A) is one or more selected from hydrogenated castor oil isostearate, dipentaerythrityl hexahydroxystearate, dipentaerythrityl hexa(hydroxystearate / hexastearic acid / hexarosinate), dipentaerythrityl tri-polyhydroxystearate, bis-diglyceryl polyacyladipate-2, phytosteryl macadamiate, phytosteryl / isostearyl / cetyl / stearyl / behenyl dimer dilinoleate, di(phytosteryl / octyldodecyl) lauroyl glutamate, di(octyldodecyl / phytosteryl / behenyl) lauroyl glutamate, and bis(behenyl / isostearyl / phytosteryl) dimer dilinoleyl dimer dilinoleate.

4. 2. The water-in-oil sunscreen cosmetic according to claim 1, wherein component (A) is one or more selected from hydrogenated castor oil isostearate, dipentaerythrityl hexahydroxystearate, dipentaerythrityl hexa(hydroxystearate / stearic acid / rosin acid), dipentaerythrityl tri-polyhydroxystearate, and bis-diglyceryl polyacyladipate-2.

5. 2. The water-in-oil sunscreen cosmetic according to claim 1, wherein the content of component (A) is 1.5 to 15% by mass of the total amount of the cosmetic.

6. 2. The water-in-oil sunscreen cosmetic according to claim 1, wherein component (B) is one or more selected from PEG-30 dipolyhydroxystearate, PEG-5 hydrogenated castor oil, PEG-10 hydrogenated castor oil, PEG-20 hydrogenated castor oil, PEG-30 hydrogenated castor oil, PEG-40 hydrogenated castor oil, PEG-50 hydrogenated castor oil, PEG-60 hydrogenated castor oil, PEG-70 hydrogenated castor oil, PEG-80 hydrogenated castor oil, PEG-90 hydrogenated castor oil, and PEG-100 hydrogenated castor oil.

7. 2. The water-in-oil sunscreen cosmetic according to claim 1, wherein the content of component (B) is 0.5 to 10% by mass of the total amount of the cosmetic.

8. 2. The water-in-oil sunscreen cosmetic according to claim 1, wherein component (C) is one or more selected from the group consisting of oxybenzone-3, t-butyl methoxydibenzoylmethane, ethylhexyl methoxycinnamate, octocrylene, ethylhexyl salicylate, homosalate, ethylhexyl dimethyl PABA, ethylhexyl triazone, bisethylhexyloxyphenol methoxyphenyl triazine, diethylamino hydroxybenzoyl hexyl benzoate, drometrizole trisiloxane, oxybenzone-4, ferulic acid, terephthalylidene dicamphorsulfonic acid, and phenylbenzimidazole sulfonic acid.

9. 2. The water-in-oil sunscreen cosmetic according to claim 1, comprising component (C) as component (C1) and component (C2).

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