JP6887765B2 - Sunscreen cosmetics - Google Patents

Description

The present invention relates to sunscreen cosmetics. More specifically, the present invention relates to a sunscreen cosmetic that does not have a dry and taut feeling on the skin after application, has an excellent usability, and has a high UV protection effect.

Sunscreen cosmetics are cosmetics that block ultraviolet rays in the sun's rays and protect the skin from ultraviolet rays. Since they are often used from spring to summer when the amount of ultraviolet rays is high, they spread well when applied and are not sticky. It is required to have a good feeling of use, to be present on the skin for a long time after application, and to have a continuous UV protection effect.

Furthermore, in recent years, outdoor sports such as walking and running have been actively carried out, and in an environment where a large amount of sweating occurs, not only sweat and water but also sebum may cause the UV protection film to easily collapse, resulting in a cosmetic film. There is a problem that the effect of protecting the skin from ultraviolet rays is reduced because it cannot be kept uniform.

In order to improve these, various studies have been made so far, and zinc oxide and trimethylsiloxysilicic acid have been used in order to obtain a cosmetic that does not easily lose makeup and has excellent long-lasting makeup. However, there is a problem that the skin after application feels dry and taut, and the applied cosmetic film feels uncomfortable.

In order to meet these demands, for example, in Patent Document 1, a cosmetic containing trimethylsiloxysilicic acid, fine particle zinc oxide, hyaluronic acid and / or a salt thereof suppresses the dryness and firmness of the skin after application. Although it has been shown that it can be applied smoothly and evenly to the skin, it was not sufficient in terms of maintaining the UV protection effect and high water resistance.

Further, Patent Document 2 discloses a sunscreen cosmetic having an extremely high water resistance effect and an excellent usability. Although the sunscreen cosmetics described in Patent Document 2 are water-in-oil emulsified preparations and have a very high water resistance effect, they have not been shown to improve the durability of the ultraviolet protective film due to the influence of sebum.

Japanese Unexamined Patent Publication No. 2013-181009 Japanese Unexamined Patent Publication No. 2014-88346

An object of the present invention is to provide a sunscreen cosmetic that forms a flexible water-repellent film, does not give a dry or taut feeling to the skin after application, has an excellent usability, and has a high ultraviolet protection effect.

The present inventors have devised the present invention as a result of diligent studies on a sunscreen cosmetic that does not have a dry or taut feeling on the skin after application, has an excellent usability, and has a high ultraviolet protection effect.

That is, the present invention has been made to solve the above-mentioned problems, and in order to solve the above-mentioned problems, the present invention provides a sunscreen cosmetic containing the following components (A) to (C). Is.
(A) Fine particle zinc oxide surface-treated with N-acylamino acid or a salt thereof (B) Volatile oil having a boiling point of 200 ° C. or less at 1 atm (C) Trimethylsiloxysilicate The sunscreen cosmetic according to the present invention. In one embodiment, the average primary particle size of the fine particle zinc oxide is 10 nm to 150 nm.
In the sunscreen cosmetic according to the present invention, in another embodiment, the N-acylamino acid or a salt thereof is in the form of an insolubilized salt with Ca, Mg, Al, or Ba, and the surface of fine particle zinc oxide is formed. I try to exist in.
In another embodiment of the sunscreen cosmetic according to the present invention, the component (B) is decamethyltetrasiloxane, hexamethyldisiloxane, dodecamethylpentasiloxane, dimethylpolysiloxane, caprylylmethicone, methyltrimethicone. , Octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, etc., selected from one or more silicone-based volatile oils.
In another embodiment, the sunscreen cosmetic according to the present invention further contains a polyether-modified silicone or a polyglycerin-modified silicone as the component (D).

According to the present invention, there is provided a sunscreen cosmetic that does not give a dry or taut feeling to the skin after application, has an excellent usability, and has a high ultraviolet protection effect.

Hereinafter, the sunscreen cosmetic according to the present invention will be described in more detail with reference to the embodiments thereof.
The sunscreen cosmetic according to the present invention comprises (A) fine particle zinc oxide surface-treated with N-acylamino acid or a salt thereof, and (B) a volatile oil having a boiling point of 200 ° C. or lower at 1 atm. C) It contains at least trimethylsiloxysilicic acid and, if necessary, other components as appropriate.

The component (A) used in the sunscreen cosmetic according to the present invention is zinc oxide, which is a metal oxide powder, surface-treated with N-acylamino acid, which is a hydrophobizing agent, or a salt thereof.

Zinc oxide is preferably a fine particle powder. The average primary particle size of such fine particle zinc oxide is preferably 10 nm to 150 nm, more preferably 15 nm to 100 nm, and even more preferably 20 nm to 80 nm. If the average primary particle size is less than 10 nm, the feeling of squeaking is strong and the feeling of use of sunscreen cosmetics deteriorates, and if it exceeds 150 nm, the UV protection effect cannot be fully exerted and the skin becomes white when applied. .. Here, the average primary particle size can be obtained as the number average particle size of the primary particle size measured by observation with a scanning electron microscope.

The shape of the fine particle zinc oxide adopted in the present invention may be hexagonal, amorphous, petal or the like. However, the shape is not particularly limited to these shapes.

As the fine particle zinc oxide, commercially available ones can be used. For example, FINEX-50, FINEX-30 (manufactured by Sakai Chemical Industry Co., Ltd.), MZ-500, and MZ-300 (manufactured by TAYCA Corporation), ZnO-650, and ZnO-610 (manufactured by Sumitomo Osaka Cement Co., Ltd.), FZO- 50, MPT-146 (manufactured by Ishihara Sangyo Co., Ltd.) and the like can be mentioned.

