JP7260215B1 - Oil-in-water UV protective cosmetics - Google Patents

Abstract

An object of the present invention is to provide an oil-in-water type UV protection cosmetic which is excellent in water resistance and has an improved UV protection effect when wetted with water. (A1) UV absorber and (A2) UV scattering agent containing at least one selected from the group consisting of (A) UV protection agent, and (B) configuration derived from hydrophobically modified polyurethane and acrylamide and (C) polyoxyalkylene glyceryl ether, wherein the content ratio of component (B) to component (C) is 0.16 or more1. An oil-in-water type UV protection cosmetic with a rating of 4 or less. [Selection figure] None

Description

TECHNICAL FIELD The present invention relates to an oil-in-water type ultraviolet protective cosmetic composition.

As a technique related to cosmetics, Patent Document 1 describes an oil-in-water emulsified cosmetic containing a hydrophobically modified polyether polyurethane. In addition, Patent Document 2 describes an external preparation for skin containing polyoxybutylene polyoxyethylene polyoxypropylene glyceryl ether. Patent Document 3 describes an oil-in-water emulsified cosmetic containing a polyacrylamide compound. Patent Document 4 describes an oil-in-water emulsified cosmetic containing a sodium acrylate/sodium acryloyldimethyltaurate copolymer.

JP 2019-094280 A JP 2014-108934 A JP 2020-164458 A Japanese Patent Application Laid-Open No. 2021-017426

An object of the present invention is to provide an oil-in-water type ultraviolet protective cosmetic which is excellent in water resistance and has an improved ultraviolet protective effect when wetted with water.

Specific means for solving the above problems are as follows, and the present invention includes the following aspects. In the first aspect, (A) an ultraviolet protective agent containing at least one selected from the group consisting of (A1) an ultraviolet absorber and (A2) an ultraviolet scattering agent, and a structural unit derived from a hydrophobically modified polyurethane and acrylamide. (B) component containing at least one selected from the group consisting of polymers containing and (C) component containing polyoxyalkylene glyceryl ether, and the content ratio of component (B) to component (C) is 0.16 or more and 1.4 or less.

In one aspect, the mass ratio of the total content of the component (B) and the component (C) to the content of the (A1) ultraviolet absorber may be 0.18 or more and 0.68 or less, and (A2) the ultraviolet scattering agent The mass ratio of the total content of components (B) and (C) to the content of may be 0.2 or more and 0.63 or less. In one aspect, the content of (A1) the ultraviolet absorber may be 8% by mass or more and 16% by mass or less, and the content of (A2) the ultraviolet scattering agent is 8% by mass or more and 20% by mass or less. good.

In one aspect, the hydrophobically modified polyurethane may comprise at least one selected from the group consisting of (PEG-240/decyltetradeceth-20/HDI) copolymer and polyurethane-62. In one aspect, the polymer containing structural units derived from acrylamide may contain at least one selected from the group consisting of (Na acrylate/Na acryloyldimethyltaurate) copolymer and polyacrylamide. In a further aspect, the polyoxyalkylene glyceryl ether is at least one selected from the group consisting of polyoxypropylene glyceryl ether, polyoxyethylene polyoxypropylene glyceryl ether and polyoxybutylene polyoxyethylene polyoxypropylene glyceryl ether. may contain.

According to the present invention, it is possible to provide an oil-in-water type UV protective cosmetic which is excellent in water resistance and which improves the UV protective effect by getting wet with water.

In this specification, the term "process" is not only an independent process, but even if it cannot be clearly distinguished from other processes, it is included in this term as long as the intended purpose of the process is achieved. . In addition, the content of each component in the composition means the total amount of the plurality of substances present in the composition unless otherwise specified when there are multiple substances corresponding to each component in the composition. Furthermore, the upper and lower limits of the numerical ranges described herein can be combined by arbitrarily selecting the numerical values exemplified as the numerical ranges. Hereinafter, embodiments of the present invention will be described in detail. However, the embodiments shown below exemplify the oil-in-water type ultraviolet protective cosmetics for embodying the technical idea of the present invention, and the present invention is the oil-in-water type ultraviolet protective cosmetics shown below. is not limited to

