Solid powder ultraviolet-protective agent, method for producing same, and cosmetic

Abstract

[Problem] To provide a solid powder ultraviolet-protective agent having improved cohesiveness and sensation upon use. [Solution] A solid powder ultraviolet-protective agent containing: (A) a hydrophobized ultraviolet-scattering agent; (B) a polysaccharide, and (C) a non-ionic surfactant having an HLB value of 10 or more; said solid powder ultraviolet-protective agent being solidified by freeze-drying.

Description

Solid powder UV protection agent, its manufacturing method, and cosmetic

[0001] The present invention relates to a solid powder ultraviolet protection agent and a method for producing the same. The present invention also relates to a cosmetic composition containing the ultraviolet protection agent.

[0002]

[0003] Solid powder cosmetics, such as powder foundations and sunscreen powders, which are prepared by solidifying powder cosmetics, have been known for some time. Such solid powder cosmetics are generally applied to the skin by taking a portion of the cosmetic from the surface using a puff or the like. However, it is extremely important that the cosmetic has an ultraviolet protection effect to protect the wearer from ultraviolet rays. Therefore, it is necessary to effectively incorporate ultraviolet scattering agents and ultraviolet absorbers into solid powder cosmetics.

[0003] For example, Patent Document 1 discloses a solid powder cosmetic that contains a pigment having an ultraviolet scattering effect, such as titanium oxide or zinc oxide, and an ultraviolet absorber, such as 2-hydroxy-4-methoxybenzophenone.

[0004] Japanese Patent Application Laid-Open No. 2022-075058 Japanese Patent Publication No. 1-57084 Japanese Patent Application Laid-Open No. 62-260716

[0005] However, there are various challenges to effectively incorporating an UV scattering agent into a solid powder cosmetic. For example, because powdered UV scattering agents have high cohesion, incorporating such agents into a cosmetic not only reduces the quality of the cosmetic, but also creates a squelchy feeling characteristic of scattering agents when applied to the skin, worsening the feel of the cosmetic in use. The squelchy feeling is an unpleasant sensation felt when the cosmetic is applied to the skin, impeding smooth movement over the surface. Therefore, in an attempt to solve the problems of cohesion and squelchy feeling of powder cosmetics, various techniques have been developed, including surface treatment techniques for modifying the surface condition of powders and powder dispersion techniques that use surfactants and water-soluble polymers in combination (e.g., Patent Documents 2 and 3). However, the surface modification and dispersion techniques for powders discovered so far have not been effective enough in improving the cohesion and feel of powders in solid powder cosmetics.

[0006] Therefore, a main object of the present invention is to provide a solid powdery ultraviolet protection agent that has improved cohesiveness and feeling when used.

[0007] The inventors of the present invention have intensively investigated means for solving the above-mentioned problems of the prior art, and have found that by blending a hydrophobically treated UV scattering agent with a polysaccharide and a highly hydrophilic nonionic surfactant, a solid powder UV protection agent with improved cohesiveness and usability can be obtained. In particular, they have found that it is preferable to solidify the UV protection agent by freeze-drying technology. Based on this finding, the inventors have conceived that the problems of the prior art can be solved and have completed the present invention. The present invention will be specifically described below.

[0008] A first aspect of the present invention is a solid powder UV protection agent. The UV protection agent contains (A) a hydrophobized UV scattering agent, (B) a polysaccharide, and (C) a nonionic surfactant having an HLB value of 10 or more. The hydrophobized UV scattering agent is an agent in which hydrophobic groups are introduced onto the surface of an inorganic substance that basically has UV scattering properties. The HLB (Hydrophilic-Lipophilic Balance) value is an index representing the balance between hydrophilicity and hydrophobicity of a nonionic surfactant, and an HLB value of 10 or more indicates that the nonionic surfactant is a highly hydrophilic surfactant (generally an agent used in O / W emulsification, etc.). The hydrophilic polysaccharide improves the viscosity of the water-containing bulk before solidification and improves the stability of the solid powder after solidification. Furthermore, when a hydrophilic nonionic surfactant having an HLB value of 10 or more is added, the dispersibility of the hydrophobized UV scattering agent in the water-containing bulk before solidification is improved due to the action of the hydrophobic groups. Furthermore, when a hydrophobized UV scattering agent is combined with a hydrophilic nonionic surfactant having an HLB value of 10 or more and a hydrophilic polysaccharide, it is believed that associations are formed through hydrophobic interactions and hydrogen bonds, and thus blending these improves the viscosity of the bulk and the stability of the solid powder after solidifying this bulk. In other words, blending components (A) to (C) produces a solid powder UV protection agent in which the UV scattering agent is effectively dispersed. This improves the cohesiveness and usability of the UV protection agent.

[0009] The UV protection agent according to the present invention is preferably solidified by lyophilization (so-called freeze-drying). Lyophilization is a technique in which a substance is frozen and then dried by sublimating the water (ice) under vacuum. The hydrophobized UV scattering agent is effectively dispersed in a bulk containing water before solidification. Therefore, by solidifying this bulk by lyophilization, the effective dispersion state of the hydrophobized UV scattering agent can be maintained even after solidification. This can further improve the cohesiveness and usability of the UV protection agent.

[0010] In the ultraviolet protection agent according to the present invention, component (A) preferably contains at least one selected from hydrophobized titanium oxide having an average particle size of 100 nm or less and hydrophobized zinc oxide having an average particle size of 100 nm or less. As shown in the examples described later, hydrophobized titanium oxide and hydrophobized zinc oxide belong to component (A1), which is a preferred example of component (A).

[0011] In the ultraviolet protection agent according to the present invention, the hydrophobic treatment of component (A) is preferably at least one treatment selected from dimethicone treatment, hydrogen dimethicone treatment, stearic acid treatment, triethoxycaprylylsilane treatment, triisostearoyl titanate treatment, lecithin treatment, and N-acylamino acid treatment.

[0012] In the UV protection agent according to the present invention, component (B) preferably contains at least one selected from polysaccharides that are solid at 25°C and mixtures of glycosyltrehalose, hydrogenated starch hydrolysate, and water.

[0013] The ultraviolet protection agent according to the present invention preferably further contains (D) a polyhydric alcohol. Hydrophobized ultraviolet scattering agents are essentially hydrophobic particles with low affinity for water contained in the bulk, but by adding a polyhydric alcohol to the bulk, the hydrophobized ultraviolet scattering agent is well dispersed in water. As a result, the ultraviolet protection agent solidified by removing water contains the polyhydric alcohol, which improves the dispersibility of the hydrophobized ultraviolet scattering agent.

[0014] In the ultraviolet protection agent according to the present invention, the ratio of the content of component (C) (nonionic surfactant) to the content of component (D) (polyhydric alcohol) is preferably component (D) / component (C) = 0.01 to 1000. Component (D) / component (C) may be 0.5 to 50, or may be 1 to 10.

[0015] In the ultraviolet protection agent according to the present invention, the ratio of the contents of component (A) (hydrophobized ultraviolet scattering agent), component (C) (nonionic surfactant), and component (D) (polyhydric alcohol) is preferably component (A) / (component (C)+component (D))=1 to 20. Component (A) / (component (C)+component (D)) may be 1 to 15, or may be 2 to 10.

[0016] The UV protection agent according to the present invention preferably further contains (E) an oily agent that is liquid at 25° C. In this way, by blending an oily agent that is liquid at room temperature or around the temperature of the human skin surface, the sensation of use of the UV protection agent can be improved.

[0017] In the ultraviolet protection agent according to the present invention, the ratio of the contents of component (C) (nonionic surfactant), component (D) (polyhydric alcohol), and component (E) (oil) is preferably component (E) / (component (C)+component (D))=0.05 to 5. Component (E) / (component (C)+component (D)) may be 0.1 to 4, or may be 1 to 3.5.

[0018] The ultraviolet protection agent according to the present invention has a density of 0.03 to 0.15 g / cm ３ The ultraviolet protection agent solidified by freeze-drying thus has a relatively low density.

[0019] A second aspect of the present invention is a cosmetic, particularly a solid powder cosmetic, containing the UV protection agent according to the first aspect. Examples of the cosmetic according to the present invention include powder foundation, skin tone control powder, and sunscreen powder.

[0020] The third aspect of the present invention relates to a method for producing a solid powder UV protection agent. First, a mixture is obtained by mixing (A) a powdered hydrophobic UV scattering agent, (B) a polysaccharide, and (C) a nonionic surfactant with an HLB value of 10 or more with water (mixing step). Next, this mixture is filled into a mold and frozen to obtain a frozen product (freezing step). Next, this frozen product is dried in a vacuum dryer (drying step). In this drying step, the water (ice) in the frozen product is sublimated to obtain a solid product.

[0021] According to the present invention, it is possible to provide a solid powdery ultraviolet protection agent having improved cohesiveness and improved usability.

[0022] Hereinafter, embodiments of the present invention will be described with reference to the drawings. The present invention is not limited to the embodiments described below, and includes appropriate modifications of the embodiments described below within the scope obvious to those skilled in the art.

[0023] In the present specification, the numerical range "A to B" means "A or more and B or less."

[0024] [1. UV Protection Agent] The UV protection agent according to the present invention is a solid powder agent obtained by solidifying powder components. The UV protection agent according to the present invention contains at least the following components (A) to (C): (A) a hydrophobized UV scattering agent, (B) a polysaccharide, and (C) a nonionic surfactant having an HLB value of 10 or more. In addition, in a preferred embodiment, the UV protection agent according to the present invention may contain the following components (D) and / or (E): (D) a polyhydric alcohol, and (E) an oil agent that is liquid at 25°C.

[0025] The present invention may be, for example, a solid powder UV protection agent composed of components (A) to (C) or components (A) to (E), but it is of course possible to add other ingredients separately as long as the UV protection effect and usability of the active ingredients are not lost and the UV protection agent is in solid powder form. The present invention may also be a solid powder cosmetic containing the above-mentioned UV protection agent. Examples of solid powder cosmetic products include, but are not limited to, powder foundation, skin tone control powder, and sunscreen powder. Each of the above components (A) to (E) will be described below.

[0026] [Component (A): Hydrophobized UV Scattering Agent] The hydrophobized UV scattering agent is a UV scattering agent that has been hydrophobized. The UV scattering agent refers to a particulate substance that can reflect or scatter UV rays to protect the skin, etc. from UV rays. This particulate substance is generally made of an inorganic substance. Examples of UV scattering agents are titanium oxide, zinc oxide, cerium oxide, and iron oxide. Furthermore, these materials may be microparticulated or composited to be used as the UV scattering agent. In consideration of the high UV scattering effect, it is preferable to use one or both of titanium oxide and zinc oxide as the UV scattering agent.