The N-acyl amino acid used for the surface treatment with respect to the above-mentioned component (A) is an acyl amino acid compound of a saturated amino acid having 8 to 30 carbon atoms and an amino acid selected from aspartic acid and glutamic acid. Here, the carboxyl group of the amino acid may be in the form of a free form (-COOH). A salt of an N-acyl amino acid having a carboxyl group of -COONa or -COOK with Na, K or the like can also be used for the surface treatment.
Further, in the form of an insolubilized salt of N-acylamino acid or N-acylamino acid with Na, K, etc. instead of Fe, Zn, Ca, Mg, Al, Ba, Li, Zr, Ti, etc. Can also be used. In this case, the insolubilized salt is treated with an alkaline aqueous solution to be solubilized before use.

Examples of saturated fatty acids having 8 to 30 carbon atoms include lauric acid and stearic acid.

As the N-acyl amino acid obtained from the saturated fatty acid and the amino acid, commercially available ones can be used. For example, Amisoft HS-11P, Amisoft HS-21P, Amisoft HAP, Amisoft MK-11, Amisoft CA, etc. (manufactured by Ajinomoto Healthy Supply Co., Ltd.), Pericea series, Aminoformer series, Aminosurfactant series, etc. (manufactured by Asahi Kasei Chemicals Co., Ltd.) Can be mentioned.

The amount of N-acylamino acid used as the surface treatment agent is 0.5 to 15.0% by mass, more preferably 1.0 to 10.0% by mass, based on 100% by mass of zinc oxide. More preferably, it is 1.5% to 5.0% by mass. If the amount of the surface treatment agent is small, the hydrophobicity is weak and the stability of the blended cosmetic may be deteriorated, and if the amount of the surface treatment agent is large, the feeling of use becomes heavy and the feeling of use of the blended cosmetic is heavy. In, stickiness may occur. Further, if the amount of the surface treatment agent is large, the dispersibility and dispersion stability deteriorate. The amount of the surface treatment agent is preferably the smallest amount that can impart hydrophobicity in consideration of the average primary particle size and specific surface area of zinc oxide used.

The surface treatment method can be used by hydrophobizing the surface by a known method, and is not particularly limited.

In general, fine particles of zinc oxide were put into warmed water, and a salt of N-acylamino acid or N-acylamino acid with Na, K, etc. was dissolved in preheated water while stirring. The aqueous solution is put into the aqueous solution and stirred. The heating temperature at this time is preferably a temperature at which the N-acyl amino acid or a salt thereof dissolves, and is generally 60 ° C. or higher and 95 ° C. or lower.

Here, i) hydroxides such as Fe, Zn, Ca, Mg, Al, Ba, Li, Zr and Ti, ii) inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid, acetic acid, or iii) hydrochloric acid, sulfuric acid and nitric acid. Inorganic acids such as or acetic acid and soluble metal salts of Fe, Zn, Ca, Mg, Al, Ba, Li, Zr, Ti and the like are slowly added. As a result, surface-treated fine particle zinc oxide is produced. Then, by drying treatment, fine particle zinc oxide [component (A)] surface-treated with a salt of N-acyl amino acid or N-acyl amino acid (generally Na salt or K salt) is obtained. Can be done.

Among the hydroxides and soluble metal salts, hydroxides and chlorides of Ca, Mg, Al and Ba, which are generally used in cosmetics, are particularly preferable.

Fine particle zinc oxide surface-treated with an N-acylamino acid using this metal salt may be used, and fine particle zinc oxide surface-treated with a hydrophobic treatment agent may be used. The hydrophobizing agent to be used is not particularly limited as long as it is a hydrophobizing agent usually used for cosmetics. For example, a silicone treatment agent, a fluorine treatment agent, an organic titanate treatment agent, a metal soap treatment agent, a lecithin treatment agent and the like can be used. Can be mentioned.

As the zinc oxide surface-treated with the N-acyl amino acid of the component (A) or a salt thereof, commercially available zinc oxide can also be used. For example, NAI-Z-300 (manufactured by Miyoshi Kasei, Inc.) in which zinc oxide having an average primary particle size of 35 nm is surface-treated with 2Na stearoyl glutamate and calcium hydroxide, and zinc oxide having an average primary particle size of 25 nm are used. Examples thereof include ASL-1MZ-500 (manufactured by Daito Kasei Kogyo Co., Ltd.) whose surface is treated with lysine Na lauroyl glutamate and magnesium chloride.

The content of zinc oxide surface-treated with the N-acyl amino acid of the component (A) or a salt thereof is appropriately determined according to the desired sunscreen effect. However, in order to sufficiently obtain the effects of the present invention, it is 3.0 to 45.0% by mass, preferably 5.0 to 35% by mass, and more preferably 10. It is 0 to 25.0% by mass.

The volatile oil having a boiling point of 200 ° C. or less at 1 atm, which can be used as an ingredient (B) in the sunscreen cosmetics according to the present invention, is used for external skin preparations such as cosmetics and pharmaceuticals. If there is, there is no particular limitation. For example, silicone-based volatile oils such as decamethyltetrasiloxane, hexamethyldisiloxane, dodecamethylpentasiloxane, dimethylpolysiloxane, caprylylmethicone, methyltrimethicone, octamethylcyclotetrasiloxane, and decamethylcyclopentasiloxane, and light liquid isoparaffin. , Hydrocarbon oils such as isododecane and isohexadecane, fluorine-based oils and the like.

In the sunscreen cosmetics according to the present invention, one or a combination of the above-mentioned components (B) may be blended as a volatile oil having a boiling point of 200 ° C. or lower under 1 atm.

