JP2020063228A - Oil-in-water emulsified cosmetic and method for producing the same - Google Patents

Abstract

To provide an oil-in-water emulsified cosmetic that has a good texture, has excellent water resistance, and can also keep high SPF.SOLUTION: An oil-in-water emulsified sunscreen cosmetic is provided that contains an ultraviolet shielding inorganic powder having a layer surface-treated in a water-repellent manner. The ultraviolet shielding inorganic powder having the layer surface-treated in the water-repellent manner is dispersed in both of an aqueous phase and an oil phase. The oil-in-water emulsified sunscreen cosmetic further contains polyhydroxystearic acid.SELECTED DRAWING: None

Description

The present invention relates to an oil-in-water emulsion cosmetic and a method for producing the same.

In recent years, daily UV care has been attracting attention due to the increased awareness of ultraviolet rays. As the cosmetics used for such UV care, many oil-in-water emulsion cosmetics are on the market because of the feeling during use and the ease of cleansing. In many of such oil-in-water emulsion cosmetics, a water-repellent inorganic powder is mainly blended in the oil phase as an ultraviolet shielding agent.

However, in recent years, cosmetics having higher and higher UV shielding performance have been demanded, and there has been a demand for improvement of the UV shielding function. However, it has been difficult for conventional oil-in-water emulsion cosmetics to obtain a remarkably higher ultraviolet ray shielding property than before.

In order to obtain a high UV shielding property, it is necessary to mix a large amount of water-repellent inorganic powder. However, when a large amount of the water-repellent inorganic powder is mixed in the oil phase, there is a problem in that squeaking occurs and the feel becomes poor. In addition, when a large amount of powder is blended, it becomes necessary to blend a large amount of the dispersant, which causes stickiness. Therefore, it becomes difficult to mix a large amount of the water-repellent inorganic powder into the oil phase of the cosmetic.

Patent Document 1 describes blending hydrophilic silica-coated inorganic powder in the water phase and water-repellent inorganic powder or an organic absorbent in the oil phase. Although a high UV-shielding property was obtained in such a formulation, squeaking and whitening due to silica occurred.

The present inventors have studied improvement of the above problems by dispersing a water repellent powder in an aqueous medium (Patent Documents 2, 3, 4). However, these oil-in-water emulsion cosmetics may have a room for improvement because the SPF value may decrease (also referred to as water resistance decrease) when sweating or in contact with water.

JP 2001-240524 A International Publication No. 2015/125622 International publication 2016/056589 gazette JP, 2016-074660, A

In view of the above, the present invention has an object to provide an oil-in-water emulsion cosmetic which has a good feel, good water resistance, and can maintain a high SPF.
As a result of examining the prior art by the present inventor, the water-repellent powder may flow down due to re-emulsification of the oil-in-water emulsion cosmetic upon contact with water, which may lead to a decrease in SPF value. I found it. Then, the ultraviolet-shielding inorganic powder having a water-repellent surface treatment layer is dispersed in both the water phase and the oil phase in the oil-in-water emulsion cosmetic, and by further containing polyhydroxystearic acid, It was possible to prevent re-emulsification and maintain a high SPF value.

The present invention is an oil-in-water type emulsion sunscreen cosmetic containing an ultraviolet-shielding inorganic powder having a water-repellent surface treatment layer,
An oil-in-water emulsion sunscreen cosmetic characterized in that an ultraviolet-shielding inorganic powder having a water-repellent surface-treated layer is dispersed in both an aqueous phase and an oil phase, and further contains polyhydroxystearic acid. is there.

The ultraviolet-shielding inorganic powder is preferably titanium oxide and / or zinc oxide.
The ultraviolet-shielding inorganic powder preferably has a median diameter of 0.2 μm or less.
The oil-in-water emulsion sunscreen cosmetic preferably further contains a film forming agent.

The present invention is an oil dispersion in which an ultraviolet-shielding inorganic powder having a water-repellent surface treatment layer is dispersed in an oil medium,
An aqueous dispersion in which an ultraviolet-shielding inorganic powder having a water-repellent surface-treated layer is dispersed in an aqueous medium, and
It is also a method for producing an oil-in-water type emulsion sunscreen cosmetic, which comprises the step of mixing with other components.

According to the present invention, a sunscreen agent which has a high UV-shielding ability and is excellent in usability because a UV-screening agent can be stably mixed in a high proportion without adversely affecting the usability. Can be obtained.

FIG. 3 is a view showing an observation result of the oil-in-water emulsion sunscreen cosmetics of Example 1 with an optical microscope. It is a figure which shows the observation result with the optical microscope of the oil-in-water type emulsion sunscreen cosmetics of the comparative example 4. It is a figure which shows the observation result with the optical microscope of the oil-in-water type emulsion sunscreen cosmetics of the comparative example 6.

Hereinafter, the present invention will be specifically described.
The present invention is an oil-in-water emulsified cosmetic composition in which the water-repellent treated UV-shielding inorganic powder is blended in the water phase and the oil phase. Can be blended with. Therefore, it is possible to obtain an oil-in-water type emulsified cosmetic which maintains a high ultraviolet shielding ability and is also excellent in water resistance.