[0027] In the present invention, UV scattering agents that have been subjected to a hydrophobic treatment are used. Preferred examples of hydrophobic treatments include dimethicone treatment, hydrogen dimethicone treatment, stearic acid treatment, triethoxycaprylylsilane treatment, triisostearoyl titanate treatment, lecithin treatment, and N-acylamino acid treatment. Dimethicone treatment is a treatment in which methylpolysiloxane is introduced onto the surface of an inorganic substance, imparting hydrophobicity derived from the siloxane skeleton to the inorganic substance. Hydrogen dimethicone treatment is a treatment in which a linear monomethylsiloxane polymer, in which some of the methyl groups of dimethicone are replaced with hydrogen, is introduced onto the surface of an inorganic substance, imparting hydrophobicity derived from the siloxane chain to the inorganic substance. Stearic acid treatment is a treatment in which stearic acid (a C18 saturated fatty acid) is immobilized onto the surface of an inorganic substance, imparting hydrophobicity derived from the alkyl chain to the inorganic substance. Triethoxycaprylylsilane treatment is a process that hydrophobicizes inorganic substances by introducing a silane coupling agent (triethoxycaprylylsilane) having a capryl group (C8 alkyl group) and an ethoxy group onto the surface of the inorganic substance. Triisostearoyl titanate treatment is a process that immobilizes an isostearoyl group (branched C18 alkyl group) onto the surface of the inorganic substance, imparting hydrophobicity derived from the isostearoyl group to the inorganic substance. Lecithin treatment is a process that hydrophobicizes inorganic substances by adsorbing lecithin onto inorganic substances, as lecithin is a natural hydrophilic phospholipid that also contains hydrophobic fatty acid residues, and orienting these fatty acid residues (hydrophobic portion) outward. N-acylamino acid treatment is a process that hydrophobicizes inorganic substances by immobilizing a hydrophobic amino acid derivative, in which an acyl group (such as a fatty acid residue) has been introduced into an amino acid, onto the surface of the inorganic substance. The hydrophobization treatment performed on such an ultraviolet scattering agent is not limited to one type, and two or more types may be performed in combination. In addition to the above-mentioned examples, the hydrophobization treatment may also be, for example, a known treatment such as isostearic acid treatment, aluminum stearate treatment, magnesium stearate treatment, simethicone treatment, octyltriethoxysilane treatment, or methylhydrogenpolysiloxane treatment.

[0028] The hydrophobized UV scattering agent preferably has an average particle size of 100 nm or less. There is no particular lower limit on the average particle size, but it is sufficient if it is 5 nm or more, and more preferably 10 nm or more. In this specification, the term "average particle size" refers to the average particle size value at 50% of the cumulative volume measured using a laser diffraction / scattering particle size distribution analyzer. By using a UV scattering agent with a relatively small average particle size of 1 to 100 nm, the dispersibility of the UV scattering agent in the UV protection agent can be improved.

[0029] Furthermore, in the present invention, inorganic substances with UV scattering effects, such as titanium oxide and zinc oxide, are used as UV scattering agents rather than as pigments. Therefore, the UV scattering agent is blended at an appropriate particle size and content so that the UV protection agent or cosmetic containing the same can exhibit a high UV scattering effect. As mentioned above, the average particle size of the UV scattering agent is preferably 5 nm to 100 nm, and the UV scattering agent is preferably contained in the UV protection agent or cosmetic at a content of 3% by mass or more. Specifically, the total amount of the UV scattering agent is preferably 1 to 50% by mass, and particularly preferably 3 to 30% by mass.

[0030] It should be noted that ultraviolet scattering agents are distinguished from ultraviolet absorbers, which have the effect of absorbing ultraviolet rays. Examples of ultraviolet absorbers include amyl paradimethylbenzoate, 2-ethylhexyl paradimethylaminobenzoate, ethyl 4-[N,N-di(2-hydroxypropyl)amino]benzoate, hexyl diethylaminohydroxybenzoylbenzoate, 2-ethylhexyl salicylate, 2-ethoxyethyl paramethoxycinnamate, 2-ethylhexyl paramethoxycinnamate, glyceryl di-paramethoxycinnamate mono-2-ethylhexanoate, 2,4,6-tris[4-(2-ethylhexyloxycarbonyl)anilino]-1,3,5-triazine, octocrylene, 4-t-butyl-4'-methoxydibenzoylmethane, dimethicodiethyl benzalmalonate, and bisethylhexyloxyphenol methoxyphenyl triazine.

[0031] [Component (B): Polysaccharides] The polysaccharides are incorporated primarily for the purpose of imparting viscosity to the bulk before solidification and improving the stability of the UV protection agent before and after solidification. The polysaccharides are not particularly limited as long as they are water-soluble polysaccharides commonly used in cosmetics. Examples of polysaccharides include water-soluble cellulose derivatives and their salts, starch, and other natural polysaccharides. Examples of water-soluble cellulose derivatives and their salts include cellulose gum (sodium carboxymethylcellulose), hydroxypropyl methylcellulose, and carboxymethylcellulose. Examples of starch include seed starches such as rice starch, wheat starch, and corn starch, and root starches such as tapioca starch and potato starch. The starch may also be a mixture of compounds containing starch, such as a mixture of glycosyl trehalose, hydrogenated starch hydrolysate, and water. Examples of natural polysaccharides include xanthan gum and sodium hyaluronate. In particular, since the UV protection agent containing the polysaccharide is in the form of a solid powder, it is preferable to use a polysaccharide that becomes solid at 25° C. Specific examples of polysaccharides that become solid at 25° C. include cellulose gum (sodium carboxymethylcellulose), hydroxypropyl methylcellulose, xanthan gum, and sodium hyaluronate. One or more of these polysaccharides can be blended.

[0032] [Component (C) Nonionic Surfactant with an HLB Value of 10 or More] The nonionic surfactant is blended primarily for the purposes of dispersing the hydrophobized UV scattering agent in the water-containing bulk before solidification and improving the cohesion of the UV scattering agent after solidification. The nonionic surfactant used is one with an HLB value of 10 or more, which exhibits hydrophilicity. The HLB value of the surfactant is sufficient as long as it is 10 or more, and there is no particular upper limit, but for example, the HLB value of the surfactant is preferably 10 to 16. Examples of nonionic surfactants include polyglycerin fatty acid esters, sorbitan fatty acid esters, glycerin fatty acid esters, propylene glycol fatty acid esters, polyoxyalkylene alkyl ethers, polyoxyalkylene fatty acid esters, polyoxyalkylene alkylphenols, polyoxyethylene sorbit fatty acid esters, polyoxyethylene alkylphenyl formaldehyde condensates, polyoxyethylene sterol and derivatives thereof, polyoxyethylene cholesterol ether, polyoxyethylene cholestanol ether, polyoxyethylene phytosterol ether and polyoxyethylene phytostanol ether, polyoxyethylene lanolin and derivatives thereof, polyoxyethylene beeswax derivatives, sugar esters, polyoxyethylene hydrogenated castor oil, and polyoxyethylene castor oil. In the examples described below, polyglyceryl-10 laurate, polyglyceryl-10 oleate, olive oil glycereth-8 esters, polysorbate 80, PEG-20 methyl glucose sesquistearate, polysorbate 60, polyoxyethylene (80) hydrogenated castor oil, polyoxyethylene (60) hydrogenated castor oil, and polyoxyethylene (20) hydrogenated castor oil are used as nonionic surfactants having an HLB value of 10 or more.

[0033] The HLB value of a nonionic surfactant is an actually measured value. The HLB value is a numerical value devised by W. C. Griffin and assigned to nonionic surfactants, and represents the balance in strength between the lipophilic group (alkyl group) and the hydrophilic group (ethylene oxide chain) of the nonionic surfactant. The HLB value is measured in accordance with the measurement of the HLB value by the emulsification method described in "Handbook - Cosmetics and Pharmaceutical Ingredients - Revised Edition," published by Nikko Chemicals Co., Ltd. on February 1, 1977, pages 854-855. Specifically, to determine the HLB value of a nonionic surfactant, the nonionic surfactant is combined with sorbitan monostearate (NIKKOL SS-10, HLB 4.7) as a standard emulsifier, and the total amounts of these two emulsifiers are kept constant while only the ratio is varied to emulsify liquid paraffin (required HLB 10.1), which is the substance to be emulsified. After leaving the mixture overnight, the optimal ratio of emulsifiers that provides stability is determined from the amount of creaming, turbidity, and water separation from the lower layer, and the HLB value x of the nonionic surfactant is calculated using the following formula (1): [Equation (1)] y = (x × amount used (mass %) + z × amount used (mass %)) / 100 In equation (1), "x" represents the HLB value of the nonionic surfactant, "y" represents the required HLB value of liquid paraffin, and "z" represents the HLB value of sorbitan monostearate (NIKKOL SS-10). The HLB value of liquid paraffin can be determined in a similar manner using a combination of sorbitan monostearate (NIKKOL SS-10, HLB 4.7) and POE sorbitan monostearate (NIKKOL TS-10, HLB 14.9).

[0034] [Component (D) Polyhydric Alcohol] The polyhydric alcohol is blended primarily for the purpose of further improving the dispersibility of the hydrophobized UV scattering agent in the water-containing bulk before solidification. The polyhydric alcohol is preferably a water-soluble polyhydric alcohol. Examples of polyhydric alcohols include glycerin, diglycerin, polyglycerin-3, polyglycerin-10, 1,3-butylene glycol, propylene glycol, 3-methyl-1,3-butanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, trimethylolpropane, pentaerythritol, hexylene glycol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,2-pentanediol, 1,2-hexanediol, 1,2-octanediol, 1,2-decanediol, polypropylene glycol, sorbitol, maltitol, and trehalose. The polyhydric alcohols may be used alone or in combination of two or more.

[0035] [Component (E) Oil that is Liquid at 25°C] The oil is blended primarily for the purpose of improving the feel of the UV protection agent on the skin when applied. The oil preferably has a melting point of 25°C or lower so that it remains liquid at room temperature or when applied to the skin surface. Examples of liquid oils include ethyl oleate, ethyl linoleate, isopropyl myristate, isopropyl palmitate, isopropyl isostearate, ethylhexyl methoxycinnamate, cetyl 2-ethylhexanoate, isocetyl 2-ethylhexanoate, isostearyl 2-ethylhexanoate, 2-ethylhexyl palmitate, 2-hexyldecyl isostearate, isostearyl isostearate, trimethylolpropane triisostearate, octyldodecyl myristate, isostearyl myristate, isocetyl myristate, hexyl laurate, decyl oleate, octyldodecyl oleate, and pili. Isostearyl valerate, isopropyl isostearate, isononyl isononanoate, 2-ethylhexyl isononanoate, isodecyl isononanoate, isotridecyl isononanoate, octyldodecyl erucate, pentaerythrityl tetraethylhexanoate, trimethylolpropane triethylhexanoate, glyceryl tri-2-ethylhexanoate, dioctyl succinate, propylene glycol dicaprylate, propylene glycol dicaprate, propylene glycol dinonanoate, propylene glycol di(caprylic / capric acid), propylene glycol diisostearate, mineral oil, dimethicone, etc.

[0036] [Optional Components] In addition to the components described above, the UV protection agent according to the present invention may contain one or more optional components commonly used in the field of cosmetics. Examples of the optional components include moisturizers, surfactants, water-soluble polymers, liquid oils, oil-soluble gelling agents, clay minerals, resins, film-forming agents, UV absorbers, powders, pigments, dyes, coloring materials, preservatives, antibacterial agents, antioxidants, salts, pH adjusters, chelating agents, fragrances, refreshing agents, antiperspirants, anti-inflammatory agents, skin activators, skin-beautifying components, mica (silica mineral), and various extracts.

[0037] [Density] As described below, the UV protection agent according to the present invention is preferably freeze-dried to form a solid powder. In freeze-drying, moisture is almost completely removed by sublimation during the process, and thus the UV protection agent solidified by freeze-drying has a characteristic that its density is low. Specifically, the density of the freeze-dried UV protection agent is 0.03 to 0.15 g / cm. ３ is preferably 0.05 to 0.12 g / cm ３ More preferably, it is 0.05 to 0.09 g / cm ３ It is particularly preferred that:

[0038] [2. Manufacturing Method of UV Protection Agent] Next, a manufacturing method of a solid powder UV protection agent will be described. The manufacturing method of the UV protection agent is mainly divided into a mixing step of obtaining a mixture of main components and a freeze-drying step of freeze-drying the obtained mixture.