Oil-in-water type UV protective cosmetic The oil-in-water type UV protective cosmetic is an UV protective agent containing at least one selected from the group consisting of (A1) UV absorber and (A2) UV scattering agent as component (A). at least one selected from the group consisting of hydrophobically modified polyurethanes and polymers containing constitutional units derived from acrylamide as component (B); and at least one polyoxyalkylene glyceryl ether as component (C). including seeds; In the oil-in-water type UV protective cosmetic, the content ratio (B/C) of component (B) to component (C) is 0.16 or more and 1.4 or less. In addition to the UV protection agent which is the component (A), by including the components (B) and (C) in a specific content ratio, it is excellent in water resistance and the effect of the UV protection agent is enhanced by getting wet with water. can be improved. Specifically, the water resistance of the oil-in-water type UV protective cosmetic is improved, and the UV protective effect after immersion treatment is further improved.

(A) UV protection agent The UV protection agent as component (A) includes at least one selected from the group consisting of (A1) UV absorbers and (A2) UV scattering agents. UV absorbers are substances that can absorb UV rays and release them as energy such as heat, infrared rays, and the like. An ultraviolet scattering agent is a substance that can absorb, reflect, and scatter ultraviolet rays to protect the skin and the like from ultraviolet rays.

(A1) UV absorbers include, for example, benzoic acid UV absorbers, anthranilic acid UV absorbers, salicylic acid UV absorbers, cinnamic acid UV absorbers, benzophenone UV absorbers, triazine UV absorbers, Examples include silicone-based ultraviolet absorbers. The ultraviolet absorber preferably contains at least one selected from the group consisting of cinnamic acid-based ultraviolet absorbers, triazine-based ultraviolet absorbers, and benzoic acid-based ultraviolet absorbers, from the viewpoint of ultraviolet protection effect, solubility, etc. you can stay Also, the ultraviolet absorber may be an oil-soluble organic ultraviolet absorber. Ultraviolet absorbers may be used alone or in combination of two or more.

Benzoic acid-based ultraviolet absorbers include para-aminobenzoic acid (PABA), glyceryl para-aminobenzoic acid, ethyldihydroxypropyl para-aminobenzoic acid, N-ethoxylate para-aminobenzoic acid ethyl ester, N-dimethyl para-aminobenzoic acid ethyl ester, N-dimethyl Para-aminobenzoic acid butyl ester, N-dimethyl para-aminobenzoic acid amyl ester, octyldimethyl para-aminobenzoic acid, diethylaminohydroxybenzoyl hexyl benzoate and the like. Examples of anthranilic acid-based ultraviolet absorbers include homomenthyl-N-acetylanthranilate. Salicylic acid-based UV absorbers include amyl salicylate, menthyl salicylate, homomenthyl salicylate, octyl salicylate, phenyl salicylate, benzyl salicylate, p-isopropanol phenyl salicylate, and the like. .

Cinnamic acid-based UV absorbers include octylcinnamate, ethyl-4-isopropylcinnamate, ethyl-2,4-diisopropylcinnamate, methyl-2,4-diisopropylcinnamate, propyl-p-methoxycinnamate, isopropyl -p-methoxycinnamate, isoamyl-p-methoxycinnamate, 2-ethylhexyl-p-methoxycinnamate, 2-ethoxyethyl-p-methoxycinnamate, cyclohexyl-p-methoxycinnamate, ethyl-α-cyano- β-phenylcinnamate, 2-ethylhexyl-α-cyano-β-phenylcinnamate, glyceryl mono-2-ethylhexanoyl dipramethoxycinnamate and the like. Benzophenone UV absorbers include 2,4-dihydroxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dihydroxybenzophenone, and 2-hydroxy-4-methoxybenzophenone. , 2-hydroxy-4-methoxy-4′-methylbenzophenone, 2-hydroxy-4-methoxybenzophenone, 4-phenylbenzophenone, 2-ethylhexyl-4′-phenylbenzophenone-2-carboxylate, 2-hydroxy-4- Examples include n-octoxybenzophenone, 4-hydroxy-3-carboxybenzophenone, and the like. Triazine-based UV absorbers include 2,4,6-tris[4-(2-ethylhexyloxycarbonyl)anilino]-1,3,5-triazine, dioctylbutamide triazone, 2,4-bis- [{4-(2-ethylhexyloxy)-2-hydroxy}-phenyl]-6-(4-methoxyphenyl)-1,3,5-triazine and the like. Dimethicodiethylbenzalmalonate etc. are mentioned as a silicone-type ultraviolet absorber.