Further, in the sunscreen cosmetic according to the present invention, the content of the volatile oil having a boiling point of 200 ° C. or less under 1 atm of the component (B) is 1.0 to 50 with respect to the total amount of the sunscreen cosmetic. It is preferably 0.0% by mass, more preferably 10.0 to 40.0% by mass, and even more preferably 15 to 35% by mass. If the content of the component (B) is less than 1.0% by mass, the feeling of use due to the volatile oil content such as familiarity with the skin at the time of application may be insufficient, and if it exceeds 50.0% by mass, the component that can be blended ( The contents of other components such as A), (C), and non-volatile oil may be relatively reduced, the effect may not be sufficiently exhibited, and dusting after the volatile oil has volatilized may be promoted.

The trimethylsiloxysilicic acid of the component (C) used in the sunscreen cosmetics according to the present invention is not limited as long as it is usually used in cosmetics. However, a compound having a crosslinked structure having a siloxane structure as a main skeleton is preferable.

Further, the trimethylsiloxysilicic acid preferably has a molecular weight of 1000 to 10000, more preferably 2000 to 9000, and further preferably 3000 to 6000 from the viewpoint of usability and long-lasting makeup.

As these components (C) trimethylsiloxysilicic acid, commercially available ones can be used. For example, KF-7312T, KF-7312J, KF-7312K (manufactured by Shin-Etsu Chemical Co., Ltd.), RSN-0749 RESIN (manufactured by Toray Dow Corning), SS4230, SS4267 (momentive performance materials) previously dissolved in a solvent. (Manufactured by Materials) and the like. Examples of flakes that are not dissolved in a solvent include MQ-1600 Solid Resin (manufactured by Toray Dow Corning) and SR1000 (manufactured by Momentive Performance Materials). Species or two or more species can also be used. In particular, it is more preferable to use trimethylsiloxysilicic acid dissolved in a solvent from the viewpoint of ease of blending into cosmetics.

The content of the above-mentioned component (C) is 0.2 to 15.0% by mass, preferably 0.5 to 10.0% by mass, as a pure content of the film forming agent with respect to the total amount of the sunscreen cosmetics. It is more preferably 1.0 to 5.0% by mass.

If the content of the component (C) is less than 0.2% by mass, the effect of water resistance is not sufficiently exhibited, and if it exceeds 15.0% by mass, the feeling of use is poor and formulation becomes difficult. Etc. may occur.

In the present invention, fine particle zinc oxide surface-treated with N-acylamino acid of component (A) or a salt thereof binds to unsaturated fatty acids contained in sebum and solidifies to form a uniform water-repellent film. By doing so, the ultraviolet protection effect can be maintained.

Here, zinc oxide surface-treated with the N-acyl amino acid of the component (A) or a salt thereof, if it contains a non-volatile oil in the cosmetic, binds to the sebum component when applied to the skin. However, it may be difficult to solidify. Therefore, when the component (A) is dispersed in the volatile oil of the component (B) using an optimal dispersant, for example, PEG-9 polydimethylsiloxyethyl dimethicone of the component (D), it is blended into the cosmetics. More preferred. Further, a paste-like commercially available product in which the component (A) is stably converted into low-order particles in the volatile oil component (B) may be used. As such, 60% by mass of NAI-Z-300 of the component (A) and 35% by mass of decamethylcyclopentasiloxane of the component (B), and PEG-9 poly which is a polyether-modified silicone as a dispersant. Examples thereof include NAI-Z-300A (manufactured by Miyoshi Kasei, Inc.) containing 5% by mass of dimethylsiloxyethyl dimethicone and dispersing these in a bead mill.

The sunscreen cosmetic according to the present invention may contain other optional ingredients usually used in cosmetics in addition to the above ingredients (A) to (C). For example, water, other oil components, powders, surfactants, polyhydric alcohols, lower alcohols, oil gelling agents, water-soluble polymers or thickeners, film-forming agents, neutralizers, pH adjusters, powders. Body components, UV scatterers, UV absorbers, metal ion blockers, preservatives and antibacterial agents, moisturizers, vitamins, beauty ingredients and / or medicinal ingredients, fragrances, etc., within the range that does not impair the effects of the present invention. Then, it can be appropriately blended according to the target product.

The water used in the present invention is not particularly limited, and examples thereof include deionized water, distilled water, purified water, hot spring water, seawater, and plant-derived steam distilled water such as rose water, lavender water, and sweet scented gecko water. be able to. These waters may be used alone or in combination of two or more.

The other oil components are not particularly limited, and in addition to the volatile oil component of the component (B), for example, fatty acids such as liquid paraffin and squalane; olive oil, jojoba oil, avocado oil, soybean oil, meadow home oil, etc. Natural animal and vegetable fats and oils such as lanolin; cetyl 2-ethylhexanoate, neopentyl glycol diethylhexanate, isononyl isononanoate, isotridecyl isononanoate, isopropyl myristate, isopropyl palmitate, 2-ethylhexyl palmitate, 2-ethylhexyl stearate, stearer Fatty acid esters such as stearyl acid; triglycerides such as tri (caprylic caprylic acid) glyceryl and glyceryl tri2-ethylhexanoate, and polyhydric alcohol fatty acid ester oils such as neopentyl glycol diethylhexanoate and neopentyl glycol dicaprate. Classes; higher alcohols such as cetyl alcohol, stearyl alcohol, isostearyl alcohol, behenyl alcohol; higher fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid; chain silicone such as dimethylpolysiloxane and methylphenylpolysiloxane Examples thereof include liquid or solid silicone oils such as oils, silicone gels and silicone powders. These oils can be used alone or in combination of two or more.

Examples of the solid oil include ozokerite, paraffin, selecin, synthetic hydrocarbon wax, fishertroph wax, microcrystalline wax, polyethylene wax, ethylene propylene copolymer, candelilla wax, honey wax, carnauba wax and the like. The solid oil content here refers to an oil agent that is solid at room temperature (for example, 15 to 25 ° C.).