[0039] In the mixing step, the aforementioned components (A) to (E) are mixed to prepare a slurry bulk before freeze-drying. In the mixing step, the components (A) to (E) may be mixed all at once, but it is preferable to mix them in the following steps:

[0040] First, (A) a hydrophobic UV scattering agent and (E) an oil are mixed, and the hydrophobic UV scattering agent is pulverized to a predetermined particle size to obtain a powdery first mixture (step 1). Meanwhile, the entire amount of (B) polysaccharide, a portion of (D) a polyhydric alcohol, and purified water are mixed to obtain a swollen product (step 2). Then, the remaining portion of (D) a polyhydric alcohol, (C) a nonionic surfactant, and purified water are mixed with this swollen product to obtain a second mixture (step 3). Then, the first mixture and the second mixture are mixed to obtain a water-containing slurry bulk (step 4). In this way, it is preferable to separately prepare a first mixture obtained by mixing a hydrophobic UV scattering agent and an oil, and a second mixture obtained by mixing other components and purified water, and finally mix the first mixture and the second mixture. The hydrophobic treated UV scattering agent is coated with an oil agent in advance, and then mixed with other components, thereby improving the dispersibility of the hydrophobic treated UV scattering agent in a bulk containing moisture.

[0041] The freeze-drying step is a step in which the bulk obtained in the mixing step is freeze-dried to form a solid powder. In the freeze-drying step, the slurry bulk is first filled into a mold (form) and frozen to obtain a frozen product (step 5). The freezing temperature is preferably −20°C or lower, and particularly preferably −50 to −20°C or −40 to −30°C. The obtained frozen product is then dried at a low temperature in a reduced pressure environment using a vacuum dryer (step 6). The atmospheric pressure condition for drying the frozen product may be, for example, 100 Pa or lower, and preferably maintained at 1 to 100 Pa or 10 to 80 Pa. The temperature condition for drying the frozen product may be −10°C or lower, at which point the water becomes solid (ice), and preferably maintained at, for example, −50 to −20°C. In this way, in a low-temperature environment where the water in the bulk becomes solid, by lowering the air pressure so that the boiling point is −50 to 30°C, more preferably −50 to −20°C, the water does not become liquid but changes from a solid to a gas (sublimes). In this way, the freeze-drying process can remove water from the bulk, resulting in a solid powder UV protection agent. Note that the freeze-drying process is publicly known, and other details may be determined according to publicly known conditions.

[0042] [1. UV Protection Agent] Tables 1 to 5 show the blending ratios of the components blended in Examples and Comparative Examples of the UV protection agent according to the present invention. The blending ratios are expressed in mass %.

[0043]

[0044]

[0045]

[0046]

[0047]

[0048]

[0049]

[0050]

[0051]

[0052]

[0053] In the above table, the numbers in parentheses, such as "(10 nm)", are the average particle size of the scattering material. In the above table, the * marks are footnote numbers that indicate the brand or product name of each component, and the details are as follows: (Footnotes) *1 MTY-110M3S (manufactured by Teika Corporation) *2 MT-01 (manufactured by Teika Corporation) *3 MTY-500SAM (manufactured by Teika Corporation) *4 MTY-700BS (manufactured by Teika Corporation) *5 MZY-505M (manufactured by Teika Corporation) *6 ASL-1 TiO ２ MP-1133 (manufactured by Daito Chemical Industry Co., Ltd.) * 7 SA-Titanium CR-50 (manufactured by Miyoshi Chemical Industry Co., Ltd.) * 8 ITT-2 TiO2 CR-50 (manufactured by Daito Chemical Industry Co., Ltd.) * 9 XZ-300F-LP (manufactured by Sakai Chemical Industry Co., Ltd.) * 10 MT-500SA (manufactured by Teika Co., Ltd.) * 11 MZ-500 (manufactured by Teika Co., Ltd.) * 12 CR-50 (manufactured by Ishihara Sangyo Kaisha, Ltd.) * 13 XZ-300F (manufactured by Sakai Chemical Industry Co., Ltd.) * 14 Metrose 65SH4000 (manufactured by Shin-Etsu Chemical Co., Ltd.) * 15 TORNARE (manufactured by Hayashibara Co., Ltd.) * 16 NIKKOL Decaglyn 1-L (manufactured by Nikko Chemicals Co., Ltd.) * 17 NIKKOL Decaglyn 1-OV (manufactured by Nikko Chemicals Co., Ltd.) *18 RESPLANTA OLIVE MB (manufactured by SHARON PERSONAL CARE S.R.L.) *19 NONION OT-221R (manufactured by NOF Corporation) *20 NIKKOL TS-10V (manufactured by Nikko Chemicals Co., Ltd.) *21 NIKKOL HCO-80 (manufactured by Nikko Chemicals Co., Ltd.) *22 NIKKOL HCO-60 (manufactured by Nikko Chemicals Co., Ltd.) *23 NIKKOL HCO-20 (manufactured by Nikko Chemicals Co., Ltd.)

[0054] Example 1 contains (A) 10% dimethicone, hydrogen dimethicone, aluminum hydroxide, and titanium dioxide treated with hydrated silica (10 nm) as a hydrophobic scattering agent, and 20% dilauroyl glutamic acid Na, lysine, magnesium chloride, and titanium dioxide treated with aluminum hydroxide (250 nm), (B) 0.1% cellulose gum (sodium carboxymethylcellulose) as a polysaccharide, (C) 2% olive oil glycereth-8 esters as a nonionic surfactant, (D) 3% tripropylene glycol as a polyhydric alcohol, (E) 7% ethylhexyl methoxycinnamate as an oil agent, and 57.9% mica. The density of the finally obtained UV protection agent was 0.072 g / cm ３ It was.

[0055] Example 2 was the same as Example 1, except that stearic acid and aluminum hydroxide-treated titanium oxide (10 nm) were contained at 10% instead of the dimethicone, hydrogen dimethicone, aluminum hydroxide, and hydrous silica-treated titanium oxide (10 nm) of Example 1. The density of the finally obtained UV protection agent was 0.073 g / cm ３ It was.

[0056] Example 3 was the same as Example 1, except that dimethicone-treated titanium oxide (35 nm) was contained at 10% instead of the dimethicone-hydrogen dimethicone-aluminum hydroxide-hydrated silica-treated titanium oxide (10 nm) of Example 1. The density of the finally obtained UV protection agent was 0.072 g / cm ３ It was.

[0057] Example 4 was the same as Example 1, except that hydrogen dimethicone-treated titanium oxide (80 nm) was contained at 10% instead of the dimethicone-hydrogen dimethicone-aluminum hydroxide-hydrated silica-treated titanium oxide (10 nm) of Example 1. The density of the finally obtained UV protection agent was 0.071 g / cm ３ It was.

[0058] Example 5 was the same as Example 1, except that dimethicone-treated zinc oxide (25 nm) was contained at 10% instead of the dimethicone-hydrogen dimethicone-aluminum hydroxide-hydrated silica-treated titanium oxide (10 nm) of Example 1. The density of the finally obtained UV protection agent was 0.074 g / cm ３ It was.

[0059] Example 6 was the same as Example 1, except that triethoxycaprylylsilane and dimethicone-treated zinc oxide (25 nm) were contained at 10% instead of the dimethicone, hydrogen dimethicone, aluminum hydroxide, and hydrous silica-treated titanium oxide (10 nm) of Example 1. The density of the finally obtained UV protection agent was 0.077 g / cm ３ It was.

[0060] Example 7 was the same as Example 2, except that dimethicone and titanium oxide treated with aluminum hydroxide (250 nm) were contained at 20% instead of the sodium dilauroyl glutamate, lysine, magnesium chloride, and titanium oxide treated with aluminum hydroxide (250 nm) of Example 2. The density of the finally obtained UV protection agent was 0.07 g / cm ３ It was.

[0061] Example 8 was the same as Example 2, except that lecithin-treated titanium oxide (250 nm) was contained at 20% instead of the sodium dilauroyl glutamate-lysine-magnesium chloride-aluminum hydroxide-treated titanium oxide (250 nm) of Example 2. The density of the finally obtained UV protection agent was 0.065 g / cm ３ It was.

[0062] Example 9 was the same as Example 2, except that 20% of isopropyl titanium triisostearate and aluminum hydroxide-treated titanium oxide (250 nm) was used instead of the sodium dilauroyl glutamate, lysine, magnesium chloride, and aluminum hydroxide-treated titanium oxide (250 nm) of Example 2. The density of the finally obtained ultraviolet protection agent was 0.073 g / cm ３ It was.

[0063] Example 10 was the same as Example 2, except that hydrogen dimethicone-treated zinc oxide (300 nm) was contained at 20% instead of the dilauroyl glutamic acid Na, lysine, magnesium chloride, and aluminum hydroxide-treated titanium oxide (250 nm) of Example 2. The density of the finally obtained UV protection agent was 0.072 g / cm ３ It was.

[0064] Example 11 did not contain the stearic acid / Al hydroxide-treated titanium oxide (10 nm) of Example 2, but contained 30% dilauroyl glutamic acid sodium / lysine / Mg chloride / Al hydroxide-treated titanium oxide (250 nm), and the rest was the same as Example 1. The density of the finally obtained UV protection agent was 0.066 g / cm ３ It was.

[0065] Example 12 was the same as Example 2, except that dipropylene glycol was contained at 3% instead of tripropylene glycol in Example 2. The density of the finally obtained UV protection agent was 0.07 g / cm ３ It was.

[0066] Example 13 was the same as Example 2, except that 3% of 1,3-butylene glycol was used instead of the tripropylene glycol used in Example 2. The density of the finally obtained UV protection agent was 0.066 g / cm ３ It was.

[0067] Example 14 was the same as Example 2, except that 3% of glycerin was used instead of tripropylene glycol. The density of the finally obtained UV protection agent was 0.063 g / cm ３ It was.

[0068] Example 15 was the same as Example 2, except that 0.1% hydroxypropyl methylcellulose was used instead of the cellulose gum (sodium carboxymethylcellulose) of Example 2. The density of the final UV protection agent was 0.071 g / cm ３ It was.

[0069] Example 16 was the same as Example 2, except that xanthan gum was used at 0.1% instead of the cellulose gum (sodium carboxymethylcellulose) used in Example 2. The density of the finally obtained UV protection agent was 0.074 g / cm ３ It was.

[0070] Example 17 was the same as Example 2, except that 0.1% sodium hyaluronate was included instead of the cellulose gum (sodium carboxymethylcellulose) of Example 2. The density of the finally obtained UV protection agent was 0.073 g / cm ３ It was.

[0071] Example 18 was the same as Example 2, except that instead of the cellulose gum (sodium carboxymethylcellulose) of Example 2, a glycosyltrehalose-hydrolyzed hydrogenated starch-water mixture was contained at 1% and mica was contained at 57%. The density of the finally obtained UV protection agent was 0.072 g / cm ３ It was.

[0072] Example 19 was the same as Example 2, except that polyglyceryl-10 laurate was used at 2% instead of the olive oil glycereth-8 esters of Example 2. The density of the finally obtained UV protection agent was 0.076 g / cm ３ It was.

[0073] Example 20 was the same as Example 2, except that 2% polyglyceryl-10 oleate was used instead of the olive oil glycereth-8 esters of Example 2. The density of the finally obtained UV protection agent was 0.075 g / cm ３ It was.