In the present invention, the ultraviolet shielding inorganic powder is not particularly limited, and titanium oxide, zinc oxide, cerium oxide and the like can be used. It is also possible to use two or more of these in combination.

The inorganic powder preferably has a median diameter of 0.2 μm or less.
Ultraviolet-shielding particles having such a median diameter are particularly preferable in that they have high visible light transparency and that the ultraviolet-shielding region is suitable. Further, if the median diameter exceeds 0.2 μm, not only the visible light transparency is deteriorated but also the ultraviolet ray shielding ability may be deteriorated.

The inorganic powder preferably has a median diameter of 10 nm or more. If the median diameter is less than 10 nm, it is not preferable in that the ultraviolet shielding ability may be deteriorated.

The median diameter (volume basis) is also referred to as D50, and refers to a diameter at which the larger side and the smaller side have the same amount when the powder is divided into two from a certain particle diameter. D50 is a value obtained by measuring the particle size distribution, but in the present invention, the particle size distribution is measured by laser diffraction / (manufactured by Horiba, Ltd., scattering type particle size distribution measuring device LA-960S). It is the measured value.

The shape of the above-mentioned inorganic powder is not particularly limited, and any shape such as spherical, rod-shaped, needle-shaped, spindle-shaped, plate-shaped or the like can be used. In addition, it is preferable to use a plate-like inorganic powder because excellent performance can be obtained in the feel when used as a cosmetic.

The above-mentioned inorganic powder may be subjected to the surface treatment of the present invention using a known composite material such as titanium oxide surface-treated with silica as a base material. Alternatively, an oxide doped with a different element such as manganese, calcium, or nitrogen, such as cerium oxide doped with Ca, may be used as the original material.

The inorganic powder of the present invention has a surface-treated layer of a water-repellent organic compound on the surface. The surface treatment here is a water-repellent treatment for reducing the affinity of the inorganic powder surface with water, and is a material which is easily dissolved in water after the treatment or a material which is dispersed in water. The surface treatment with does not correspond to the “water repellent treatment” of the present invention.

The water-repellent organic compound is not particularly limited, but it is preferable that it has strong water repellency. A compound that chemically bonds with the inorganic powder is preferable, but a compound that physically adsorbs can obtain some effect. Specific examples of the water-repellent organic compound include silicone oil, alkylsilane, alkyl titanate, alkyl aluminate, polyolefin, polyester, metal soap, amino acid, amino acid salt and the like. Of these, silicone oil is preferable because of its chemical stability. Specific examples of this silicone oil include dimethylpolysiloxane (for example, KF-96A-100cs manufactured by Shin-Etsu Chemical Co., Ltd., DM10 manufactured by Asahi Kasei Wacker Silicone), methylhydrogenpolysiloxane (for example, KF-99P manufactured by Shin-Etsu Chemical Co., Toray. SH1107C manufactured by Dow Corning), (dimethicone / methicone) copolymer (for example, KF-9901 manufactured by Shin-Etsu Chemical Co., Ltd.), methylphenyl silicone (for example, KF-50-100cs manufactured by Shin-Etsu Chemical Co., Ltd.), amino-modified silicone (for example, Shin-Etsu Chemical Co., Ltd.) KF-8015 manufactured by Toray, Dow Corning Toray JP-8500 Conditioning Agent, ADM6060 manufactured by Asahi Kasei Wacker Silicone, triethoxysilylethyl polydimethylsiloxyethyl dimethicone (for example, Shin-Etsu Chemical) Industrial KF-9908), triethoxysilylethyl polydimethylsiloxyethylhexyl dimethicone (for example, Shin-Etsu Chemical KF-9909), and the like. Among them, dimethylpolysiloxane, methylhydrogenpolysiloxane, and copolymers of both monomers (dimethicone / methicone) are inexpensive and highly stable due to their simple structure and have strong water repellency. Copolymers are especially preferred. Further, a coupling agent such as a silane coupling agent or a titanium coupling agent can also be used. Surface treatment may be performed with at least one compound selected from these water-repellent organic compounds.

The treatment amount of the water repellent organic compound is preferably 2 to 15% by weight based on the inorganic powder. If it is less than 2% by weight, the amount of eluted ions may increase. On the other hand, if it exceeds 15% by weight, not only the cost increases but also the effect may reach the limit.

The oil-in-water emulsion sunscreen cosmetic of the present invention contains an ultraviolet-shielding inorganic powder having a water-repellent surface-treated layer in both the water phase and the oil phase. This makes it possible to incorporate a high proportion of the ultraviolet-shielding inorganic powder having the water-repellent surface-treated layer. Furthermore, each of the problems in the case of being mixed in the water phase and the problems in the case of being mixed in the oil phase can be compensated for, and a cosmetic having excellent properties such as feeling in use and sweat resistance can be obtained.

The state where the water-repellent treated UV-shielding inorganic powder is present in both the water phase and the oil phase means that both the water phase forming the sea structure of the oil-in-water structure and the oil phase forming the island structure. It means a state in which the powder is present. This can be confirmed by observation with an optical microscope.

In the present invention, it is preferable to contain the ultraviolet-shielding inorganic powder having the water-repellent surface-treated layer in a proportion of 6 to 40 mass% in the total amount of the cosmetic. The effect of the present invention is particularly remarkable in such a blending amount range. The lower limit is more preferably 10% by mass and even more preferably 14% by mass. The upper limit is more preferably 36% by mass, and further preferably 30% by mass.