Other organic UV absorbers include 3-(4′-methylbenzylidene)-dl-camphor, 3-benzylidene-dl-camphor, urocanic acid ethyl ester, 2-phenyl-5-methylbenzoxazole, 2,2 '-hydroxy-5-methylphenylbenzotriazole, 2-(2'-hydroxy-5-t-octylphenyl)benzotriazole, dibenzalazine, dianisoylmethane, 4-methoxy-4'-t-butyldibenzoylmethane, 5 -(3,3-dimethyl-2-norbonylidene)-3-pentan-2-one, benzene bis-1,3-diketone derivatives described in JP-A-2-212579, JP-A-3-220153 benzoylpinacolone derivatives and the like.

(A2) Examples of the ultraviolet scattering agent include metal oxide fine particles. Metal oxides include zinc oxide, titanium oxide, zirconium oxide, aluminum oxide, cerium oxide, iron oxide and chromium oxide. Among these, at least one selected from the group consisting of zinc oxide, titanium oxide and cerium oxide is preferred, at least one selected from the group consisting of zinc oxide and titanium oxide is more preferred, and zinc oxide is particularly preferred. The surface of the metal oxide fine particles may be surface-treated with at least one of an inorganic compound and an organic compound. Examples of inorganic compounds used for surface treatment include silicon oxide and aluminum oxide. Examples of organic compounds used for surface treatment include fatty acid metal soaps, alkoxysilanes such as octyltriethoxysilane, silicones such as hydrogen dimethicone, and dextrin fatty acids such as dextrin palmitate.

The shape of the metal oxide fine particles is not particularly limited, and examples thereof include spherical, plate-like, rod-like, spindle-like, needle-like, and irregular shapes. The average particle size of the metal oxide fine particles may be, for example, 0.01 μm or more, preferably 0.012 μm or more, 0.015 μm or more, 0.02 μm or more, or 0.03 μm or more. The average particle size of the metal oxide fine particles may be, for example, 1 µm or less, preferably 0.8 µm or less, 0.5 µm or less, 0.2 µm or less, 0.1 µm or less, 0.08 µm or less, or 0.8 µm or less. 04 μm or less. A specific range of the average particle size may be, for example, a range of 0.01 μm or more and 1 μm or less, preferably 0.012 μm or more and 0.8 μm or less, 0.015 μm or more and 0.5 μm or less, or 0.015 μm or more. It may be 0.2 μm or less. In addition, the average particle size of the metal oxide fine particles means the volume average particle size measured by a laser diffraction scattering method. The ultraviolet scattering agents may be used alone or in combination of two or more.

The (A) component UV protection agent may contain only at least one UV absorber, may contain only at least one UV scattering agent, or may contain at least one UV absorber. and at least one UV scattering agent.

The content of component (A) in the oil-in-water type UV protective cosmetic may be, for example, 5% by mass or more and 40% by mass or less. The content of component (A) may preferably be 6% by mass or more, 12% by mass or more, or 15% by mass or more. Moreover, the content of component (A) may preferably be 30% by mass or less, or 20% by mass. When the content of the component (A) is within the above range, a sufficient UV protection effect is obtained, and the stability and feel during use are excellent.

The content of the (A1) ultraviolet absorber in the oil-in-water type ultraviolet protective cosmetic may be, for example, 30% by mass or less. (A1) The content of the ultraviolet absorber is preferably 20% by mass or less, 18% by mass or less, or 16% by mass or less, and is preferably 4% by mass or more, 6% by mass or more, or 8% by mass. or more. (A1) When the content of the ultraviolet absorber is within the above range, a sufficient ultraviolet protection effect is obtained, and the stability and feel during use are excellent. The oil-in-water type UV protective cosmetic composition may contain (A1) UV absorbers singly or in combination of two or more.