[0074] Example 21 was the same as Example 2, except that 2% polysorbate 80 was used instead of the olive oil glycereth-8 esters of Example 2. The density of the finally obtained UV protection agent was 0.074 g / cm ３ It was.

[0075] Example 22 was the same as Example 2, except that 2% PEG-20 methyl glucose sesquistearate was used instead of the olive oil glycereth-8 esters of Example 2. The density of the final UV protection agent was 0.072 g / cm ３ It was.

[0076] Example 23 was the same as Example 2, except that 2% polysorbate 60 was used instead of the olive oil glycereth-8 esters of Example 2. The density of the finally obtained UV protection agent was 0.07 g / cm ３ It was.

[0077] Example 24 was the same as Example 2, except that 2% polyoxyethylene (80) hydrogenated castor oil was used instead of the olive oil glycereth-8 esters of Example 2. The density of the finally obtained UV protection agent was 0.069 g / cm ３ It was.

[0078] Example 25 was the same as Example 2, except that 2% polyoxyethylene (60) hydrogenated castor oil was used instead of the olive oil glycereth-8 esters of Example 2. The density of the finally obtained UV protection agent was 0.068 g / cm ３ It was.

[0079] Example 26 was the same as Example 2, except that 2% polyoxyethylene (20) hydrogenated castor oil was used instead of the olive oil glycereth-8 esters of Example 2. The density of the finally obtained UV protection agent was 0.066 g / cm ３ It was.

[0080] Example 27 was the same as Example 2, except that 7% of glyceryl tri-2-ethylhexanoate was used instead of ethylhexyl methoxycinnamate. The density of the finally obtained UV protection agent was 0.072 g / cm ３ It was.

[0081] Example 28 was the same as Example 2, except that mineral oil was used at 7% instead of ethylhexyl methoxycinnamate in Example 2. The density of the finally obtained UV protection agent was 0.07 g / cm３ It was.

[0082] Example 29 was the same as Example 2, except that dimethicone was contained at 7% instead of ethylhexyl methoxycinnamate in Example 2. The density of the finally obtained UV protection agent was 0.068 g / cm ３ It was.

[0083] Example 30 contained 10% of olive oil glycereth-8 esters as the (C) nonionic surfactant, 0.1% of tripropylene glycol as the (D) polyhydric alcohol, and 52.8% of mica, and was otherwise the same as Example 2. The density of the finally obtained UV protection agent was 0.069 g / cm ３ It was.

[0084] Example 31 contained 0.01% of olive oil glycereth-8 esters as the nonionic surfactant (C), 10% of tripropylene glycol as the polyhydric alcohol (D), and 52.89% of mica, and was otherwise the same as Example 2. The density of the finally obtained UV protection agent was 0.07 g / cm ３ It was.

[0085] Example 32 contained, as (A) hydrophobic scattering agents, 1% of stearic acid / Al hydroxide-treated titanium oxide (10 nm) and 4% of dilauroyl glutamic acid Na / lysine / Mg chloride / Al hydroxide-treated titanium oxide (250 nm), and contained 82.9% mica, and the rest was the same as Example 2. The density of the finally obtained UV protection agent was 0.072 g / cm ３ It was.

[0086] Example 33 contains, as (A) hydrophobic scattering agents, 10% of stearic acid / Al hydroxide treated titanium oxide (10 nm), 10% of triethoxycaprylylsilane / dimethicone treated zinc oxide (25 nm), 15% of dilauroyl glutamic acid Na / lysine / Mg chloride / Al hydroxide treated titanium oxide (250 nm) and 15% of hydrogen dimethicone treated zinc oxide (300 nm), and 37.9% of mica, and the rest was the same as Example 2. The density of the finally obtained UV protection agent was 0.076 g / cm ３It was.

[0087] Example 34 contained, as (A) hydrophobic scattering agents, 20% of titanium oxide (10 nm) treated with stearic acid and aluminum hydroxide, and 50% of titanium oxide (250 nm) treated with sodium dilauroyl glutamate, lysine, magnesium chloride, and aluminum hydroxide, and 17.9% of mica, and the rest was the same as Example 2. The density of the finally obtained ultraviolet protection agent was 0.08 g / cm. ３ It was.

[0088] Example 35 contained 0.5% ethylhexyl methoxycinnamate as the (E) oil agent and 64.4% mica, and the rest was the same as Example 2. The density of the finally obtained ultraviolet protection agent was 0.07 g / cm ３ It was.

[0089] Example 36 contained 10% ethylhexyl methoxycinnamate as the (E) oil agent and 54.9% mica, and the rest was the same as Example 2. The density of the finally obtained ultraviolet protection agent was 0.082 g / cm ３ It was.

[0090] Example 37 contained 7% ethylhexyl methoxycinnamate and 7% glyceryl tri-2-ethylhexanoate as the (E) oil agent, and contained 50.9% mica, and the rest was the same as Example 2. The density of the finally obtained UV protection agent was 0.084 g / cm ３ It was.

[0091] Example 38 did not contain (D) polyhydric alcohol and contained 60.9% mica, and the rest was the same as Example 2. The density of the finally obtained ultraviolet protection agent was 0.070 g / cm ３ It was.

[0092] Example 39 did not contain the oil (E) and contained 57.9% mica, and the rest was the same as Example 2. The density of the finally obtained ultraviolet protection agent was 0.072 g / cm ３ It was.

[0093] In Example 40, the mixing ratio of the powder component (100%) to the non-prescribed purified water (50%) was 2:1, and the amount of purified water was half that of the examples, but the rest was the same as Example 2. The density of the finally obtained UV protection agent was 0.116 g / cm ３ It was.

[0094] Comparative Example 1 did not contain the hydrophobic scattering agent (A) and contained 87.9% mica, and was otherwise the same as Example 2.

[0095] Comparative Example 2 was the same as Example 2, except that (A) the hydrophobic scattering material was replaced with 30% of aluminum hydroxide / hydrated silica-treated titanium oxide (35 nm) as a hydrophilic scattering agent.

[0096] Comparative Example 3 was the same as Example 2, except that (A) the hydrophobic scattering material was replaced with 30% zinc oxide (25 nm) as a hydrophilic scattering agent.

[0097] Comparative Example 4 was the same as Example 2, except that (A) the hydrophobic scattering material was replaced with 30% of titanium oxide (250 nm) treated with aluminum hydroxide as a hydrophilic scattering agent.

[0098] Comparative Example 5 was the same as Example 2, except that (A) the hydrophobic scattering material was replaced with 30% zinc oxide (300 nm) as a hydrophilic scattering agent.

[0099] Comparative Example 6 did not contain (B) polysaccharides and contained 58% mica, and was otherwise the same as Example 2.

[0100] Comparative Example 7 was the same as Example 2, except that it did not contain the surfactant (C) and contained 59.9% mica.

[0101] Comparative Example 8 was the same as Example 2, except that instead of the olive oil glycereth-8 esters of Example 2, 2% polyglyceryl tristearate was used as a nonionic surfactant with an HLB value of less than 10.

[0102] Comparative Example 9 was the same as Example 2, except that instead of the olive oil glycereth-8 esters of Example 2, sorbitan sesquioleate was used as a nonionic surfactant with an HLB value of less than 10 at 2%.

[0103] Comparative Example 10 was the same as Example 2, except that instead of the olive oil glycereth-8 esters of Example 2, lecithin was used as a surfactant at 2%.

[0104] As shown in Tables 1 to 4 above, Examples 1 to 37 all contained component (A) a hydrophobic scattering agent, component (B) a polysaccharide, component (C) a nonionic surfactant, component (D) a polyhydric alcohol, and component (E) an oil. Furthermore, as shown in Table 5, Example 38 did not contain component (D) a polyhydric alcohol, but contained the other components (A) to (C) and (E). Furthermore, Example 39 did not contain component (E) an oil, but contained the other components (A) to (D). Furthermore, each Example contained mica in addition to the above components.

[0105] Each example was produced using the following steps: (1) Component A and mica were mixed to obtain a mixture. (2) Component E was added to the mixture (1) and mixed to obtain a mixture. (3) The mixture (2) was pulverized to obtain a powdered first mixture. (4) Component B, a portion of Component D, and a portion of purified water were mixed to obtain a swollen product. (5) The remaining portion of Component D, Component C, and the remaining portion of purified water were added to the swollen product (4) and mixed to obtain a second mixture. (6) The powdered first mixture (3) was added to the second mixture (5) and mixed to obtain a bulk. (7) The bulk (6) was poured into a silicone mold and flash-frozen in a flash freezer to obtain a frozen sample. The temperature inside the flash freezer was set to -40°C, and the cooling time was 60 minutes. (8) The frozen sample (7) was freeze-dried in a vacuum dryer while maintaining the frozen state, to obtain the final UV protection agent. The temperature inside the vacuum dryer was set to -40°C and the pressure was set to 50Pa.

[0106] In Example 38, component (D) was not contained, and therefore addition of component (D) was omitted in the above steps (4) and (5). In Example 39, component (E) was not contained, and therefore step (2) was omitted. In Examples 38 and 39, UV protection agents were produced according to the above steps.

[0107] As shown in Table 5 above, Comparative Example 1 did not contain component (A) hydrophobic scattering agent, but contained other components (B) to (E). Comparative Examples 2 to 5 did not contain component (A) hydrophobic scattering agent, but instead contained a hydrophilic scattering agent, and also contained other components (B) to (E). Comparative Example 6 did not contain component (B) polysaccharide, but contained other components (A), (C) to (E). Comparative Examples 7 to 10 did not contain component (C) nonionic surfactant, but contained other components (A), (B), (D), and (E). Each Comparative Example contained mica in addition to the above components, as in each Example.

[0108] Each comparative example was basically produced using the same steps as the above-mentioned examples. However, since comparative example 1 did not contain component (A), step (1) was omitted, and mica and component (E) were mixed in step (2) to obtain a mixture. Furthermore, comparative examples 2 to 5 contained a hydrophilic scattering agent instead of component (A), so the hydrophilic scattering agent and mica were mixed in step (1). Furthermore, comparative example 6 did not contain component (B), so the addition of component (B) was omitted in step (4). Furthermore, comparative examples 7 to 10 did not contain component (C), so component (C) was omitted in step (5). In all other comparative examples, ultraviolet protection agents were produced according to the above-mentioned steps.

[0109] As shown in Tables 1 to 5, for each Example and Comparative Example, the UV protection improvement effect, the appropriate amount of application, adhesion to the skin, and smooth feel during use were measured or evaluated. The methods for measuring or evaluating each effect or performance are as follows.