In the present invention, it is preferable that the oil phase contains the ultraviolet-shielding inorganic powder having the water-repellent surface-treated layer at a ratio of 3 to 20% by mass (a ratio to the total amount of the cosmetic). It is preferable to mix the ultraviolet-shielding inorganic powder having the water-repellent surface-treated layer in the oil phase in such a ratio from the viewpoint that a feeling of use, water resistance, and a high ultraviolet-shielding effect can be obtained. The lower limit is more preferably 5% by mass, further preferably 7% by mass. The upper limit is more preferably 18% by mass and even more preferably 15% by mass.

In the present invention, it is preferable to contain the ultraviolet-shielding inorganic powder having the water-repellent surface-treated layer in a proportion of 3 to 20% by mass (ratio to the total amount of cosmetics) in the aqueous phase. It is preferable to mix the UV-shielding inorganic powder having the water-repellent surface-treated layer in the water phase in such a ratio in that the feeling of use, water resistance, and a high UV-shielding effect can be obtained. The lower limit is more preferably 5% by mass, further preferably 7% by mass. The upper limit is more preferably 18% by mass and even more preferably 15% by mass.

The oil-in-water emulsion sunscreen cosmetic of the present invention contains polyhydroxystearic acid. When the cosmetic of the present invention contains the compound, it is particularly difficult to re-emulsify when the cosmetic of the present invention comes into contact with water, so that the water resistance is improved and the problem of runoff during sweating is improved, which is preferable.

The blending amount of the polyhydroxystearic acid is preferably 0.2 to 5.0% by mass (ratio to the total amount of cosmetics). The lower limit is more preferably 0.3% by mass, and the upper limit is more preferably 4.0% by mass. The above ratio is particularly preferable in that the water resistance is improved.

The production method of the oil-in-water emulsion cosmetic of the present invention is not particularly limited. Specifically, for example, an aqueous dispersion in which an ultraviolet shielding inorganic powder having a water repellent surface treatment layer is dispersed in an aqueous medium, and an ultraviolet shielding inorganic powder having a water repellent surface treatment layer in an oil medium. It can be obtained by preparing an oily dispersion in which each is dispersed, using these as raw materials, and mixing with other components.

In the above-mentioned production method, the aqueous dispersion used may be one described in the above-mentioned International Publication No. 2015/125622. That is, a hydrophobic inorganic surface-treated fine inorganic powder, a polyhydric alcohol, water, and an aqueous dispersion containing a nonionic surfactant, wherein the nonionic surfactant is 1,3-butylene. An aqueous dispersion which is transparently dissolved and / or slightly turbid (20% by mass concentration, 35 ° C.) in glycol and which contains the fine particle inorganic powder in an amount of 30% by mass or more can be preferably used.

Specifically, the polyhydric alcohol is preferably one and / or two or more selected from propylene glycol, butylene glycol, pentanediol, dipropylene glycol, hexanediol and heptanediol, and particularly, butylene glycol and pentane. Diol, dipropylene glycol and hexanediol are preferred. Only one nonionic surfactant may be used, or two or more nonionic surfactants may be used in combination. Specifically, polyoxyalkylene alkyl ether, polyoxyalkylene fatty acid ester, polyoxyalkylene sorbitan fatty acid ester, polyoxyalkylene castor oil, polyoxyalkylene hydrogenated castor oil, polyoxyalkylene sorbitol tetra fatty acid ester, glycerin fatty acid ester, sorbitan Examples thereof include fatty acid ester, polyglycerin fatty acid ester, sucrose fatty acid ester, polyoxyalkylene group-containing organopolysiloxane, polyglycerin group-containing organopolysiloxane, and sugar chain-containing organopolysiloxane.
Examples of water include ordinary water, purified water, hard water, soft water, natural water, deep sea water, electrolyzed alkaline ionized water, electrolyzed acidic ionized water, ionized water and cluster water.
Further, use of titanium oxide aqueous dispersion DIS-AB-10W, zinc oxide aqueous dispersion DIF-AB-33W, zinc oxide aqueous dispersion DIF-AB-3CS, etc., which are commercially available from Sakai Chemical Industry Co., Ltd. You can also

In the above-mentioned production method, the oily dispersion used may be one in which an ultraviolet-shielding inorganic powder having a water-repellent surface-treated layer is dispersed in an oily medium in the presence of a dispersant. The oily medium here is not particularly limited, and any one that can be used as an oil agent for cosmetics can be used. Specifically, one or a mixture of two or more of those exemplified below can be appropriately used.
Isotridecyl isononanoate, isononyl isononanoate, ethylhexyl isononanoate, ethylhexyl palmitate, propylene glycol dicaprate, neopentylene glycol dicaprate, neopentylene glycol diethylhexanoate, ester oils such as cetyl ethylhexanoate, and cyclopentasiloxane , Silicone oils such as dimethicone and trimethicone, triglycerin, polyolefins, liquid paraffin and the like.