The content of the (A2) ultraviolet scattering agent in the oil-in-water type ultraviolet protective cosmetic may be, for example, 30% by mass or less. (A2) The content of the ultraviolet scattering agent is preferably 20% by mass or less, 18% by mass or less, or 16% by mass or less, and is preferably 4% by mass or more, 6% by mass or more, or 8% by mass. or more. (A2) When the content of the ultraviolet scattering agent is within the above range, a sufficient ultraviolet protection effect is obtained, and the stability and feel during use are excellent. The oil-in-water type UV protective cosmetic composition may contain (A2) UV scattering agent singly or in combination of two or more.

When the oil-in-water type UV protective cosmetic contains (A1) a UV absorber and (A2) a UV scattering agent, the mass ratio (A1/A2) of the content of (A1) the UV absorbing agent to the (A2) UV scattering agent may be, for example, 0.01 or more and 30 or less. The mass ratio (A1/A2) may preferably be 0.2 or more, or 0.5 or more, and preferably 20 or less, 10 or less, 5 or less, or 2 or less.

(B) Polymer Containing Structural Units Derived from Hydrophobic-Modified Polyurethane and Acrylamide The oil-in-water type UV protective cosmetic is at least selected from the group consisting of polymers containing structural units derived from hydrophobically-modified polyurethane and acrylamide. One polymer is included as the (B) component. The component (B) functions, for example, as a polymer emulsifier and thickener, and contributes to the stability, dispersibility, water resistance, etc. of the oil-in-water type UV protective cosmetic. The oil-in-water type UV protective cosmetic may contain the component (B) singly or in combination of two or more.

Hydrophobic-modified polyurethanes include, for example, polyurethanes formed from alkylene diisocyanates such as hexamethylene diisocyanate and hydrophobically modified with polyethylene glycol ether of decyltetradecanol, hexamethylene diisocyanate, PEG-200, and methyl gluceth-10. and trideceth-6 copolymer whose terminals are blocked with an aliphatic alcohol having from 16 to 20 carbon atoms. Specific examples include (PEG-240/decyltetradeceth-20/HDI) copolymer, polyurethane-62, and the like. The hydrophobically modified polyurethane preferably contains at least one selected from the group consisting of (PEG-240/decyltetradeceth-20/HDI) copolymer and polyurethane-62, and at least (PEG-240/decyltetradeceth-20/HDI). Deceth-20/HDI) copolymer.

Examples of polymers containing structural units derived from acrylamide include copolymers containing at least one of polyacrylamide, acrylamide and acryloyldimethyltaurine as a structural unit. Copolymers containing at least one of acrylamide and acryloyldimethyltaurine as structural units include copolymers of acrylate and acryloyldimethyltaurate, copolymers of acrylamide and acrylate, and acrylic acid, acrylamide and acrylic acid. A copolymer of a salt and an acryloyldimethyltaurate salt, a copolymer of vinylpyrrolidone and an acryloyldimethyltaurate salt, and the like can be mentioned. Among these, copolymers of acrylate and acryloyldimethyltaurate are preferred. Here, the polymer containing a structural unit derived from acrylamide preferably does not contain a structural unit derived from an acrylic acid ester.

More specifically, the polymer containing structural units derived from acrylamide includes polyacrylamide, (Na acrylate/Na acryloyldimethyltaurate) copolymer, (acrylamide/ammonium acrylate) copolymer, (acrylic acid/acryloyldimethyltaurine/dimethyl acrylamide) crosspolymer, (acryloyldimethyltaurate ammonium/vinylpyrrolidone) copolymer, acrylic acid/acrylamide/acrylic acid Na/acryloyldimethyltaurate Na) copolymer, (acryloyldimethyltaurate ammonium/beheneth-25 methacrylate) crosscopolymer, (acryloyldimethyl and ammonium taurine/steareth methacrylate-25) crosspolymer. The polymer containing structural units derived from acrylamide may contain at least one selected from the group consisting of polyacrylamide and (Na acrylate/Na acryloyldimethyltaurate) copolymers.

Component (B) in the oil-in-water type UV protective cosmetic preferably contains at least one selected from the group consisting of hydrophobically modified polyurethane, polyacrylamide, and a copolymer of acrylate and acryloyldimethyltaurate. .