Examples of the surfactant include nonionic surfactants, silicone-based surfactants such as polyether-modified silicones and polyglycerin-modified silicones, anionic surfactants, cationic surfactants, amphoteric surfactants and the like. Can be done. Preferably, it is a nonionic surfactant and a silicone-based surfactant, and these may be used alone or in combination of two or more.

Nonionic surfactants include polyoxyethylene glycol oil, polyoxyethylene hydrogenated castor oil and derivatives thereof; sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan coconut oil, sorbitan tristearate. , Solbitan fatty acid esters such as sorbitan trioleate; polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan trioleate, etc. Polyoxyethylene sorbitan fatty acid ester; polyoxyethylene sorbit monolaurate, polyoxyethylene sorbit fatty acid ester tetrastearate; glyceryl monostearate, self-emulsifying glyceryl monostearate, glyceryl monoisostearate, etc. Polyoxyethylene glycerin fatty acid esters such as polyoxyethylene glyceryl acid, polyoxyethylene glyceryl monoisostearate, polyoxyethylene glyceryl tristearate, polyoxyethylene glyceryl triisostearate, polyoxyethylene glyceryl trioleate; polyoxyethylene lauryl Polyoxyethylene alkyl ethers such as ethers, polyoxyethylene cetyl ethers, polyoxyethylene stearyl ethers, polyoxyethylene oleyl ethers, and polyoxyethylene octyldodecyl ethers; polyethylene glycol fatty acid esters such as polyethylene glycol monolaurate and polyethylene glycol monooleate. Examples thereof include polyglycerin fatty acid esters such as polyglyceryl monolaurate, polyglyceryl monomyristate, polyglyceryl monostearate, polyglyceryl monooleate, polyglyceryl tristearate, and polyglyceryl trioleate.

Examples of the polyether-modified silicone include PEG-3 dimethicone, PEG-9 methyl ether dimethicone, PEG-10 dimethicone, PEG-10 methyl ether dimethicone, PEG-12 dimethicone, PEG-23 methyl ether dimethicone, and PEG-9 polydimethylsiloxyethyl. Examples thereof include dimethicone, PEG / PPG-19 / 19 dimethicone, polysilicone-13, lauryl PEG-9 polydimethylsiloxyethyl dimethicone, lauryl PEG-10 tris (trimethylsiloxy) silylethyl dimethicone and the like.

Examples of the polyglycerin-modified silicone include polyglyceryl-3 disiloxane dimethicone, polyglyceryl-3 polydimethylsiloxyethyl dimethicone, and lauryl polyglyceryl-3 polydimethylsiloxyethyl dimethicone.
When a polyether-modified silicone or a polyglycerin-modified silicone is blended as a surfactant as a component (D), fine particle zinc oxide surface-treated with the N-acylamino acid of the component (A) or a salt thereof is uniformly contained in the oil. It can be expected to be effective as a dispersant that forms a uniform cosmetic film even when it is dispersed and applied to the skin. In particular, PEG-9 polydimethylsiloxyethyl dimethicone, lauryl PEG-9 polydimethylsiloxyethyl dimethicone, and polyglyceryl-3 disiloxane dimethicone are highly effective as dispersants, and are particularly preferable. PEG-9 polydimethylsiloxy, which is a polyether-modified silicone. Ethyldimethicone is more preferable, and it is excellent in terms of dispersibility and uniformity of the component (A).

As the polyhydric alcohol, those generally used in cosmetic compositions can be used. For example, 1,3-butylene glycol, dipropylene glycol, propylene glycol, glycerin, 1,2-pentanediol, isoprene glycol, polyethylene glycol, methyl glucoside, sorbitol, diglycerin and the like can be mentioned.

Examples of the lower alcohol include ethanol, isopropanol and the like.

Examples of the oil gelling agent include amino acid derivatives such as N-lauroyl-L-glutamic acid, dextrin fatty acid esters such as dextrinpurumic acid ester, dextrin stearic acid ester, dextrin 2-ethylhexanoic acid palmitic acid ester, and sucrose palmitic acid ester. Examples thereof include sucrose fatty acid esters such as sucrose stearic acid ester, and organically modified clay minerals such as dimethylbenzyldodecylammonium montmorillonite clay and dimethyldioctadecilammonium montmorillonite clay.

Water-soluble polymers or thickeners include gum arabic, tragacant gum, galactan, guar gum, carrageenan, pectin, agar, quince seed, dextran, dextrin, purulan, carboxymethyl starch, collagen, casein, gelatin, methylcellulose, methylhydroxypropyl. Examples thereof include cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, sodium carboxymethyl cellulose, sodium alginate, sodium carboxymethyl dextrin, carboxyvinyl polymer, and bentonite.

Examples of the film-forming agent include alkyl polyacrylate, eicosen / vinylpyrrolidone polymer, ester gum, and the like, in addition to the trimethylsiloxysilicic acid component (C).

Examples of the neutralizing agent include potassium hydroxide, sodium hydroxide, triethanolamine, sodium carbonate and the like.

Examples of the pH adjuster include lactic acid, citric acid, glycolic acid, succinic acid, tartaric acid, dl-malic acid, potassium carbonate, sodium hydrogencarbonate, ammonium hydrogencarbonate and the like.