The dispersant used in the oily dispersion is not particularly limited, and for example, polyhydroxystearic acid or the like can be used. The use of polyhydroxystearic acid is particularly preferable in that it enables good dispersion even in a small amount and makes it difficult for the ultraviolet-shielding inorganic powder having a water-repellent surface-treated layer to flow in water even during use. The oily dispersion preferably contains the fine particle inorganic powder in an amount of 30% by mass or more.
Further, zinc oxide ester dispersions DIF-PC-3W, DIF-OP-3W, DIF-TL-3W, DIF-OP-3ST, DIF-TL-3ST, titanium oxide, which are commercially available from Sakai Chemical Industry Co., Ltd. Ester dispersions DIS-PC-10C, DIS-TL-10A, DIS-TL-10C, DIS-OP-10A and the like can also be used.

The cosmetic of the present invention may be used in combination with any of the above-mentioned components, and any aqueous component or oil component that can be used in the field of cosmetics. The above-mentioned aqueous component and oily component are not particularly limited, and examples thereof include oils, surfactants, humectants, higher alcohols, sequestering agents, water-soluble natural and semi-synthetic polymers, synthetic polymers, water-soluble and oil-soluble components. Molecules, organic UV-screening agents, various extracts, and the like can be mentioned.
In addition, if necessary, various powders such as inorganic and organic pigments, inorganic and organic clay mineral powders, inorganic soap and organic pigments treated with metal soap or silicone, coloring agents such as organic dyes, and other drug components. As an antiseptic, antioxidant, pigment, thickener, emulsion thickener, pH adjuster, fragrance, cooling sensation, antiperspirant, bactericide, skin activator, anti-inflammatory agent, whitening agent, film agent It may contain components such as. Specifically, one or two or more of the ingredients listed below can be arbitrarily blended to produce a desired cosmetic by a conventional method. The blending amount of these blending components is not particularly limited as long as the effects of the present invention are not impaired.

The oil is not particularly limited, and examples thereof include avocado oil, camellia oil, turtle oil, macadamia nut oil, corn oil, mink oil, olive oil, rapeseed oil, egg yolk oil, sesame oil, persic oil, wheat germ oil, southern oil, castor oil. Oil, linseed oil, safflower oil, cottonseed oil, eno oil, soybean oil, peanut oil, tea seed oil, kaya oil, rice bran oil, cinnamon oil, Japanese chili oil, jojoba oil, germ oil, triglycerin, glyceryl trioctanoate, Glycerin triisopalmitate, cocoa butter, coconut oil, horse fat, hardened coconut oil, palm oil, beef tallow, mutton fat, hardened beef tallow, palm kernel oil, lard, beef bone oil, sorghum kernel oil, hardened oil, cow leg Fat, wax, castor oil, beeswax, candelilla wax, cotton wax, carnauba wax, bayberry wax, ivorot wax, whale wax, montan wax, nuka wax, Norolin, Kapok wax, Lanolin acetate, Liquid lanolin, Sugar cane wax, Lanolin fatty acid isopropyl, Hexyl laurate, Reduced lanolin, Jojoba wax, Hard lanolin, Shellac wax, POE Lanolin alcohol acetate, POE Lanolin alcohol acetate, POE cholesterol ether, Lanolin fatty acid polyethylene glycol , POE hydrogenated lanolin alcohol ether, liquid paraffin, ozokerite, pristane, paraffin, ceresin, squalene, petrolatum, microcrystalline wax, propylene glycol dicaprate, ethylhexyl palmitate, isotridecyl isononanoate, and the like.

The surfactant is not particularly limited, and examples thereof include a lipophilic nonionic surfactant, a hydrophilic nonionic surfactant, and other surfactants.
The lipophilic nonionic surfactant is not particularly limited, and examples thereof include sorbitan monooleate, sorbitan monoisostearate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan sesquioleate, sorbitan trioleate. Ate, sorbitan fatty acid esters such as penta-2-ethylhexylate diglycerol sorbitan, tetra-2-ethylhexylate diglycerol sorbitan, monocotton oil fatty acid glycerin, monoerucate glycerin, sesquioleate glycerin, monostearate glycerin, α, α Glycerin polyglycerin fatty acids such as glycerin pyroglutamate oleate, glyceryl monostearate malic acid, and propylene glycol such as propylene glycol monostearate. It can be exemplified glycol fatty acid esters, hardened castor oil derivatives, glycerin alkyl ether.