The content of component (B) in the oil-in-water type UV protective cosmetic may be, for example, 0.1% by mass or more and 10% by mass or less. The content of component (B) in the oil-in-water type UV protective cosmetic is preferably 0.5% by mass or more, or may be 0.9% by mass or more, and is preferably 5% by mass or less, or 2.0% by mass. % by mass or less. Moreover, the content of the component (B) in the oil-in-water type UV protective cosmetic may be, for example, 0.1% by mass or more and 10% by mass or less when the component (B) contains a hydrophobically modified polyurethane. The content of component (B) in the oil-in-water type UV protective cosmetic is preferably 0.5% by mass or more, or 0.9% by mass or more, and preferably 5% by mass or less, or 2% by mass. may be: Furthermore, the content of component (B) in the oil-in-water type UV protective cosmetic is, for example, 0.1% by mass or more and 10% by mass or less when the component (B) contains a polymer containing a structural unit derived from acrylamide. It can be. The content of component (B) in the oil-in-water type UV protective cosmetic is preferably 0.5% by mass or more, or may be 0.9% by mass or more, and is preferably 5% by mass or less, or 2.0% by mass. % by mass or less.

The content ratio (B/A) of component (B) to component (A) in the oil-in-water type UV protective cosmetic may be, for example, 0.01 or more and 0.5 or less. The content ratio (B/A) is preferably 0.02 or more, 0.03 or more, or 0.04 or more, and is preferably 0.2 or less, 0.1 or less, 0.08 or less, or It may be 0.06 or less.

(C) Polyoxyalkylene Glyceryl Ether The oil-in-water type UV protective cosmetic contains at least one polyoxyalkylene glyceryl ether as the (C) component. The component (C) functions, for example, as a moisturizing agent, an emulsifying aid, a texture improving agent, etc., and improves the usability and stability of the oil-in-water type UV protective cosmetic. The oil-in-water type UV protective cosmetic may contain the component (C) singly or in combination of two or more.

Polyoxyalkylene glyceryl ether is an ether compound composed of polyalkylene glycol and glycerin. The polyalkylene glycol that constitutes the polyoxyalkylene glyceryl ether may include polyalkylene glycols such as polyethylene glycol (PEG), polypropylene glycol (PPG) and polybutylene glycol (PBG). Moreover, the polyalkylene glycol glyceryl ether may contain a water-soluble alkylene oxide derivative represented by the following formula (1).
Gly-[O-(PO) _m (EO) _n (BO) _p -H] (1)

In formula (1), Gly is a residue obtained by removing a hydroxyl group from glycerin, PO is an oxypropylene group, EO is an oxyethylene group, and BO is an oxybutylene group. m and n are the average added mole numbers of the oxypropylene group PO and the oxyethylene group EO, respectively, and may be 0≦m≦50 and 0≦n≦50. p is the average number of added moles of the oxyalkylene group BO, and may have a value of 1≦p≦5. However, m and n are not 0 at the same time. When neither m nor n is 0, the mass ratio of PO to EO (PO/EO) may be, for example, 1/5 or more and 5/1 or less. EO, PO and BO may be added randomly or in blocks, and random portions and block portions may be mixed.

Polyalkylene glycol constituting polyoxyalkylene glyceryl ether is composed of polyethylene glycol (PEG), polypropylene glycol (PPG), polybutylene glycol (PBG) and an oxyalkylene group having 3 or 4 carbon atoms and an oxyethylene group. It may contain at least one selected from the group consisting of polyalkylene glycols.

Specifically, the polyoxyalkylene glyceryl ether contains at least one selected from the group consisting of polyoxypropylene glyceryl ether, polyoxyethylene polyoxypropylene glyceryl ether and polyoxybutylene polyoxyethylene polyoxypropylene glyceryl ether. is preferred.

The content of component (C) in the oil-in-water type UV protective cosmetic may be, for example, 0.1% by mass or more and 9% by mass or less. The content of component (C) in the oil-in-water type UV protective cosmetic is preferably 0.5% by mass or more, or 2% by mass or more, and preferably 7% by mass or less, or 5% by mass or less. It's okay.