[0110] [UV Protection Improvement Effect] For each Example and Comparative Example, a sample of the UV protection agent was prepared by freeze-drying (steps (7) and (8) above) and a sample of the UV protection agent was prepared by conventional drying. Furthermore, 0.35 g of each sample was applied with a finger to a 5 cm x 5 cm PMMA plate, and the SPF value was measured using a UV-2000S SPF Analyzer (manufactured by Labshere, USA). The obtained measured value was applied to the following formula to confirm the UV protection improvement effect of freeze-drying: (Formula) (Measured value of freeze-dried sample / Measured value of conventionally dried sample) * 100. Note that for conventional drying, the bulk obtained in step (6) above was filled into a metal dish and press-molded (water that seeped out during pressing was removed by press suction, if necessary), and then dried for 12 hours in a constant temperature bath at 40°C. The value calculated by the above formula was evaluated according to the following criteria, A to D. (Evaluation Criteria) A: 1.25 or more B: 1.15 times or more and less than 1.25 times C: 1.05 times or more and less than 1.15 times D: Less than 1.05 times

[0111] [Appropriate amount of training] A use test was conducted on the samples of each Example and Comparative Example by a panel of 20 experts, and each panelist evaluated them on a four-point scale using the absolute criteria below. The average score was calculated from the total score of all the panelists, and the average score was evaluated from A to D according to the criteria below. Specifically, the amount of training of powder on the mat when each sample was rubbed against the mat was evaluated. (Absolute criteria) 3: The amount of training is appropriate 2: The amount of training is slightly insufficient or slightly excessive 1: The amount of training is slightly insufficient or slightly excessive 0: The amount of training is insufficient or excessive (Evaluation criteria) A: 2.5 points or more B: 2 points or more but less than 2.5 points C: 1 point or more but less than 2 points D: Less than 1 point

[0112] [Adhesion to skin] A use test was conducted on the samples of each Example and Comparative Example by a panel of 20 experts, who each evaluated them on a four-point scale using the absolute criteria below. The average score was calculated from the total scores of all the panelists, and the score was evaluated from A to D according to the following criteria. Specifically, an appropriate amount of each sample was applied to the skin, and the level of adhesion of the cosmetic upon application was evaluated. (Absolute criteria) 3: Very noticeable 2: noticeable 1: Slightly noticeable 0: Not noticeable (Evaluation criteria) A: 2.5 points or more B: 2 points or more but less than 2.5 points C: 1 point or more but less than 2 points D: Less than 1 point

[0113] [Smooth feel when used] A use test was conducted on the samples of each Example and Comparative Example by 20 expert panelists, who each evaluated them on a four-point scale using the absolute criteria below. The average score was calculated from the total scores of all panelists, and the results were evaluated from A to D according to the following criteria. Specifically, an appropriate amount of each sample was applied to the skin, and the smoothness upon application (absence of squeaky or sticky feeling) was evaluated. (Absolute criteria) 3: Very smooth with no squeaky or sticky feeling 2: Smooth with no squeaky or sticky feeling 1: Slight squeaky or sticky feeling, but smooth 0: Slight squeaky or sticky feeling, not smooth (Evaluation criteria) A: 2.5 points or more B: 2 points or more but less than 2.5 points C: 1 point or more but less than 2 points D: Less than 1 point

[0114] In view of the above-mentioned effect measurements and evaluation of usability, it can be said that the influence of each of the components (A) to (D) on the UV protection effect and usability generally tends to be as shown in Table 6. However, the extent of the influence varies depending on the compounded components.

[0115]

[0116] Specifically, it was found that by blending components (A) to (E), when a UV protection agent was prepared by freeze-drying, the UV protection effect was significantly improved compared to when a UV protection agent was prepared by conventional drying. This is evident, for example, from a comparison of all the Examples and all the Comparative Examples. However, since the rate of increase in UV protection improvement effect tends to decrease depending on the nonionic surfactant component (C), it is preferable to select component (C) from the group of component (C1) shown in each table, i.e., polyglyceryl-10 laurate, polyglyceryl-10 oleate, olive oil glycereth-8 esters, polysorbate 80, PEG-20 methyl glucose sesquistearate, and polysorbate 60.

[0117] Furthermore, it was found that the incorporation of components (A) to (D), especially components (A) to (C), improved the cohesion of the UV protection agent, particularly the hydrophobic scattering agent, which is a particulate component, resulting in an appropriate amount of torrential rain. This is evident, for example, from a comparison of all the Examples and all the Comparative Examples, particularly a comparison of Example 39 and other Comparative Examples. It was also found that the incorporation of the hydrophobized UV scattering agent of component (A) significantly contributed to improved adhesion to the skin and a smooth feel in use. For example, as is clear from a comparison of Examples 1 to 10 with Comparative Examples 2 to 5, even when the same UV scattering agents, such as zinc oxide and titanium oxide, were incorporated, the UV protection agents containing the hydrophobized UV scattering agents of Examples 1 to 10 exhibited significantly improved adhesion to the skin and a smooth feel in use (improved squeaky feeling, etc.) compared to the UV protection agents containing the hydrophilic UV scattering agents of Comparative Examples 2 to 5 that were not hydrophobized.

[0118] [2. Solid Powder Cosmetic] Formulation examples for solid powder cosmetics containing the aforementioned UV protection agent are shown below. In the formulation examples below, the "remaining amount" in the blending amount (% by mass) means the amount that makes the total amount 100% by weight.

[0119] Formulation Example 1: Powder Foundation (Ingredients) (% by mass) 1. Dimethicone, hydrogen dimethicone, aluminum hydroxide, hydrated silica-treated titanium dioxide (average particle size 10 nm) (ingredient A) (ingredient A1) (*1) 5.0% 2. Stearic acid, aluminum hydroxide-treated titanium dioxide (average particle size 10 nm) (ingredient A) (ingredient A1) (*2) 2.0% 3. Dimethicone-treated titanium dioxide (average particle size 35 nm) (ingredient A) (ingredient A1) (*3) 1.0% 4. Hydrogen dimethicone-treated titanium dioxide (average particle size 80 nm) (ingredient A) (ingredient A1) (*4) 0.5% 5. Dimethicone-treated zinc oxide (average particle size 25 nm) (ingredient A) (ingredient A1) (*5) 0.5% 6. 1. Triethoxycaprylylsilane / Dimethicone-treated Zinc Oxide (Average Particle Diameter 25nm) (Component A) (Component A1) 0.5% 2. Triethoxycaprylylsilane / Dimethicone-treated Zinc Oxide (Average Particle Diameter 25nm) (Component A) (*6) 0.5% 3. Dimethicone / Dimethicone-treated Titanium Oxide (Average Particle Diameter 250nm) (Component A) (*7) 0.5% 4. Dimethicone / Dimethicone-treated Titanium Oxide (Average Particle Diameter 250nm) (Component A) (*8) 0.5% 5. Dimethicone / Dimethicone-treated Titanium Oxide (Average Particle Diameter 250nm) (Component A) (*9) 0.5% 6. Dimethicone / Dimethicone-treated Titanium Oxide (Average Particle Diameter 250nm) (Component A) (*9) 0.5% 7. Dimethicone / Dimethicone-treated Titanium Oxide (Average Particle Diameter 250nm) (Component A) (*1) 0.5% 8. Dimethicone / Dimethicone-treated Titanium Oxide (Average Particle Diameter 250nm) (Component A) (*1) 0.5% 9. Dimethicone / Dimethicone-treated Titanium Oxide (Average Particle Diameter 250nm) (Component A) (*1) 0.5% 11. Titanium oxide treated with aluminum hydroxide and hydrous silica (average particle size 35 nm) (*10) 0.5% 12. Zinc oxide (average particle size 25 nm) (*11) 0.5% 13. Zinc oxide (average particle size 25 nm) (*11) 0.5% 14. Titanium oxide treated with aluminum hydroxide (average particle size 250 nm) (*12)0.5% 15. Zinc oxide (average particle size 300 nm) (*13) 0.5% 16. Red iron oxide 0.25% 17. Yellow iron oxide 2.5% 18. Black iron oxide 0.2% 19. Boron nitride (*24) 2.5% 20. Boron nitride (*25) 2.5% 21. Synthetic phlogopite (*26) 0.5% 22. Dimethicone-treated synthetic phlogopite (*27) 0.5% 23. Dimethiconol-aminopropyltriethoxysilane-treated mica (*28) 15.0% 24. Amodimethicone-treated mica (*29) 5.0% 25. Mica (*30) remaining 26. Dimethicone-treated talc (*31) 1.0% 27. Dimethiconol-aminopropyltriethoxysilane-treated talc (*32) 5.0% 29. Talc (*33) 4.0% 30. (Fluoride / Hydroxylation / Oxidation) / (Mg / K / Silicon) (*34) 1.0% 31. Nylon-12 (*35) 0.5% 32. Silica (*36) 0.5% 33. Silica (*37) 2.0% 34. Silica (*38) 1.0% 35. Silica (*39) 0.5% 36. Polymethylmethacrylate (*40) 1.5% 37. (HDI / PPG / Polycaprolactone) Crosspolymer-Silica (*41) 0.5% 38. (Vinyl dimethicone / methicone silsesquioxane) crosspolymer(*42) 2.0% 39. Mixture of glycine, theanine, and serine 0.1% 40. BHT 0.01% 41. Chlorphenesin 0.2% 42. Tripropylene glycol (ingredient D) (ingredient D1) 2.5% 43. Dipropylene glycol (ingredient D) 0.2% 44. 1,3-butylene glycol (ingredient D) 0.2% 45. Diglycerin (ingredient D) 0.1% 46. Cellulose gum (ingredient B) (ingredient B1) 0.1% 47. Hydroxypropyl methylcellulose (ingredient B) (ingredient B1) (*14) 0.01% 48. Xanthan gum (ingredient B) 0.01% 49. Sodium hyaluronate (ingredient B) 0.01% 50. Glycosyl trehalose, hydrolyzed hydrogenated starch, and water mixture (ingredient B) 0.01% 51. Polyglyceryl-10 oleate (ingredient C) (ingredient C1) (*17) 1.0% 52. Olive oil glycereth-8 esters (ingredient C) (ingredient C1) (*18) 1.0% 53. Ethylhexyl methoxycinnamate (ingredient E) (ingredient E1) 7.0% 54. Glyceryl tri-2-ethylhexanoate (ingredient E) 0.3% 55. Mineral oil (ingredient E) 0.1% 56. Dimethicone (ingredient E) 0.1% 57. Fragrance 0.2% 58. A mixture of lavender oil, almond oil, macadamia nut oil, camellia oil, refined jojoba oil, apricot kernel oil, corn oil, grape seed oil, sunflower oil, hazelnut oil, and rosehip oil (a mixture of beauty ingredients) (ingredient E) 0.1%59. Mixture of Hitorishige Extract, Asparagus Extract, Artemia Extract, Guava Extract, Coffee Extract, Chinese Herb Extract, Grape Leaf Extract, Burnt Extract, Peppermint Leaf Extract, Prunus Sinensis Flower Extract, Sambucus Nigra Flower Extract, Tea Leaf Extract, Angelica Extract, Jasminum Sambac Flower Extract, Rosa Multiflora Fruit Extract, Rugosa Rose Flower Extract, Rosa Izayoi Extract, Royal Jelly Extract, Angelica Root Extract, Rosa Centifolia Flower Extract, Rosa Damascena Flower Water, Rosemary Leaf Extract, Acerola Fruit Extract, Iris Root Extract, Sage Leaf Extract, and Rosemary Leaf Extract (Mixture of Cosmetic Ingredients) 0.2% Purified water (non-prescription) 100.0% (Footnotes) (*24) SHP-3 (manufactured by Mizushima Ferroalloy Co., Ltd.) (*25) CCS102-JA Boron Nitride Powder (manufactured by Momentive Performance Materials Japan LLC) (*26) PDM-10L (manufactured by Topy Industries Ltd.) (*27) SA-PDM-10L (manufactured by Miyoshi Kasei Co., Ltd.) (*28) SE-MA-23 (manufactured by Miyoshi Kasei Co., Ltd.) (*29) Mica Y-2300WA3 (manufactured by Yamaguchi Mica Co., Ltd.) (*30) Mica Y-3000 (manufactured by Yamaguchi Mica Co., Ltd.) (*31) SA-Talc JA-46R (manufactured by Miyoshi Kasei Co., Ltd.) (*32) SE-TA-13 (manufactured by Miyoshi Chemicals Co., Ltd.) (*33) Talc EX-15 (manufactured by Yamaguchi Mica Co., Ltd.) (*34) Micromica MK-200 (manufactured by Katakura Co-op Agri Co., Ltd.) (*35) Toray Nylon SP-500 (manufactured by Toray Industries, Inc.) (*36) Silica Microbead P-1505 (manufactured by JGC Catalysts and Chemicals Co., Ltd.) (*37) COSMESILICA CQ 4 (manufactured by Fuji Silysia Chemical Ltd.) (*38) God Ball D11-796C (manufactured by Suzuki Yushi Kogyo Co., Ltd.) (*39) God Ball E2-824C (manufactured by Suzuki Yushi Kogyo Co., Ltd.) (*40) Matsumoto Microsphere M101 (manufactured by Matsumoto Yushi Pharmaceutical Co., Ltd.) (*41) CS-400 (manufactured by Toshiki Pigment Co., Ltd.) (*42) KSP-100 (Shin-Etsu Chemical Co., Ltd.)