The hydrophilic nonionic surfactant is not particularly limited, and examples thereof include POE sorbitan monooleate, POE sorbitan monostearate, POE sorbitan tetraoleate, and other POE sorbitan fatty acid esters (eg, polysorbate 60), POE sorbit mono. POE sorbit fatty acid esters such as laurate, POE sorbit monooleate, POE sorbit pentaoleate, POE sorbit monostearate, POE glycerin monostearate, POE glycerin monoisostearate, POE glycerin triisostearate and other POEs Glycerin fatty acid esters, POE monooleate, POE distearate, POE dioleate, POE fatty acid esters such as ethylene glycol distearate, PO POE alkyl ethers such as lauryl ether, POE oleyl ether, POE stearyl ether, POE behenyl ether, POE 2-octyldodecyl ether, POE cholestanol ether, POE octylphenyl ether, POE nonylphenyl ether, POE dinonylphenyl ether, etc. Alkyl phenyl ethers, Pluronic types such as Bourronic, POE / POP cetyl ether, POE / POP 2-decyl tetradecyl ether, POE / POP monobutyl ether, POE / POP hydrogenated lanolin, POE / POP glycerin ether and other POE / POP Alkyl ethers, Tetronic and other tetra-POE / tetra-POP ethylenediamine condensates, POE castor oil, POE hydrogenated castor oil, OE hydrogenated castor oil monoisostearate, POE hydrogenated castor oil triisostearate, POE hydrogenated castor oil monopyroglutamic acid monoisostearate diester, POE hydrogenated castor oil maleic acid and other POE castor oil hydrogenated castor oil derivatives, POE sorbit beeswax, etc. POE beeswax lanolin derivative, coconut oil fatty acid diethanolamide, lauric acid monoethanolamide, fatty acid isopropanolamide and other alkanolamides, POE propylene glycol fatty acid ester, POE alkylamine, POE fatty acid amide, sucrose fatty acid ester, POE nonylphenylformaldehyde Examples thereof include condensates, alkylethoxydimethylamine oxide, trioleyl phosphoric acid and the like.

Examples of the above other surfactants include anionic surfactants such as fatty acid soap, higher alkyl sulfate ester salt, POE lauryl sulfate triethanolamine, and alkyl ether sulfate ester salt, alkyltrimethylammonium salt, alkylpyridinium salt, and alkyltetraalkylammonium salt. Stable cationic surfactants such as primary ammonium salts, alkyldimethylbenzyl ammonium salts, POE alkylamines, alkylamine salts, polyamine fatty acid derivatives, and amphoteric surfactants such as imidazoline-based amphoteric surfactants and betaine-based surfactants You may mix | blend in the range which does not have a problem in the property and skin irritation.

The humectant is not particularly limited, and examples thereof include xylitol, sorbitol, maltitol, chondroitin sulfate, hyaluronic acid, mucoitin sulfate, caronic acid, atelocollagen, cholesteryl-12-hydroxystearate, sodium lactate, bile salt, dl- Examples thereof include pyrrolidone carboxylate, short-chain soluble collagen, diglycerin (EO) PO adduct, yellow sardine extract, yarrow extract, and merrilot extract.

The higher alcohol is not particularly limited, and examples thereof include linear alcohols such as lauryl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, myristyl alcohol, oleyl alcohol, cetostearyl alcohol, monostearyl glycerin ether (batyl alcohol), and 2-decyl. Branched chain alcohols such as tetradecynol, lanolin alcohol, cholesterol, phytosterol, hexyldecanol, isostearyl alcohol, and octyldodecanol can be mentioned.

The sequestering agent is not particularly limited, and examples thereof include 1-hydroxyethane-1,1-diphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid tetrasodium salt, sodium citrate, sodium polyphosphate, and metaphosphoric acid. Examples thereof include sodium, gluconic acid, phosphoric acid, citric acid, ascorbic acid, succinic acid, and edetic acid.

The natural water-soluble polymer is not particularly limited, and examples thereof include gum arabic, tragacanth gum, galactan, guar gum, carob gum, karaya gum, carrageenan, pectin, agar, quince seed (quince seed), arge colloid (cassius extract), starch (rice). , Corn, potato, wheat), plant-based polymers such as glycyrrhizinate, microbial polymers such as xanthan gum, dextran, succinoglucan, pullulan, and animal-based polymers such as collagen, casein, albumin, and gelatin. it can.

The semi-synthetic water-soluble polymer is not particularly limited, and examples thereof include carboxymethyl starch, starch-based polymers such as methyl hydroxypropyl starch, methyl cellulose, nitrocellulose, ethyl cellulose, methyl hydroxypropyl cellulose, hydroxyethyl cellulose, sodium cellulose sulfate, Examples thereof include cellulosic polymers such as hydroxypropyl cellulose, sodium carboxymethyl cellulose (CMC), crystalline cellulose and cellulose powder, and alginic acid polymers such as sodium alginate and propylene glycol alginate.

The synthetic water-soluble polymer is not particularly limited, and examples thereof include vinyl-based polymers such as polyvinyl alcohol, polyvinyl methyl ether, and polyvinylpyrrolidone, and polyoxyethylene-based polymers such as polyethylene glycol 20,000, 40,000, 60,000. Examples thereof include polymers, polyoxyethylene-polyoxypropylene copolymer-based polymers, acrylic polymers such as sodium polyacrylate, polyethyl acrylate and polyacrylamide, polyethyleneimine and cationic polymers.

The inorganic water-soluble polymer is not particularly limited, and examples thereof include bentonite, AlMg silicate (veegum), laponite, hectorite, and silicic acid anhydride.