The content ratio (B/C) of component (B) to component (C) in the oil-in-water type UV protective cosmetic may be, for example, 0.16 or more, preferably 0.18 or more, or 0.2 or more. It can be. The content ratio (B/C) may preferably be 10 or less, 4 or less, 1.4 or less, 1.2 or less, 1 or less, 0.8 or less, 0.6 or less, or 0.5 or less. The content ratio (B/C) may be 0.16 or more and 1.4 or less, preferably 0.18 or more and 1.2 or less, or 0.18 or more and 1 or less.

The content ratio (C/A) of component (C) to component (A) in the oil-in-water type UV protective cosmetic may be, for example, 0.01 or more and 0.45 or less. The content ratio (C/A) is preferably 0.02 or more, 0.04 or more, 0.06 or more, 0.08 or more, or 0.10 or more, and preferably 0.3 or less, 0 0.26 or less, 0.24 or less, 0.22 or less, 0.2 or less, 0.16 or less, or 0.14 or less.

The ratio of the total content of components (B) and (C) to the content of component (A) in the oil-in-water type UV protective cosmetic ((B+C)/A) is, for example, 0.05 or more and 0.5 or less. It's okay. The ratio ((B+C)/A) may preferably be 0.07 or more, 0.09 or more, 0.12 or more, or 0.14 or more, and preferably 0.33 or less, 0.3 or less, It may be 0.28 or less, 0.26 or less, or 0.2 or less.

When the oil-in-water type UV protective cosmetic contains (A1) a UV absorber, the total content of components (B) and (C) with respect to the content of (A1) UV absorber in the oil-in-water type UV protective cosmetic The ratio ((B+C)/A1) may be, for example, 0.05 or more and 1 or less, or 0.1 or more and 0.8 or less. The ratio ((B+C)/A1) may preferably be 0.15 or more, 0.18 or more, 0.24 or more, or 0.28 or more, and preferably 0.7 or less, 0.68 or less, It may be 0.58 or less, or 0.46 or less.

When the oil-in-water type UV protective cosmetic contains (A2) a UV scattering agent, the total content of the component (B) and the component (C) with respect to the content of the UV scattering agent (A2) in the oil-in-water type UV protective cosmetic. The ratio ((B+C)/A2) may be, for example, 0.05 or more and 1 or less, or 0.1 or more and 0.8 or less. The ratio ((B+C)/A2) may preferably be 0.15 or more, 0.2 or more, or 0.24 or more, and preferably 0.7 or less, 0.63 or less, 0.6 or less, It may be 0.5 or less, or 0.4 or less.

The oil-in-water type UV protective cosmetic contains, in addition to the UV protective agent, a hydrophobically modified polyurethane, a polymer containing a structural unit derived from acrylamide, and a polyoxyalkylene glyceryl ether, other substances that can be usually incorporated in the UV protective cosmetic. It may contain optional ingredients. Other optional ingredients include, for example, liquid oils, water-soluble polymers, oil-soluble polymers, solid oils such as waxes, lower alcohols, moisturizing ingredients, surfactants, powder ingredients, antiseptic ingredients, drugs, and the like. , but not limited to these examples.

Liquid oils include silicone oils, hydrocarbon oils, vegetable oils, ester oils, high molecular weight polyoxyalkylene glycols, and the like. Specific examples include silicone oils such as dimethicone, diphenyl dimethicone, and cyclopentasiloxane; linseed oil, camellia oil, macadamia nut oil, corn oil, olive oil, avocado oil, sasanqua oil, castor oil, safflower oil, Chinese ginseng oil, and cinnamon oil. , jojoba oil, grape oil, almond oil, rapeseed oil, sesame oil, sunflower oil, wheat germ oil, rice germ oil, rice bran oil, cottonseed oil, soybean oil, peanut oil, tea seed oil, evening primrose oil, egg yolk oil, cod liver oil, Liquid oils such as triglycerin, glyceryl trioctanoate, and glyceryl triisopalmitate; octanoic acid esters such as cetyl octanoate; isooctanoic acid esters such as glyceryl tri-2-ethylhexanoate and pentaerythrityl tetra-2-ethylhexanoate , Laurate esters such as hexyl laurate, Myristate esters such as isopropyl myristate and Octyldodecyl myristate, Palmitate esters such as octyl palmitate, Stearate esters such as isocetyl stearate, Isostearates such as Isopropyl isostearate , isopalmitate such as octyl isopalmitate, oleate such as isodecyl oleate, adipate diester such as diisopropyl adipate, sebacate diester such as diethyl sebacate, ester oil such as diisostearyl malate; Hydrocarbon oils such as paraffin and squalane; polyoxybutylene, polyoxypropylene glycol and the like.