Examples of the powder component include talc, kaolin, sericite, mica, synthetic mica, synthetic fluorine gold mica, magnesium carbonate, aluminum silicate, magnesium silicate, aluminum magnesium silicate, calcium silicate, magnesium stearate, and stear. Zinc acid, magnesium myristate, boron nitride, magnesium oxide, silicic anhydride, alumina, barium sulfate, bentonite, titanium oxide-coated mica, iron oxide-coated mica, iron oxide-coated mica titanium, organic pigment-coated mica titanium, mica titanium, oxy Bismus chloride, calcium carbonate, smectite, nylon powder, polymethylmethacrylate powder, acrylonitrile-methacrylic acid copolymer powder, vinylidene chloride-methacrylic acid copolymer powder, polyethylene powder, polystyrene powder, organopolysiloxane elastomer powder, polymethylsil Examples thereof include sesquioxane powder, polyurethane powder, wool powder, silk powder, cellulose powder, N-silicate lysine powder and the like. Inorganic white pigments, red No. 201, red No. 202 and other organic pigments can be mentioned, and these powders may be used alone or in combination of two or more.

These powder components are not particularly limited by the shapes such as spherical, plate-like, and needle-like, the particle size such as fumes, fine particles, and pigment grade, and the particle structure such as porous and non-porous, and any shape. , Particle size and particle structure may be used.

Further, as the powder, a powder which has been surface-treated (hydrophobicized) with a fluorine compound, a silicone compound, metal soap, wax, a surfactant, an oil or fat, a hydrocarbon or the like may be used. For example, a powder surface-treated with a silicone compound such as methylpolysiloxane (dimethicone), methylhydrogenpolysiloxane, triethoxycaprylylsilane, or trimethylsiloxysilicic acid can be preferably used.

As the ultraviolet scattering agent, in addition to the fine particle zinc oxide surface-treated with the N-acyl amino acid of the component (A) or a salt thereof, the ultraviolet blocking effect of fine particle titanium oxide, fine particle zinc oxide, fine particle cerium oxide, fine particle zirconium oxide and the like Can be mentioned as a metal oxide having. These ultraviolet scattering agents may be used alone or in combination of two or more. The shape of these ultraviolet scattering agents is not particularly limited, such as spherical, plate-shaped, needle-shaped, and spindle-shaped, and any shape may be used.

In addition, the ultraviolet scattering agent is used in a state where it has been surface-treated (hydrophobized) with a silicone compound, a fluorine compound, an organic titanate compound, metal soap, wax, lecithin, a surfactant, an oil or fat, a hydrocarbon, or the like. You may. For example, an ultraviolet scattering agent surface-treated with a silicone compound such as methylpolysiloxane (dimethicone), methylhydrogenpolysiloxane, triethoxycaprylylsilane, or trimethylsiloxysilicic acid can be preferably used.

Examples of the ultraviolet absorber include 2-ethylhexyl paramethoxycinerate, hexyl 2- (4-diethylamino-2-hydroxybenzoyl) benzoate, benzyl paramethoxycinerate, 2-ethylhexyl paramethoxycinerate, and paramethoxy. Silica-based ultraviolet absorbers such as 2-ethoxyethyl silicate, mono-2-ethylhexarate glyceryl silicate, isopropyl diisopropyl silicate ester of paramethoxycinerate, hydroxymethoxybenzophenone, Benzophenone-based UV absorbers such as hydroxymethoxybenzophenone sulfonic acid, sodium hydroxymethoxybenzophenone sulfonate, dihydroxymethoxybenzophenone, sodium dihydroxymethoxybenzophenone disulfonate, dihydroxybenzophenone, tetrahydroxybenzophenone, paraaminobenzoic acid, ethyl paraaminobenzoate, paraaminobenzoic acid Glyceryl, amyl paradimethylaminobenzoate, octyl paradimethylaminobenzoate, ethyl 4- [N, N-di (2-hydroxypropyl) amino] benzoate, 2- (4-diethylamino-2-hydroxybenzoyl) -benzoate Benzophenone ester-based UV absorbers such as acid hexyl ester, salicylic acid-based UV absorbers such as ethylene glycol salicylate, phenyl salicylate, octyl salicylate, benzyl salicylate, p-tert-butylphenyl salicylate, homomentyl salicylate, 2,4,6- Triazine-based UV absorbers such as trianilino-p- (carbo-2'-ethylhexyl-1'-oxy) -1,3,5-triazine, 4-tert-butyl-4'-methoxydibenzoylmethane, oxybenzophenone, octocrylene , Menthyl anthranilate, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2-ethylhexyl dimethoxybenzidenedioxoimidazolidine propionate, 2-phenylbenzimidazole-5-sulfonic acid, 2-cyano-3,3 -Diphenyl acrylate or the like can be used.

Examples of the sequestrant include edetates such as disodium ethylenediaminetetraacetate, edetic acid, and sodium edetate.

Examples of preservatives and antibacterial agents include benzoic acid, salicylic acid, phenolic acid, sorbic acid, paraoxybenzoic acid ester, parachlormethacresol, hexachlorophene, benzalkonium chloride, chlorhexidine chloride, trichlorocarbanilide, photosensitizer, phenoxyethanol and the like. Can be mentioned.

Examples of the moisturizer include hyaluronic acid, collagen, elastin, sodium lactate, cyclodextrin, pyrrolidonecarboxylic acid and salts thereof, natural and synthetic ceramides and the like.