The UV-screening agent is not particularly limited, and examples thereof include para-aminobenzoic acid (hereinafter abbreviated as PABA), PABA monoglycerin ester, N, N-dipropoxy PABA ethyl ester, N, N-diethoxy PABA ethyl ester, N, N-dimethyl. Benzoic acid-based UV screening agents such as PABA ethyl ester and N, N-dimethyl PABA butyl ester; Anthranilic acid-based UV screening agents such as homomenthyl-N-acetylanthranilate; amyl salicylate, menthyl salicylate, homomenthyl salicylate, octyl salicylate , Phenyl salicylate, benzyl salicylate, p-isopropanol phenyl salicylate, and other salicylic acid-based UV screening agents; ethylhexyl p-methoxycinnamate, octylcinnamate, ethyl-4-isoproyl Lucinnamate, methyl-2,5-diisopropylcinnamate, ethyl-2,4-diisopropylcinnamate, methyl-2,4-diisopropylcinnamate, propyl-p-methoxycinnamate, isopropyl-p-methoxycinnamate, isoamyl- p-methoxycinnamate, 2-ethoxyethyl-p-methoxycinnamate, cyclohexyl-p-methoxycinnamate, ethyl-α-cyano-β-phenylcinnamate, 2-ethylhexyl-α-cyano-β-phenylcinnamate , Glyceryl mono-2-ethylhexanoyl-diparamethoxycinnamate and other cinnamic acid type UV-screening agents; 2,4-dihydroxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy- 4,4'- Dimethoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2-hydroxy-4-methoxybenzophenone-5 -Sulfonate, 4-phenylbenzophenone, 2-ethylhexyl-4'-phenyl-benzophenone-2-carboxylate, 2-hydroxy-4-n-octoxybenzophenone, 4-hydroxy-3-carboxybenzophenone and other benzophenone series UV shielding agent: 3- (4'-methylbenzylidene) -d, l-camphor, 3-benzylidene-d, l-camphor, urocanic acid, urocanic acid ethyl ester, 2-phenyl-5-methylbenzoxazole, 2 , 2'-hydroxy -5-methylphenylbenzotriazole, 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, dibenzalazine, dianisoylmethane, 4-methoxy-4'-t-butyldibenzoylmethane, 5- (3,3-dimethyl-2-norbornylidene) -3-pentan-2-one and the like can be mentioned.

Other drug components are not particularly limited, and examples thereof include vitamin A oil, retinol, retinol palmitate, inosit, pyridoxine hydrochloride, benzyl nicotinate, nicotinamide, DL-α-tocopherol nicotinate, magnesium ascorbyl phosphate, 2 -O-α-D-glucopyranosyl-L-ascorbic acid, vitamins D2 (ergocasiferol), dl-α-tocopherol, dl-α-tocopheryl acetate, pantothenic acid, vitamins such as biotin; estradiol, ethinyl estradiol, etc. Hormones; amino acids such as arginine, aspartic acid, cystine, cysteine, methionine, serine, leucine and tryptophan; anti-inflammatory agents such as allantoin and azulene; whitening agents such as arbutin; astringents such as tannic acid; L Menthol, cooling agents and sulfur camphor such as, lysozyme chloride, it can be mentioned pyridoxine chloride, and the like.

The various extracts are not particularly limited and include, for example, Dokudami extract, psyllium extract, merilote extract, odorophyllum extract, licorice extract, peony extract, saponsou extract, loofah extract, kina extract, snow crab extract, clara extract, kohone extract, fennel. Extract, primrose extract, rose extract, sage extract, lemon extract, shikon extract, aloe extract, ginger root extract, eucalyptus extract, horsetail extract, sage extract, thyme extract, tea extract, seaweed extract, cucumber extract, clove extract, raspberry extract, melissa extract. , Carrot extract, horse chestnut extract, peach extract, peach leaf extract, mulberry extract, cornflower extract, hamamelis extract, placenta extract, thymus extract, silk extract, licorice Mention may be made of the kiss and the like.

The film forming agent is not particularly limited and includes, for example, acrylates copolymer, (acrylates / VA) copolymer, acrylates copolymer ammonium, (acrylates / ethylhexyl acrylate) copolymer, (styrene / acrylates) copolymer, (styrene / acrylates) copolymer. Ammonium and the like can be mentioned, and as product names, DERMACRYL AQF (Akrezzo Copolymer manufactured by Akzo Nobel: 45% by weight of active ingredient), YODOSOL GH800F (Akreants Copolymer ammonium manufactured by Akzo Nobel: 45% by weight of active ingredient) ), DAITOL 4000 SJT (manufactured by Daito Kasei Kogyo Co., Ltd. (Acrylate / Ethylhexyl acrylate) copolymer: 40% by weight of active ingredient), Vinizole 1086WP Daido Chemical Industry Co., Ltd. acrylated retaining clips polymer ammonium: active matter content 40%), and the like. The amount of the coating agent added is preferably 10% by weight or less, and more preferably 2 to 5% by weight, calculated as the active ingredient (for example, acrylates copolymer). The film forming agent may be contained in either the water phase or the oil phase. The present invention particularly preferably contains a film forming agent. By containing a film-forming agent, not only the water resistance is improved but also re-emulsification is difficult.

As the various powders, red iron oxide, yellow iron oxide, black iron oxide, mica titanium, iron oxide-coated mica titanium, bright color pigments such as titanium oxide-coated glass flakes, mica, talc, kaolin, sericite, titanium dioxide, Examples thereof include inorganic powder such as silica, and organic powder such as polyethylene powder, nylon powder, crosslinked polystyrene, cellulose powder, and silicone powder. Preferably, a part or all of the powder component is treated with a substance such as silicones, fluorine compounds, metal soaps, oils, and acylglutamates by a known method to improve organoleptic properties and makeup lasting. You may use it.