Water-soluble polymers include carboxyvinyl polymer, ammonium polyacrylate, sodium polyacrylate, sodium acrylate/alkyl acrylate/sodium methacrylate/alkyl methacrylate copolymer, carrageenan, pectin, mannan, curdlan, and chondroitin. Sulfate, starch, glycogen, gum arabic, sodium hyaluronate, gum tragacanth, xanthan gum, mucoitin sulfate, hydroxyethyl guar gum, carboxymethyl guar gum, guar gum, dextran, kerato sulfate, locust bean gum, succinoglucan, chitin, chitosan, carboxymethyl chitin , agar and the like are exemplified.

Examples of oil-soluble polymers include trimethylsiloxysilicate, alkyl-modified silicone, polyamide-modified silicone, dimethicone crosspolymer, (dimethicone/vinyl dimethicone) crosspolymer, and polymethylsilsesquioxane.

Examples of waxes include beeswax, candelilla wax, carnauba wax, lanolin, liquid lanolin, and jojoba wax.

Lower alcohols include alcohols having 1 to 5 carbon atoms such as ethanol and isopropanol. Examples of moisturizing ingredients include polyhydric alcohols such as ethylene glycol, propylene glycol, 1,3-butylene glycol, dipropylene glycol and polybutylene glycol.

Surfactants include anionic, cationic, nonionic, or amphoteric surfactants, including silicone-based or hydrocarbon-based surfactants. Examples of the powder component include nylon, acrylic polymer spherical powder, silica powder, silicone powder, cellulose powder, starch powder, silk powder and the like.

Drugs include salts of L-ascorbic acid and its derivatives, dipotassium glycyrrhizinate, glycyrrhizic acid and its derivatives such as monoammonium glycyrrhizinate, glycyrrhetic acid and its derivatives such as stearyl glycyrrhetinate, allantoin, tranexamic acid and salts of its derivatives. , alkoxysalicylic acid and its derivative salts, glutathione and its derivative salts, allantoin, azulene and the like.

Other ingredients include sugars such as trehalose and erythritol, polysaccharides such as hyaluronic acid and acetylated hyaluronic acid, amino acids such as serine, glycine, hydroxyproline, glutamic acid and alanine, silk extract, chlorella extract, and hydrolyzed pearl protein. , corn extract, tencha extract, yeast extract, inositol, licorice extract, burnet extract, rose extract, coix seed extract, and the like.

Specific formulations of the oil-in-water type UV protective cosmetics are formulations such as sunscreen milky lotion and sunscreen cream, and can be produced using a conventional method suitable for each formulation.

The present invention may further include the following aspects.
[1] (A1) an ultraviolet absorber and (A2) an ultraviolet light scattering agent containing at least one selected from the group consisting of (A) an ultraviolet light blocking agent, and a polymer containing structural units derived from hydrophobically modified polyurethane and acrylamide A component (B) containing at least one selected from the group consisting of coalescence and a component (C) containing a polyoxyalkylene glyceryl ether, wherein the content ratio of the component (B) to the component (C) is 0 .18 or more and 1 or less oil-in-water type ultraviolet protective cosmetics.

[2] The oil-in-water ultraviolet light according to [1], wherein the mass ratio of the total content of the components (B) and (C) to the content of the (A1) ultraviolet absorber is 0.18 or more and 0.68 or less. protective cosmetics.

[3] (A2) The mass ratio of the total content of components (B) and (C) to the content of the ultraviolet scattering agent is 0.2 or more and 0.63 or less. Oil-in-water type UV protective cosmetics.

[4] (A1) The oil-in-water UV protective cosmetic composition according to any one of [1] to [3], wherein the content of the UV absorber is 8% by mass or more and 16% by mass or less.