Vitamins, as cosmetic ingredients and / or medicinal ingredient, for example, coenzyme Q10, vitamin A oil, vitamin A such as retinol, vitamin B ₂ such as riboflavin, B ₆ such as pyridoxine hydrochloride, L- ascorbic acid , Vitamin Cs such as magnesium L-ascorbic acid phosphate, L-ascorbic acid monopalmitic acid ester, L-ascorbic acid dipalmitic acid ester, L-ascorbic acid-2-glucoside, pantothenic acids such as calcium pantothenate, vitamins mention may be made of alpha-tocopherol, tocopherol acetate, vitamins of vitamin E such as nicotinic acid DL-alpha-tocopherol; D _2, vitamin D such as cholecalciferol. Whitening agents such as albutin, ellagic acid, tranexamic acid, placenta extract, glutathion, yukinoshita extract, skin activators such as royal jelly, bunanoki extract, capsaicin, zingeron, cantalis tincture, ictamol, caffeine, tannic acid, γ-orizanol Such as blood circulation promoters, glycyrrhizic acid derivatives, glycyrrhetinic acid derivatives, anti-inflammatory agents such as azulene and alitein, amino acids such as arginine, serine, leucine and tryptophan. In addition, sardine seed extract, chamomile flower extract, soybean extract, button extract, parsley extract, bunanoki extract, wine yeast extract, grapefruit extract, watermelon extract, rice extract, grape extract, hop extract, rice bran extract, biwa extract, sardine extract, yokunin extract. , Senburi extract, Merilot extract, Birch extract, Kanzo extract, Shakuyaku extract, Sabonsou extract, Hechima extract, Togarashi extract, Lemon extract, Gentiana extract, Perilla extract, Aloe extract, Rosemary extract, Sage extract, Keihi extract, Thyme extract, Tea extract, seaweed extract, cucumber extract, chowji extract, carrot extract, marronnier extract, hamamelis extract, kuwa extract, ginger extract, otogirisou extract, sardine extract, tsubokusa extract, kudzu root grain extract, artichoke leaf extract, ages extract, edelweiss extract, Various extracts such as laminaria ochlorosquid extract can be mentioned.

Examples of the fragrance include known synthetic fragrances, animal fragrances, natural essential oils, synthetic oil refineries and the like.

The sunscreen cosmetic of the present invention can be produced according to a usual method, but can be easily adjusted by water-in-oil emulsification. Since the water-in-oil emulsification is an emulsification method having excellent water resistance, it is more preferable to use a water-in-oil emulsification composition.
In addition, the present invention is likely to be effective as a sunscreen cosmetic. However, it can also be suitably used for foundations and makeup bases having an ultraviolet protection effect.

The dosage form of the sunscreen cosmetic of the present invention is arbitrary, and can be applied to liquid, milky, creamy, paste, solid, powder, etc., and further, the shape to be impregnated in the sheet and foam, and the shape to be impregnated. It can also be applied as a spray or mousse.

Next, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples. The blending amount shown below is mass%.

[Test example]
A model sebum consisting of 3 g each of the fine particle zinc oxide of Test Examples 1 to 4 and the fine particle titanium oxide of Test Example 5, and 37.5% by mass of squalane, 37.5% by mass of olive oil, and 25% by mass of oleic acid was prepared. .. Next, each of these powders and model sebum were placed in a glass bottle and mixed with a propeller mixer at 1,500 rpm for 1 minute. After allowing to stand, in order to observe the state of the mixture after 1 minute, 3 minutes, and 10 minutes, the glass bottle was tilted and visually evaluated according to the following criteria.

⊚: Completely solidified.
◯: The liquid level was considerably thickened, but when tilted, the liquid level moved even slightly and was not solidified.
Δ: Slightly thickened.
×: No change.

＊１：ステアロイルグルタミン酸２Ｎａ２％、水酸化カルシウム０．３％処理微粒子酸化亜鉛（三好化成社製）
＊２：ジラウリルグルタミン酸リジンＮａ１％、塩化マグネシウム０．１７％処理微粒子酸化亜鉛（大東化成工業社製）
＊３：メチルハイドロジェンポリシロキサン２．９％処理微粒子酸化亜鉛（テイカ社製）
＊４：未処理微粒子酸化亜鉛（テイカ社製）
＊５：未処理微粒子酸化チタン（石原産業社製） Further, only for the solidified mixture, the needle insertion load value (g) was measured using a rheometer (COMPAC-100II manufactured by Sun Scientific Co., Ltd.). The measurement conditions were that the adapter used was φ3 mm and the needle insertion speed was 2 cm / min, and the needle insertion load value when a 3 mm needle was inserted was measured.

* 1: Stearoyl glutamic acid 2Na 2%, calcium hydroxide 0.3% treated fine particle zinc oxide (manufactured by Miyoshi Kasei, Inc.)
* 2: Lysine Na 1% dilauryl glutamic acid, 0.17% magnesium chloride treated fine particle zinc oxide (manufactured by Daito Kasei Kogyo Co., Ltd.)
* 3: Methylhydrogenpolysiloxane 2.9% treated fine particle zinc oxide (manufactured by TAYCA)
* 4: Untreated fine particle zinc oxide (manufactured by TAYCA)
* 5: Untreated fine particle titanium oxide (manufactured by Ishihara Sangyo Co., Ltd.)

As is clear from Table 1, all of the fine particle zinc oxides of Test Examples 1 to 4 solidify the model sebum, and in particular, the fine particle oxidation surface-treated with the N-acylamino acid of Test Examples 1 and 2 or a salt thereof. Zinc was completely solidified even after 1 minute. Furthermore, since the solidified mixture does not change significantly in the needle-insertion hardness value over time, it is considered that it solidifies with a small amount of sebum component, does not absorb excess sebum component, and fine particle zinc oxide may aggregate. It is considered that there is no such thing. As a result, when applied to sunscreen cosmetics, when applied to the skin, it adsorbs a small amount of sebum on the skin, instantly forms a uniform cosmetic film, does not absorb more sebum components than necessary, and dries. It is thought that it forms a film that does not feel sensation and does not crumble easily.