The cosmetics are not particularly limited, but can be incorporated into cosmetics for external use on the skin or hair such as skin care products, hair products, makeup products, and UV protection products. Further, the form of the product is not particularly limited, and it can be applied to emulsion, cream, solid, paste, gel, multi-layer, mousse, spray and the like.

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples. In the following description, there is no particular limitation, and "%" means "% by weight".

(Aqueous dispersion and oil dispersion)
In the following examples, water-repellent treated titanium oxide, water-repellent zinc oxide aqueous dispersion and oil dispersion were used as raw materials.
As these raw materials, commercially available products from Sakai Chemical Industry Co., Ltd. are used, and their formulations are as shown in Table 1 below. The ester dispersion and the cyclopentasiloxane dispersion in Tables 1 and 2 are oily dispersions.

FINEX-33W-LP2: Zinc oxide primary coated with silica and outermost surface coated with 4% silicone Zinc oxide STR-100C-LP: Primary coated with aluminum hydroxide, outermost layer oxidized with 4% silicone Titanium STR-100A-LP: primary coating with silica and aluminum hydroxide, outermost layer coated with 4% silicone Titanium oxide STR-100W-LP: primary coating with silica, outermost layer coated with 8% silicone Titanium oxide hydrophilically treated titanium oxide: Titanium oxide whose outermost layer is coated with silica

(Dispersion manufacturing method)
50 g of a mixed liquid of each powder, each solvent, and each dispersant, which were weighed in the ratio as shown in the above table, and 50 g of φ0.5 mm zirconia beads were put in a 200 ml mayonnaise bottle and dispersed for 60 minutes with a paint shaker, Each dispersion was obtained.

Further, the median diameter (volume basis) of zinc oxide and titanium oxide contained in each of the above dispersions is a value as shown in Table 2 below. The median diameter was measured using a laser diffraction / scattering particle size distribution analyzer LA-960S (manufactured by Horiba Ltd.). The cyclopentasiloxane dispersion was measured using an IPA solvent, and the aqueous dispersion was added dropwise to a water solvent and stirred by hand to make a measurement. For the ester dispersion, the stock solution was measured with a paste cell.

(Examples 1 to 6, Comparative Examples 1 to 8)
(Preparation of oil-in-water emulsion sunscreen cosmetics)
Oil-in-water emulsion sunscreen cosmetics were produced using the materials shown in Tables 3-5. The manufacturing method is as follows. The obtained oil-in-water emulsion sunscreen cosmetics were evaluated by the following methods. The results are shown in Tables 6-8.

(Production method)
A: Components 1 to 15 are mixed in each of Examples and Comparative Examples and heated to 80 degrees.
B: Components 16 to 21 are mixed in each of Examples and Comparative Examples and heated to 80 degrees.
C: A was added to B to emulsify, cooled to 60 ° C. or lower, and components 22 to 26 were added and mixed to obtain each sunscreen O / W cream.

(Examples 7 to 9)
(Preparation of oil-in-water emulsion sunscreen cosmetics 2)
An oil-in-water type emulsion sunscreen cosmetic, which emphasizes refreshing feeling more than Examples 1 to 6, was produced using the materials shown in Table 9. The manufacturing method is as follows. The obtained oil-in-water emulsion sunscreen cosmetics were evaluated by the following methods. The results are shown in Table 10.

(Manufacturing method 2)
A: Components 1 to 3 are mixed in each example and heated to 80 degrees.
B: Ingredients 4 to 10 are mixed in each example and heated to 80 degrees.
C: A was added to B to emulsify, cooled to 60 ° C. or lower, and component 11 was added and mixed to obtain each sunscreen O / W cream.

(Examples 10 and 11)
(Preparation of oil-in-water emulsion sunscreen cosmetics 3)
An oil-in-water type emulsion sunscreen cosmetic in consideration of storage stability for a longer period than in Examples 7 to 9 was prepared using the materials shown in Table 11. The manufacturing method is as follows. The obtained oil-in-water type emulsion sunscreen cosmetics were evaluated by the following methods. The results are shown in Table 12.

(Manufacturing method 3)
A: Components 1 to 7 are mixed in each of the examples and heated to 80 degrees.
B: Ingredients 8 to 13 are mixed in each of the examples and heated to 80 degrees.
C: A was added to B to emulsify, cooled to 60 ° C. or lower, and component 14 was added and mixed to obtain each sunscreen O / W cream.

(Evaluation methods)
(Water resistance test method)
Each sample was applied on a slide glass with a bar coater # 6, dried at 50 ° C. for 3 hours, and then the transmittance was measured with an ultraviolet-visible near-infrared spectrophotometer (V-770 manufactured by JASCO Corporation). The SPF value (A) of the obtained transmittance was calculated using SPF calculation software.
2 L of pure water was placed in a 2 L glass beaker equipped with a propeller stirrer, and the prepared coating film was immersed for 90 minutes while stirring at 500 rpm. Then, it was dried again at 50 ° C. for 1 hour, and the transmittance was measured with an ultraviolet-visible near-infrared spectrophotometer (V-770 manufactured by JASCO Corporation). The SPF value (B) of the obtained transmittance was measured by an SPF / PA value calculation program of an ultraviolet near infrared spectrophotometer (V-500 manufactured by JASCO Corporation).
The SPF maintenance rate (%) was calculated from the obtained SPF value using the following calculation formula.
Calculation formula SPF maintenance rate (%) = SPF value (B) / SPF value (A) x 100
The measurement was performed twice and the higher result was adopted.