[0120] (Manufacturing Method) A. Components 1 to 41 were mixed to obtain a mixture. B. Components 53 to 58 were added to the mixture obtained in A and mixed to obtain a mixture. C. The mixture obtained in B was pulverized to obtain a powdery composition. D. A portion of component 42 was mixed with components 46 to 50 and a portion of component 60 (purified water not included in the formulation) to obtain a swollen product. E. The remaining components 42, 43 to 45, 51 to 52, 59 and the remaining component 60 were added to the swollen product obtained in D and mixed to obtain a mixture. F. The powdery composition obtained in C was added to the mixture obtained in E and mixed to obtain a mixture. G. The mixture obtained in F was poured into a silicone mold and flash-frozen at -40°C. H. The flash-frozen sample obtained in G was removed from the silicone mold and dried in a vacuum dryer while maintaining the frozen state to obtain a solid powder cosmetic.

[0121] (Evaluation) The powder foundation of Formulation Example 1 was confirmed to have excellent UV protection effects, a moderate amount of application, adhesion to the skin, and a smooth feel (no creaky powder feeling, no sticking to the skin). Here, the total amount of component (A) was 25.5%, and the total amount of component (A1) was 9.5%. The total amount of component (B) was 0.14%, and the total amount of component (B1) was 0.11%. The total amount of component (C) was 2.0%, and the total amount of component (C1) was 2.0%. The total amount of component (D) was 3.0%, and the total amount of component (D1) was 2.5%. The total amount of component (E) was 7.5%, and the total amount of component (E1) was 7.0%. Therefore, the mass ratio relationship was as follows: (D) / (C) was 1.50. (A) / ((C)+(D)) was 5.10. (E) / ((C)+(D)) was 1.50. The density was 0.072.

[0122] Formulation Example 2: Powder Foundation (Ingredients) (% by mass) 1. Dimethicone, hydrogen dimethicone, aluminum hydroxide, hydrated silica-treated titanium dioxide (average particle size 10 nm) (ingredient A) (ingredient A1) (*1) 5.0% 2. Stearic acid, aluminum hydroxide-treated titanium dioxide (average particle size 10 nm) (ingredient A) (ingredient A1) (*2) 5.0% 3. Triethoxycaprylylsilane, dimethicone-treated zinc oxide (average particle size 25 nm) (ingredient A) (ingredient A1) 10.0% 4. sodium dilauroyl glutamate, lysine, magnesium chloride, aluminum hydroxide-treated titanium dioxide (average particle size 250 nm) (ingredient A) (*6) 3.0% 5. lecithin 0.5%-treated titanium dioxide (average particle size 250 nm) (ingredient A) 2.0% 6. 1. Aluminum hydroxide-treated titanium dioxide (average particle size 250 nm) (*12) 2.5% 2.5% 3. Zinc oxide (average particle size 300 nm) (*13) 2.5% 4. Iron oxide red 0.2% 5. Iron oxide yellow 2.0% 6. Iron oxide black 0.1% 7. Boron nitride (*24) 3.0% 8. Dimethiconol-aminopropyltriethoxysilane-treated mica (*28) 30.0% 9. Amodimethicone-treated mica (*29) 10.0% 10. Mica (*30) balance 11. Silica (*37) 2.5% 12. (Vinyl dimethicone / methicone silsesquioxane) crosspolymer (*42) 3.0% 13. Glycine, theanine, serine mixture 0.1% 18. BHT 0.01%19. Chlorphenesin 0.15% 20. Tripropylene glycol (ingredient D) (ingredient D1) 3.0% 21. Cellulose gum (ingredient B) (ingredient B1) 0.08% 22. Hydroxypropyl methylcellulose (ingredient B) (ingredient B1) (* 14) 0.07% 23. Olive oil glyceryl-8 esters (ingredient C) (ingredient C1) (* 18) 1.0% 24. Polysorbate 80 (ingredient C) (ingredient C1) (* 19) 0.5% 25. Polysorbate 60 (ingredient C) (ingredient C1) (* 20) 0.5% 26. Polyoxyethylene (60) hydrogenated castor oil (ingredient C) (* 22) 0.2% 27. Sorbitan sesquioleate 0.1% 28. Ethylhexyl methoxycinnamate (ingredient E) (ingredient E1) 5.0% 29. Dimethicone (ingredient E) 0.5% 30. Diphenylsiloxyphenyl trimethicone (ingredient E) 2.0% 31. Fragrance 0.15% 32. Mixture of lavender oil, almond oil, macadamia nut oil, camellia oil, refined jojoba oil, apricot kernel oil, corn oil, grape seed oil, sunflower oil, hazelnut oil, and rosehip oil (mixture of beauty ingredients) (ingredient E) 0.1%33. Gentian Extract, Hydrolyzed Silk Liquid, Hydrolyzed Rice Extract, Seaweed Extract, Iris Iris Leaf Extract, Artemisia Capillaris Flower Extract, Alpinia Speciosa Leaf Extract, Saccharomyces Cerevisiae Extract, Pomegranate Fruit Extract, Pomegranate Peel Extract, Galium Thunbergii Fruit Extract, Eggplant Fruit Extract, Harpagophytum Root Extract, Parsley Extract, Royal Jelly Extract, Rosa Alba Flower Extract, Avocado Extract, Gynostemma Pentaphyllum Extract, Chamomilla Recutita (Matricaria) Water, Barberry Fruit Extract, Apple Extract, lemongrass extract, Hitoshi Shizu extract, asparagus extract, artemia extract, guava extract, coffee extract, taiso extract, grape leaf extract, burnet extract, artemisia capillaris extract, Rosa rosa extract, flower extract, elderberry extract, tea leaf extract, angelica root extract, jasmine flower extract, angelica acutiloba root extract, rosa centifolia flower extract, damask rose flower water, rosemary leaf extract (mixture of beauty ingredients) 0.4% 34. Purified water (non-prescription) 75.0%

[0123] (Manufacturing Method) A. Components 1 to 19 were mixed to obtain a mixture. B. Components 28 to 32 were added to the mixture obtained in A and mixed to obtain a mixture. C. The mixture obtained in B was pulverized to obtain a powdery composition. D. A portion of component 20 was mixed with components 21 and 22 and a portion of component 34 (purified water not included in the formulation) to obtain a swollen product. E. The remaining components 20, 23 to 27, component 33 and the remaining component 34 were added to the swollen product obtained in D and mixed to obtain a mixture. F. The powdery composition obtained in C was added to the mixture obtained in E and mixed to obtain a mixture. G. The mixture obtained in F was poured into a silicone mold and flash-frozen at -40°C. H. The flash-frozen sample obtained in G was removed from the silicone mold and dried in a vacuum dryer while maintaining the frozen state to obtain a solid powder cosmetic.

[0124] (Evaluation) The powder foundation of Formulation Example 2 was confirmed to have excellent UV protection effects, a moderate amount of application, adhesion to the skin, and a smooth feel (no creaky powder feeling, no sticking to the skin). Here, the total amount of component (A) was 25.0%, and the total amount of component (A1) was 20.0%. The total amount of component (B) was 0.15%, and the total amount of component (B1) was 0.15%. The total amount of component (C) was 2.30%, and the total amount of component (C1) was 2.0%. The total amount of component (D) was 3.0%, and the total amount of component (D1) was 3.0%. The total amount of component (E) was 7.5%, and the total amount of component (E1) was 5.0%. Therefore, the mass ratio relationship was as follows: (D) / (C) was 1.30. (A) / ((C)+(D)) was 4.72. (E) / ((C)+(D)) was 1.42. The density was 0.095.

[0125] Formulation Example 3: Skin Color Control Powder (Ingredients) (% by mass) 1. Dimethicone, hydrogen dimethicone, aluminum hydroxide, hydrated silica-treated titanium dioxide (average particle size 10 nm) (ingredient A) (ingredient A1) (* 1) 1.0% 2. Stearic acid, aluminum hydroxide-treated titanium dioxide (average particle size 10 nm) (ingredient A) (ingredient A1) (* 2) 1.0% 3. hydrogen dimethicone-treated titanium dioxide (average particle size 80 nm) (ingredient A) (ingredient A1) (* 4) 1.0% 4. sodium dilauroyl glutamate, lysine, magnesium chloride, aluminum hydroxide-treated titanium dioxide (average particle size 250 nm) (ingredient A) (* 6) 1.0% 5. dimethicone, aluminum hydroxide-treated titanium dioxide (average particle size 250 nm) (ingredient A) (* 7) 1.0% 6. 1. Red iron oxide 0.05% 2. Yellow iron oxide 0.5% 3. Black iron oxide 0.02% 4. Boron nitride (*24) 5.0% 5.0% 6. Dimethicone-treated synthetic phlogopite (*27) 1.0% 7. Dimethiconol-aminopropyltriethoxysilane-treated mica (*28) 40.0% 8. Mica (*30) balance 9. Dimethiconol-aminopropyltriethoxysilane-treated talc (*32) 20.0% 10. Red iron oxide 0.05% 11. Yellow iron oxide 0.5% 12. Black iron oxide 0.02% 13. Dimethiconol-aminopropyltriethoxysilane-treated talc (*32) 20.0% 14. Silica (*37) 4.0% 15. Silica (*39) 2.0% 16. Mixture of glycine, theanine, and serine 0.1% 17. BHT 0.01% 18. Chlorphenesin 0.2% 19. Tripropylene glycol (component D) (component D1)0.5% 20. Cellulose Gum (Component B) (Component B1) 0.2% 21. Polyglyceryl-10 Oleate (Component C) (Component C1) (* 17) 1.0% 22. Olive Oil Glycereth-8 Esters (Component C) (Component C1) (* 18) 0.5% 23. Polysorbate 60 (Component C) (Component C1) (* 20) 1.5% 24. Ethylhexyl Methoxycinnamate (Component E) (Component E1) 7.0% 25. Isotridecyl Isononanoate (Component E) 2.5% 26. Mineral Oil (Component E) 2.0% 27. Diphenylsiloxyphenyl Trimethicone (Component E) 3.0% 28. Polysilicone-15 (Component E) 3.0% 29. Fragrance 0.2% 30. Mixture of lavender oil, almond oil, macadamia nut oil, camellia oil, refined jojoba oil, apricot kernel oil, corn oil, grape seed oil, sunflower oil, hazelnut oil, and rosehip oil (mixture of beauty ingredients) (ingredient E) 0.1% 31. 31. Mixture of beauty ingredients: 0.3% Hitori Shizuku extract, asparagus extract, artemia extract, guava extract, coffee extract, taiso extract, grape leaf extract, burnet extract, peppermint leaf extract, cherry blossom flower extract, elderberry flower extract, tea leaf extract, cinnamon extract, jasmine flower extract, multiflora rose fruit extract, rosehip flower extract, rosa izayoi extract, royal jelly extract, angelica root extract, rosa centifolia flower extract, damask rose flower water, rosemary leaf extract, acerola fruit extract, iris root extract, sage leaf extract, and rosemary leaf extract.