The silicone-treated fine particle zinc oxide of Test Example 3 is a fine particle zinc oxide that has been widely used in sunscreen cosmetics, but it takes time from the adsorption of sebum to the solidification, and the needle of the mixture. The zinc oxide value was high and tended to be agglomerated. Therefore, when it is added to sunscreen cosmetics, when it is applied to the skin, it may gradually adsorb sebum and aggregate with a hard film, resulting in a feeling of dryness, tension, and squeak. ..

Since the fine particle zinc oxide of Test Example 4 was not surface-treated, it resulted in solidification after 10 minutes. No change in the state of the fine particle titanium oxide of Test Example 5 was confirmed, and the result was that it did not solidify.

Examples 1 and 2 and Comparative Examples 1 to 5: Water-in-oil emulsified sunscreen emulsion (two-layer type)
A water-in-oil emulsifier-type sunscreen emulsion was prepared according to the composition shown in Table 2 and the following production method. The obtained cosmetics were evaluated by the following methods, and the results are also shown in Table 2.

[Use characteristic test]
We asked 5 female subjects (30 to 50 years old) to use the sunscreen emulsion shown in Table 2, and at that time, "no stickiness" and "no squeaky feeling", and "no feeling of dryness and tension". Each person evaluated according to the following evaluation criteria, and the average score of 5 persons was judged according to the following judgment criteria.

Evaluation criteria:
[Evaluation result]: [Score]
Very good: 5 points Good: 4 points Normal: 3 points Slightly defective: 2 points Bad: 1 point Judgment criteria:
[Average score on score]: [Judgment]
4.5 or higher: ◎
3.5 or more and less than 4.5: ○
1.5 or more and less than 3.5: △
Less than 1.5: ×

[UV protection effect]
The sunscreen emulsion shown in Table 2 was uniformly applied on a 5 cm x 5 cm square polymethyl methacrylate plate (manufactured by Sanyo Trading Co., Ltd.) at ^{a ratio of 2} mg / cm 2 each, and an SPF analyzer (UV-1000S manufactured by Labsphere) was applied. The SPF value was measured, the transmittance in the ultraviolet region of 290 nm to 380 nm was calculated, and the determination was made using the following criteria.

(Criteria)
(Judgment): (Evaluation)
◎: Transmittance is less than 10%, UV protection effect is very good ○: Transmittance is 10% or more and less than 30%, UV protection effect is good Δ: Transmittance is 30% or more and less than 50%, UV protection The effect is slightly inferior ×: The transmittance is 50% or more, and the UV protection effect is inferior.

[Water resistance test]
The sunscreen emulsion shown in Table 2 was uniformly applied on a 5 cm x 5 cm square polymethyl methacrylate plate (manufactured by Sanyo Trading Co., Ltd.) at ^{a ratio of 2} mg / cm 2 each, and an SPF analyzer (UV-1000S manufactured by Labsphere). The SPF value was measured using. Subsequently, the polymethyl methacrylate plate was immersed in water at 30 ° C. for 80 minutes, dried, and then the SPF value was measured again using an SPF analyzer (UV-1000S manufactured by Labsphere).

Next, the persistence of SPF was calculated from each SPF value.
SPF persistence (%) = (SPF value after water treatment / SPF value before water treatment) x 100
SPF sustainability was judged according to the following criteria and used as an index of water resistance.
(Criteria)
(Judgment): (Evaluation)
⊚: SPF persistence 90% or more: very high water resistance ○: SPF persistence 70% or more and less than 90%: slightly high water resistance Δ: SPF persistence 50% or more and less than 70%: water resistance Low

（組成の各数値は質量％を示す）

(Each numerical value of composition indicates mass%)

* 6: KF-7312J (manufactured by Shin-Etsu Chemical Co., Ltd.)
* 7: 670 FLUID (manufactured by Toray Dow Corning)

(Production method)
Ingredients 1 to 6 are mixed and dispersed at room temperature with a disper (3000 rpm, 30 minutes), components 7 to 16 are added to this mixture, and the mixture is stirred and mixed by a disper (3000 rpm, 5 minutes) at 70 ° C. to obtain an oil phase component. And said. Next, the components 17 to 21 were stirred at 70 ° C. to dissolve them, gradually added to the oil phase components, and emulsified with a homomixer (5000 rpm, 5 minutes).

The container was cooled to room temperature and filled to obtain a sunscreen emulsion.
As is clear from the results in Table 2, the sunscreen emulsions of Examples 1 and 2, which are the products of the present invention, are "non-sticky" and "non-squeaky" even when a high amount of fine particle zinc oxide is added. , It was an excellent cosmetic in the item of "no feeling of dryness and tension". In addition, the results were very excellent in terms of UV protection effect and water resistance effect.

On the other hand, in Comparative Example 1 in which fine particle zinc oxide treated with methylhydrogenpolysiloxane was blended instead of the component (A), the applied skin had a dry and taut feeling, and the sunscreen emulsion of Example 2 was produced. Compared with the fine particle zinc oxide, the dispersibility was poor and the UV protection effect was also inferior. Further, Comparative Example 2 in which fine particle titanium oxide was blended instead of the component (A) and Comparative Example 3 in which the component (B) was not blended resulted in a squeaky feeling and stickiness. Further, Comparative Example 4 in which the component (C) is not blended has a reduced water resistance effect, and Comparative Example 5 in which the component (C) is replaced with a different film-forming agent causes stickiness and is used satisfactorily. I didn't get a feeling. From the above results, by combining each component of the present invention, sebum on the skin is not absorbed more than necessary and solidifies to form a uniform film, so that the skin feels dry and taut after application. It was shown that a sunscreen cosmetic having excellent usability, high UV protection and water resistance can be obtained.