(Difficulty in re-emulsification)
A use test was carried out by 20 professional evaluation panels, the oil-in-water type emulsion sunscreen cosmetics of the examples were applied on the skin, left for 20 minutes, and then the difficulty of re-emulsification in running water was evaluated. The evaluation was performed based on the following criteria.
[Evaluation criteria]
Does not re-emulsify under running water, does not re-emulsify by rubbing: 4 points Does not re-emulsify under running water, but slightly re-emulsifies by rubbing: 3-points Does not re-emulsify under running water, but re-emulsifies by rubbing: Re-emulsifies under 2-point running water Emulsify: 1 point
[Judgment]
Average score of 3.5 or more: ◎
Average score of 2.5 or more and less than 3.5: ○
Average score of 1.5 to less than 2.5: △
Average score less than 1.5: ×

(Stickiness)
A use test was conducted by 20 professional evaluation panels, and the oil-in-water emulsion sunscreen cosmetics of the examples were applied on the skin to evaluate the non-greasiness. The evaluation was performed based on the following criteria.
[Evaluation criteria]
Very good: 5 points good: 4 points normal: 3 points somewhat poor: 2 points bad: 1 point
[Judgment]
Average score of 4.5 or more: ◎
Average score of 3.5 to less than 4.5: ○
Average score of 2.5 points or more and less than 3.5 points: △
Average score less than 2.5: ×

From the results of the above Examples and Comparative Examples, the oil-in-water emulsion sunscreen cosmetics of the present invention can be said to have a high SPF, and in addition, the water resistance was remarkably improved. In addition, it is also less sticky and squeaky, and can be made to have an excellent feeling in use.
On the other hand, the oil-in-water emulsion sunscreen cosmetics of Comparative Example have a lower SPF value than those of the Examples, and are more likely to be re-emulsified when contacted with water, resulting in insufficient water resistance. it is obvious.

It was also confirmed that redispersion was difficult in Example 6 using the water-repellent treated titanium oxide aqueous dispersion having a median diameter of 0.2 μm or more, but the dispersion state having a median diameter of 0.2 μm or less was more preferable. It was difficult to re-emulsify and was preferred.

The oil-in-water emulsion sunscreen cosmetics of each Example and Comparative Example were observed with an optical microscope. As a result, in Examples 1 to 11 and Comparative Examples 7 to 8, the ultraviolet-shielding inorganic powder having the water repellent surface treatment layer was observed in both the water phase and the oil phase. In Comparative Examples 1 to 6, the ultraviolet-shielding inorganic powder having the water-repellent surface-treated layer was observed only in one of the layers blended as the raw material. In addition, the combination of titanium oxide having a water-repellent surface-treated layer in the oil phase, which is the inner phase of the oil-in-water cosmetic, and zinc oxide having a water-repellent surface-treated layer, which is the water phase, in the outer phase is more repellent to the oil phase. The retention rate tended to be relatively higher than in the case where zinc oxide having an aqueous surface treatment and titanium oxide having a water-repellent surface treatment were combined in the aqueous phase.

The results of observation with the optical microscope of Example 1 and Comparative Examples 4 and 6 are shown in FIGS. 1, 2 and 3, respectively.
As a result, in Example 1 (FIG. 1), it can be judged from the photograph that the powder is blended in both the outer water phase and the inner oil phase. In contrast, in Comparative Example 4 (FIG. 2) and Comparative Example 6 (FIG. 3), it is clear that there is a phase in which the powder is not dispersed.

INDUSTRIAL APPLICABILITY The present invention can be used as a sunscreen cosmetic having a high SPF value, excellent water resistance and a good feeling in use.

Claims (5)

An oil-in-water type emulsion sunscreen cosmetic containing an ultraviolet-shielding inorganic powder having a water-repellent surface treatment layer,
An oil-in-water type emulsion sunscreen cosmetic characterized in that an ultraviolet-shielding inorganic powder having a water-repellent surface treatment layer is dispersed in both an aqueous phase and an oil phase, and further contains polyhydroxystearic acid. The oil-in-water type emulsion sunscreen cosmetic according to claim 1, wherein the ultraviolet-shielding inorganic powder is titanium oxide and / or zinc oxide. The oil-in-water type emulsion sunscreen cosmetic according to claim 1 or 2, wherein the ultraviolet-shielding inorganic powder has a median diameter of 0.2 µm or less. The oil-in-water emulsion sunscreen cosmetic according to claim 1, further comprising a film forming agent. An oil-based dispersion in which an ultraviolet-shielding inorganic powder having a water-repellent surface treatment layer is dispersed in an oil medium,
An aqueous dispersion in which an ultraviolet-shielding inorganic powder having a water-repellent surface-treated layer is dispersed in an aqueous medium, and
The method for producing an oil-in-water type emulsion sunscreen cosmetic according to claim 1, 2, 3 or 4, further comprising the step of mixing with other components.

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