[0126] (Manufacturing Method) A. Components 1 to 18 were mixed to obtain a mixture. B. Components 24 to 30 were added to the mixture obtained in A and mixed to obtain a mixture. C. The mixture obtained in B was pulverized to obtain a powdery composition. D. A portion of component 19 was mixed with a portion of component 20 and component 32 (purified water not included in the formulation) to obtain a swollen product. E. The remaining components 19, components 21 to 23, component 31, and the remaining component 32 were added to the swollen product obtained in D and mixed to obtain a mixture. F. The powdery composition obtained in C was added to the mixture obtained in E and mixed to obtain a mixture. G. The mixture obtained in F was poured into a silicone mold and flash-frozen at -40°C. H. The flash-frozen sample obtained in G was removed from the silicone mold and dried in a vacuum dryer while maintaining the frozen state, to obtain a solid powder cosmetic.

[0127] (Evaluation) The skin color control powder of Formulation Example 3 was confirmed to have excellent UV protection improvement effect, appropriate amount of application, adhesion to the skin, and smooth feel (no creaky powder feeling, no sticking to the skin). Here, the total amount of component (A) was 5.0%, the total amount of component (A1) was 3.0%, the total amount of component (B) was 0.2%, the total amount of component (B1) was 0.2%, the total amount of component (C) was 3.0%, the total amount of component (C1) was 3.0%, the total amount of component (D) was 0.50%, the total amount of component (D1) was 0.50%, the total amount of component (E) was 14.5%, and the total amount of component (E1) was 7.0%. Therefore, the mass ratio relationship was as follows: (D) / (C) was 0.17. (A) / ((C)+(D)) was 1.43. (E) / ((C)+(D)) was 4.14. The density was 0.118.

[0128] Formulation Example 4: Skin Color Control Powder (Ingredients) (% by mass) 1. Titanium dioxide treated with stearic acid and aluminum hydroxide (average particle size 10 nm) (ingredient A) (ingredient A1) (*2) 3.0% 2. Sodium dilauramidoglutamide, lysine, magnesium chloride, and aluminum hydroxide (average particle size 250 nm) (ingredient A) (*6) 1.0% 3. Titanium dioxide treated with 0.5% lecithin (average particle size 250 nm) (ingredient A) 1.0% 4. Red iron oxide 0.03% 5. Yellow iron oxide 0.3% 6. Black iron oxide 0.01% 7. Synthetic phlogopite (*26) 10.0% 8. Mica (*30) balance 9. Talc (*33) 20.0% 10. (Fluoride / Hydroxylation / Oxidation) / (Mg / K / Silicon) (*34) 10.0% 11. Silica (*39) 1.0% 12. Mixture of Glycine, Theanine, and Serine 0.1% 13. BHT 0.01% 14. Chlorphenesin 0.2% 15. Tripropylene Glycol (Component D) (Component D1) 5.0% 16. Cellulose Gum (Component B) (Component B1) 0.1% 17. Hydroxypropyl Methylcellulose (Component B) (Component B1) (*14) 0.1% 18. Olive Oil Glycereth-8 Esters (Component C) (Component C1) (*18) 0.01% 19. Ethylhexyl Methoxycinnamate (Component E) (Component E1) 2.0% 20. Fragrance 0.2%21. Gentian Extract, Hydrolyzed Silk Liquid, Hydrolyzed Rice Extract, Seaweed Extract, Iris Iris Leaf Extract, Artemisia Capillaris Flower Extract, Alpinia Speciosa Leaf Extract, Saccharomyces Cerevisiae Extract, Pomegranate Fruit Extract, Pomegranate Peel Extract, Galium Thunbergii Fruit Extract, Eggplant Fruit Extract, Harpagophytum Root Extract, Parsley Extract, Royal Jelly Extract, Rosa Alba Flower Extract, Avocado Extract, Gynostemma Pentaphyllum Extract, Chamomilla Recutita (Matricaria) Water, Barberry Fruit Extract, Apple 21. Mixture of beauty ingredients: 0.2% 22. Purified water (non-prescription): 100.0% 23. Mixture of: Lemongrass extract, Hitoshi Shizu extract, Asparagus extract, Artemia extract, Guava extract, Coffee extract, Taiso extract, Grape leaf extract, Burnt extract, Artemisia capillaris extract, Rosa rosa extract, Ophiopogon extract, Sambucus nigra flower extract, Tea leaf extract, Angelica acutiloba root extract, Rosa centifolia flower extract, Rosa damask flower water, Rosemary leaf extract (mixture of beauty ingredients) 0.2% 24. Mixture of beauty ingredients: 0.2% 25. Mixture of beauty ingredients: Lemongrass extract, Hitoshi Shizu extract, Asparagus extract, Artemia extract, Guava extract, Coffee extract, Taiso extract, Grape leaf extract, Burnt extract, Artemisia capillaris extract, Rosa rosa extract, Ophiopogon extract, Sambucus nigra flower extract, Tea leaf extract, Angelica acutiloba root extract, Rosa centifolia flower extract, Rosa damask flower water, Rosemary leaf extract (mixture of beauty ingredients) 0.2% 26. Mixture of beauty ingredients: 0.2% 27. Mixture of beauty ingredients: Lemongrass extract, Hitoshi Shizu extract, Asparagus extract, Artemisia extract,

[0129] (Manufacturing Method) A. Components 1 to 14 were mixed to obtain a mixture. B. Components 19 and 20 were added to the mixture obtained in A and mixed to obtain a mixture. C. The mixture obtained in B was pulverized to obtain a powdery composition. D. A portion of component 15 was mixed with components 16 and 17 and a portion of component 22 (purified water not included in the formulation) to obtain a swollen product. E. The remaining components 15, 18, 21 and 22 were added to the swollen product obtained in D and mixed to obtain a mixture. F. The powdery composition obtained in C was added to the mixture obtained in E and mixed to obtain a mixture. G. The mixture obtained in F was poured into a silicone mold and flash-frozen at -40°C. H. The flash-frozen sample obtained in G was removed from the silicone mold and dried in a vacuum dryer while maintaining its frozen state to obtain a solid powder cosmetic.

[0130] (Evaluation) The skin color control powder of Formulation Example 4 was confirmed to have excellent UV protection effects, a moderate amount of application, adhesion to the skin, and a smooth feel (no creaky powder feeling, no sticking to the skin). Here, the total amount of component (A) was 5.0%, and the total amount of component (A1) was 3.0%. The total amount of component (B) was 0.20%, and the total amount of component (B1) was 0.20%. The total amount of component (C) was 0.01%, and the total amount of component (C1) was 0.01%. The total amount of component (D) was 5.0%, and the total amount of component (D1) was 5.0%. The total amount of component (E) was 2.0%, and the total amount of component (E1) was 2.0%. Therefore, the weight ratio relationship was as follows: (D) / (C) was 500.0. (A) / ((C)+(D)) was 1.00. (E) / ((C)+(D)) was 0.40. The density was 0.067.

[0131] Formulation Example 5: Sunscreen Powder (Ingredients) (% by mass) 1. Dimethicone-treated zinc oxide (average particle size 25 nm) (ingredient A) (ingredient A1) (* 5) 10.0% 2. Triethoxycaprylylsilane / dimethicone-treated zinc oxide (average particle size 25 nm) (ingredient A) (ingredient A1) 10.0% 3. Hydrogen dimethicone-treated zinc oxide (average particle size 300 nm) (ingredient A) (* 9) 5.0% 4. Dimethiconol / aminopropyltriethoxysilane-treated mica (* 28) 10.0% 5. Mica (* 30) balance 6. Triethoxycaprylylsilane 2%-treated mica 5.0% 7. Isopropyl titanium triisostearate 2%-treated mica 5.0% 8. Silica (* 36) 0.5% 9. 10. Glycine, theanine, serine mixture 0.1% 11. Chlorphenesin 0.2% 12. Tripropylene glycol (ingredient D) (ingredient D1) 1.0% 13. Dipropylene glycol (ingredient D) 0.3% 14.1,3-Butylene Glycol (Component D) 0.1% 15. Diglycerin (Component D) 0.1% 16. Cellulose Gum (Component B) (Component B1) 0.02% 17. Hydroxypropyl Methylcellulose (Component B) (Component B1) (*14) 0.1% 18. Polyglyceryl-10 Oleate (Component C) (Component C1) (*17) 0.2% 19. Olive Oil Glycereth-8 Esters (Component C) (Component C1) (*18) 0.3% 20. Glyceryl Tri-2-Ethylhexanoate (Component E) 2.0% 21. Diphenylsiloxyphenyl Trimethicone (Component E) 2.0% 22. Fragrance 0.2% 23. 23. A mixture of lavender oil, almond oil, macadamia nut oil, camellia oil, refined jojoba oil, apricot kernel oil, corn oil, grape seed oil, sunflower oil, hazelnut oil, and rosehip oil (mixture of beauty ingredients) (ingredient E) 0.1% 24. A mixture of Hitotsujyū extract, asparagus extract, artemia extract, guava extract, coffee extract, taiso extract, grape leaf extract, burnet extract, peppermint leaf extract, cherry blossom flower extract, elderberry flower extract, tea leaf extract, Chinese tea extract, Jasminum sambac flower extract, Rosa multiflora fruit extract, Rugosa rose flower extract, Rosa izayoi extract, royal jelly extract, Angelica acutiloba root extract, Rosa centifolia flower extract, Rosa damask flower water, rosemary leaf extract, acerola fruit extract, iris root extract, sage leaf extract, and rosemary leaf extract (mixture of beauty ingredients) 0.2% 25. Purified water (non-prescription) 100.0%,

[0132] (Manufacturing Method) A. Components 1 to 11 were mixed to obtain a mixture. B. Components 20 to 23 were added to the mixture obtained in A and mixed to obtain a mixture. C. The mixture obtained in B was pulverized to obtain a powdery composition. D. A portion of component 12 was mixed with components 16-17 and a portion of component 25 (purified water not included in the formulation) to obtain a swollen product. E. The remaining components 12, 13-15, 18-19, 24 and the remaining component 25 were added to the swollen product obtained in D and mixed to obtain a mixture. F. The powdery composition obtained in C was added to the mixture obtained in E and mixed to obtain a mixture. G. The mixture obtained in F was poured into a silicone mold and flash-frozen at -40°C. H. The flash-frozen sample obtained in G was removed from the silicone mold and dried in a vacuum dryer while maintaining the frozen state to obtain a solid powder cosmetic.

[0133] (Evaluation) The sunscreen powder of Formulation Example 5 was confirmed to have excellent UV protection effects, a moderate amount of application, adhesion to the skin, and a smooth feel when used (no creaky powder feeling, no sticking to the skin). Here, the total amount of component (A) was 25.0%, and the total amount of component (A1) was 20.0%. The total amount of component (B) was 0.12%, and the total amount of component (B1) was 0.12%. The total amount of component (C) was 0.50%, and the total amount of component (C1) was 0.50%. The total amount of component (D) was 1.50%, and the total amount of component (D1) was 1.0%. The total amount of component (E) was 4.0%, and the total amount of component (E1) was 0.0%. Therefore, the mass ratio relationship was as follows: (D) / (C) was 3.00. (A) / ((C)+(D)) was 12.50. (E) / ((C)+(D)) was 2.00. The density was 0.069.