Example 3: Water-in-oil emulsified sunscreen lotion (two-layer type)
Ingredient amount%
(1) NAI-Z-300A [Component (A)] (* 4) 55
(2) Stearic acid-treated fine particle titanium oxide 5
(3) Methylpolysiloxane (1.5cs) [Component (B)] 15
(4) Isodecyl neopentanoate 2
(5) Squalene 1
(6) Trimethylsiloxysilicic acid [component (C)] (* 2) 3
(7) Polyglyceryl-3 polydimethylsiloxyethyl dimethicone 3
(8) Dimethyl distearyl ammonium hectorite 0.5
(9) Polymethylsilsesquioxane 3
(10) Remaining amount of purified water (11) Glycerin 3
(12) 1,3 Butylene glycol 2
(13) Sodium chloride 1
* 4: A paste-like premix product containing NAI-Z-300A (NAI-Z-300 [component (A)], decamethylcyclopentasiloxane (component (B)), and PEG-9 polydimethylsiloxyethyl dimethicone (Miyoshi). Kasei)))

Production method: Ingredients 1 to 9 were mixed and stirred. Then, the aqueous phases of the mixed and dissolved components 10 to 14 were added and emulsified to obtain the desired water-in-oil emulsified sunscreen lotion.

(Evaluation)
The obtained water-in-oil emulsified sunscreen lotion was evaluated in the same manner as in Examples 1 and 2 and Comparative Examples 1 to 5, and found to be an excellent sunscreen lotion in all items.

Example 4: Water-in-oil emulsified sunscreen cream Ingredients mass%
(1) NAI-Z-300 [Component (A)] 10
(2) Silicone-treated fine particle titanium oxide 3
(3) PEG-9 polydimethylsiloxyethyl dimethicone 2
(4) Decamethylcyclopentasiloxane [Component (B)] 15
(5) 2-Ethylhexyl paramethoxycinnamate 5
(6) Triethylhexanoin 3
(7) Trimethylsiloxysilicic acid [component (C)] (* 2) 2
(8) Diethylaminohydroxybenzoyl hexyl benzoate 1
(9) Lauryl PEG-9 Polydimethylsiloxyethyl Dimethicone 1
(10) Sorbitan sesquiisostearate 1
(11) Dimethyl distearyl ammonium hectorite 1
(12) Organopolysiloxane elastomer spherical powder 1
(13) Remaining amount of purified water (14) Glycerin 5
(15) 1,3 Butylene glycol 3
(16) Bis PEG-18 Methyl Ether Dimethyl Silane 2
(17) Magnesium sulfate 1
(18) Phenoxyethanol 0.5

Production method: Ingredients 1 to 4 were mixed and dispersed, and components 5 to 12 were added to this mixture, and the mixture was mixed and stirred. Then, the aqueous phases of the mixed and dissolved components 13 to 18 were added and emulsified to obtain the desired water-in-oil emulsified sunscreen cream.

(Evaluation)
The obtained water-in-oil emulsified sunscreen cream was evaluated in the same manner as in Examples 1 and 2 and Comparative Examples 1 to 5, and found to be an excellent sunscreen cream in all items.
Further, as can be understood from the above results, by blending PEG-9 polydimethylsiloxyethyl dimethicone, even if the component (A) is highly blended, it is uniformly dispersed in the cosmetics, resulting in a squeaky feeling. Is further reduced, and it is understood that a high UV protection effect can be obtained.
The claims described in the claims at the time of filing the application of the present application were as follows.
Claim 1:
A sunscreen cosmetic containing the following components (A) to (C).
(A) Fine particle zinc oxide surface-treated with N-acylamino acid or a salt thereof
(B) Volatile oil having a boiling point of 200 ° C or less under 1 atm
(C) Trimethylsiloxysilicic acid
Claim 2:
The sunscreen cosmetic according to claim 1, wherein the average primary particle size of the fine particle zinc oxide is 10 nm to 150 nm.
Claim 3:
The sunscreen cosmetic according to claim 1 or 2, wherein the N-acylamino acid or a salt thereof is in the form of an insolubilized salt with Ca, Mg, Al, or Ba and is present on the surface of fine particle zinc oxide. Fee.
Claim 4:
The component (B) is one of decamethyltetrasiloxane, hexamethyldisiloxane, dodecamethylpentasiloxane, dimethylpolysiloxane, caprylylmethicone, methyltrimethicone, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and the like. The sunscreen cosmetic according to any one of claims 1 to 3, which is selected from two or more kinds of silicone-based volatile oils.
Claim 5:
The sunscreen cosmetic according to any one of claims 1 to 4, further containing a polyether-modified silicone or a polyglycerin-modified silicone as the component (D).

Claims (4)

Ingredient (A) Fine particle zinc oxide surface-treated with N-acylamino acid or a salt thereof
Component (B) Volatile oil having a boiling point of 200 ° C or less under 1 atm, and
Containing component (C) trimethylsiloxysilicic acid,
The N-acyl amino acid is an acyl amino acid compound of a saturated fatty acid having 8 to 30 carbon atoms and an amino acid selected from aspartic acid and glutamic acid.
A sunscreen cosmetic in which the N-acylamino acid or a salt thereof is in the form of an insolubilized salt with Ca, Mg, Al, or Ba and is present on the surface of fine particle zinc oxide. The sunscreen cosmetic according to claim 1, wherein the average primary particle size of the fine particle zinc oxide is 10 nm to 150 nm. The component (B) is one of decamethyltetrasiloxane, hexamethyldisiloxane, dodecamethylpentasiloxane, dimethylpolysiloxane, caprylylmethicone, methyltrimethicone, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and the like. The sunscreen cosmetic according to any one of claims 1 and 2 , which is selected from two or more kinds of silicone-based volatile oils. The sunscreen cosmetic according to any one of claims 1 to 3 , further containing a polyether-modified silicone or a polyglycerin-modified silicone as the component (D).