[0134] Formulation Example 6: Sunscreen Powder (Ingredients) (% by mass) 1. Dimethicone-treated zinc oxide (average particle size 25 nm) (ingredient A) (ingredient A1) (* 5) 20.0% 2. Hydrogen dimethicone-treated zinc oxide (average particle size 300 nm) (ingredient A) (* 9) 5.0% 3. Dimethiconol-aminopropyltriethoxysilane-treated mica (* 28) 30.0% 4. Mica (* 30) balance 5. Dimethiconol-aminopropyltriethoxysilane-treated talc (* 32) 10.0% 6. Silica (* 37) 3.0% 7. Silica (* 38) 2.0% 8. Mixture of glycine, theanine, and serine 0.1% 9. BHT 0.01% 10. Chlorphenesin 0.15% 11. Tripropylene glycol (ingredient D) (ingredient D1) 2.0% 12. Cellulose gum (ingredient B) (ingredient B1) 0.15% 13. Olive oil glyceryl-8 esters (ingredient C) (ingredient C1) (*18) 2.0% 14. Ethylhexyl methoxycinnamate (ingredient E) (ingredient E1) 7.0% 15. Polysilicone-15 (ingredient E) 1.0% 16. Diethylamino hydroxybenzoyl hexyl benzoate 2.0% 17. Bis-ethylhexyloxyphenol methoxyphenyl triazine 2.0% 18. Ethylhexyl triazone 1.0% 19. Phenylbenzimidazole sulfonic acid 1.0% 20. Triethanolamine 0.5% 21. Fragrance 0.5%22. Mixture of lavender oil, almond oil, macadamia nut oil, camellia oil, refined jojoba oil, apricot kernel oil, corn oil, grape seed oil, sunflower oil, hazelnut oil, and rosehip oil (mixture of beauty ingredients) (ingredient E) 0.1% 23. Mixture of Hitotsujyū extract, asparagus extract, artemia extract, guava extract, coffee extract, taiso extract, grape leaf extract, burnet extract, peppermint leaf extract, cherry blossom flower extract, elderberry flower extract, tea leaf extract, Chinese tea extract, Jasminum sambac flower extract, Rosa multiflora fruit extract, Rugosa rose flower extract, Rosa izayoi extract, royal jelly extract, Angelica acutiloba root extract, Rosa centifolia flower extract, Rosa damask flower water, rosemary leaf extract, acerola fruit extract, iris root extract, sage leaf extract, and rosemary leaf extract (mixture of beauty ingredients) 0.2% 24. Purified water (non-prescription) 100.0%

[0135] (Manufacturing Method) A. Components 1 to 10 were mixed to obtain a mixture. B. Components 14 to 18 were heated and mixed, and then components 21 and 22 were added to the mixture obtained in A, and the mixture was added and mixed to obtain a mixture. C. The mixture obtained in B was pulverized to obtain a powdery composition. D. A portion of component 11 was mixed with a portion of component 12 and component 24 (purified water not included in the formulation) to obtain a swollen product. E. The remaining components 11, 13, 19-20, 23, and the remaining component 24 were added to the swollen product obtained in D, and mixed to obtain a mixture. F. The powdery composition obtained in C was added to the mixture obtained in E, and mixed to obtain a mixture. G. The mixture obtained in F was poured into a silicone mold and flash-frozen at -40°C. H. The flash-frozen sample obtained in G was removed from the silicone mold and dried in a vacuum dryer while maintaining the frozen state, to obtain a solid powder cosmetic preparation.

[0136] (Evaluation) The sunscreen powder of Formulation Example 7 was confirmed to have excellent UV protection effects, a moderate amount of application, adhesion to the skin, and a smooth feel when used (no creaky powder feeling, no sticking to the skin). Here, the total amount of component (A) was 25.0%, and the total amount of component (A1) was 20.0%. The total amount of component (B) was 0.15%, and the total amount of component (B1) was 0.15%. The total amount of component (C) was 2.0%, and the total amount of component (C1) was 2.0%. The total amount of component (D) was 2.0%, and the total amount of component (D1) was 2.0%. The total amount of component (E) was 7.0%, and the total amount of component (E1) was 7.0%. Therefore, the mass ratio relationship was as follows: (D) / (C) was 1.00. (A) / ((C)+(D)) was 6.25. (E) / ((C)+(D)) was 1.75. The density was 0.084.

[0137] Formulation Example 8: Sunscreen Powder (Ingredients) (% by mass) 1. Dimethicone-treated zinc oxide (average particle size 25 nm) (ingredient A) (ingredient A1) (* 5) 5.0% 2. Mica (* 43) balance 3. Silica (* 37) 2.0% 4. Silica (* 38) 1.0% 5. Silica (* 39) 1.0% 6. BHT 0.01% 7. Chlorphenesin 0.15% 8. Tripropylene glycol (ingredient D) (ingredient D1) 4.0% 9. Cellulose gum (ingredient B) (ingredient B1) 0.12% 10. Hydroxypropyl methylcellulose (ingredient B) (ingredient B1) (* 14) 0.08% 11. 11. Olive oil glyceryl-8 esters (ingredient C) (ingredient C1) (*18) 0.05% 12. Ethylhexyl methoxycinnamate (ingredient E) (ingredient E1) 7.0% 13. Diethylamino hydroxybenzoyl hexyl benzoate 0.5% 14. Bis-ethylhexyloxyphenol methoxyphenyl triazine 2.5% 15. Fragrance 0.3%16. Gentian Extract, Hydrolyzed Silk Liquid, Hydrolyzed Rice Extract, Seaweed Extract, Iris Iris Leaf Extract, Artemisia Capillaris Flower Extract, Alpinia Speciosa Leaf Extract, Saccharomyces Cerevisiae Extract, Pomegranate Fruit Extract, Pomegranate Peel Extract, Galium Thunbergii Fruit Extract, Eggplant Fruit Extract, Harpagophytum Root Extract, Parsley Extract, Royal Jelly Extract, Rosa Alba Flower Extract, Avocado Extract, Gynostemma Pentaphyllum Extract, Chamomilla Recutita (Matricaria) Water, Barberry Fruit Extract, Apple Extract, lemongrass extract, Hitoshi Shizu extract, asparagus extract, artemia extract, guava extract, coffee extract, taiso extract, grape leaf extract, burnet extract, artemisia capillaris extract, Rosa rosa extract, flower extract, elderberry extract, tea leaf extract, angelica root extract, jasmine flower extract, angelica acutiloba root extract, rosa centifolia flower extract, damask rose flower water, rosemary leaf extract (mixture of beauty ingredients) 0.1% 17. Purified water (non-prescription) 100.0% (Footnote) (*43) Mica Y-3000 (manufactured by Yamaguchi Mica Co., Ltd.)

[0138] (Manufacturing Method) A. Components 1 to 7 were mixed to obtain a mixture. B. Components 12 to 14 were heated and mixed, and then component 15 was added to the mixture obtained in A, and the mixture was added and mixed to obtain a mixture. C. The mixture obtained in B was pulverized to obtain a powdery composition. D. A portion of component 8 was mixed with components 9 to 10 and a portion of component 17 (purified water not included in the formulation) to obtain a swollen product. E. The remaining components 8, 11, 16 and 17 were added to the swollen product obtained in D, and mixed to obtain a mixture. F. The powdery composition obtained in C was added to the mixture obtained in E, and mixed to obtain a mixture. G. The mixture obtained in F was poured into a silicone mold and flash-frozen at -40°C. H. The flash-frozen sample obtained in G was removed from the silicone mold and dried in a vacuum dryer while maintaining the frozen state, to obtain a solid powder cosmetic.

[0139] (Evaluation) The sunscreen powder of Formulation Example 8 was confirmed to have excellent UV protection effects, a moderate amount of application, adhesion to the skin, and a smooth feel when used (no creaky powder feeling, no sticking to the skin). Here, the total amount of component (A) was 5.0%, and the total amount of component (A1) was 5.0%. The total amount of component (B) was 0.20%, and the total amount of component (B1) was 0.20%. The total amount of component (C) was 0.05%, and the total amount of component (C1) was 0.05%. The total amount of component (D) was 4.0%, and the total amount of component (D1) was 4.0%. The total amount of component (E) was 7.0%, and the total amount of component (E1) was 7.0%. Therefore, the mass ratio relationship was as follows: (D) / (C) was 80.0. (A) / ((C)+(D)) was 1.23. (E) / ((C)+(D)) was 1.73. The density was 0.078.

[0140] In the above, the present specification has described the embodiments and examples of the present invention in order to express the contents of the present invention. However, the present invention is not limited to the above embodiments and examples, and includes modifications and improvements that are obvious to those skilled in the art based on the matters described in the present specification.

[0141] The present invention relates to a solid powder ultraviolet protection agent, a method for producing the same, and a cosmetic composition. Accordingly, the present invention can be suitably used in the cosmetics manufacturing industry.

Claims

1. A solid powder ultraviolet protection agent containing (A) a hydrophobized ultraviolet scattering agent, (B) a polysaccharide, and (C) a nonionic surfactant having an HLB value of 10 or more.

2. The ultraviolet protection agent according to claim 1, which has been solidified by freeze-drying.

3. The ultraviolet protection agent according to claim 1 or 2, wherein component (A) comprises at least one selected from hydrophobized titanium oxide and hydrophobized zinc oxide, which are component (A1), each having an average particle size of 100 nm or less.

4. The ultraviolet protection agent according to claim 1 or 2, wherein the hydrophobic treatment of component (A) is at least one treatment selected from the group consisting of dimethicone treatment, hydrogen dimethicone treatment, stearic acid treatment, triethoxycaprylylsilane treatment, triisostearoyl titanate treatment, lecithin treatment, and N-acylamino acid treatment.

5. The UV protection agent according to claim 1 or 2, wherein component (B) comprises at least one selected from polysaccharides that are solid at 25°C and mixtures of glycosyltrehalose, hydrogenated starch hydrolysate, and water.

6. The ultraviolet protection agent according to claim 1 or 2, further comprising (D) a polyhydric alcohol.

7. The ultraviolet protection agent according to claim 6, wherein the ratio of the content of component (C) to the content of component (D) is component (D) / component (C)=0.01 to 1,000.

8. The ultraviolet protection agent according to claim 6, wherein the ratio of the contents of component (A), component (C), and component (D) is component (A) / (component (C)+component (D))=1 to 20.

9. The ultraviolet protection agent according to claim 1 or claim 2, further comprising (E) an oil agent that is liquid at 25°C.

10. The ultraviolet protection agent according to claim 9, further comprising (D) a polyhydric alcohol, wherein the ratio of the contents of components (C), (D), and (E) is component (E) / (component (C)+component (D))=0.05 to 5.

11. Density is 0.03 to 0.15 g / cm ３ 3. The ultraviolet protection agent according to claim 1 or 2, wherein 12. A cosmetic preparation containing the ultraviolet protection agent according to claim 1.

13. A method for producing a solid powdered ultraviolet protection agent, comprising the steps of: obtaining a mixture by mixing (A) a powdered hydrophobic treated ultraviolet scattering agent, (B) a polysaccharide, and (C) a nonionic surfactant having an HLB value of 10 or more with water; filling the mixture into a mold and freezing it to obtain a frozen product; and drying the frozen product in a vacuum dryer.

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