[5] (A2) The oil-in-water type UV protective cosmetic composition according to any one of [1] to [4], wherein the content of the UV scattering agent is 8% by mass or more and 20% by mass or less.

[6] The hydrophobically modified polyurethane contains at least one selected from the group consisting of (PEG-240/decyltetradeceth-20/HDI) copolymer and polyurethane-62. The oil-in-water type ultraviolet protective cosmetic composition described in Cr.

[7] The polymer containing structural units derived from acrylamide contains at least one selected from the group consisting of (Na acrylate/Na acryloyldimethyltaurate) copolymer and polyacrylamide of [1] to [6]. The oil-in-water type ultraviolet protective cosmetic composition according to any one of the above.

[8] The polyoxyalkylene glyceryl ether contains at least one selected from the group consisting of polyoxypropylene glyceryl ether, polyoxyethylene polyoxypropylene glyceryl ether and polyoxybutylene polyoxyethylene polyoxypropylene glyceryl ether [ The oil-in-water type UV protective cosmetic composition according to any one of 1] to [7].

EXAMPLES The present invention will be specifically described below by way of examples, but the present invention is not limited to these examples.

Examples 1 to 6 and Comparative Examples 1 to 6
A sample of an oil-in-water type UV protection cosmetic composition was produced by uniformly mixing the components with the label names listed in Table 1 so that the content (%) was as listed in Table 1. The details of the components in Tables 1 to 4 below will be described later. In addition, a blank (-) in the table indicates that it is not blended or evaluated.

Using the obtained samples, the "SPF increasing effect (SPF increasing rate)" was evaluated as follows. Table 1 shows the results.

Evaluation method SPF increase effect (SPF increase rate)
For the evaluation of the SPF increasing effect, each sample obtained above was applied to a PMMA plate (HELIOPLATE HD 6 manufactured by Labsphere) at 1.33 mg/cm ² and then air-dried for 15 minutes. After that, the SPF value of the PMMA plate coated with the sample was measured using an SPF analyzer (Labsphere; UV-2000 S) before the water immersion treatment. Thereafter, the PMMA plate coated with the sample was placed in a petri dish, fixed with the coated surface facing upward, immersed in tap water at room temperature, and continuously shaken on a shaking table (Rocking Mixer RM-80, manufactured by AS ONE) for 20 minutes. After replacing the tap water and repeating the same operation twice, the PMMA plate was left to dry for 30 minutes or more. Again, the SPF value after the water immersion treatment was measured with the SPF analyzer. The SPF increase rate was calculated by the following formula from the initial SPF value and the post-treatment value, and the SPF increase effect was determined according to the following criteria.
SPF increase rate (%) = (SPF value after flooding treatment) / (SPF value before flooding treatment) x 100

Criteria S: The SPF increase rate was 120% or more.
A: The SPF increase rate was 105% or more and less than 120%.
B: The SPF increase rate was 90% or more and less than 105%.
C: The SPF increase rate was less than 90%.

Examples 7 to 10, Comparative Example 7
Ingredients with display names listed in Table 2 were uniformly mixed so that the content (%) listed in Table 2 was obtained, and a sample of an ultraviolet protective cosmetic was produced.

Using the obtained samples, the "SPF increasing effect" was evaluated in the same manner as described above. Table 2 shows the evaluation results.

Examples 11 to 13
Ingredients with display names listed in Table 3 were uniformly mixed so that the content (%) listed in Table 3 was obtained to produce a sample of an ultraviolet protective cosmetic composition.

Using the obtained samples, the "SPF increasing effect" was evaluated in the same manner as described above. Table 3 shows the evaluation results.

Examples 14 to 16 and Comparative Example 8
Ingredients with display names listed in Table 4 were uniformly mixed so that the content (%) listed in Table 4 was obtained, and a sample of an ultraviolet protective cosmetic was produced.

Using the obtained samples, the "SPF increasing effect" was evaluated in the same manner as described above. Table 4 shows the evaluation results.

Examples 17 and 18
Ingredients with display names listed in Table 5 were uniformly mixed so that the content (%) listed in Table 5 was obtained, and a sample of an ultraviolet protective cosmetic was produced.

Using the obtained samples, the "SPF increasing effect" was evaluated in the same manner as described above. Table 5 shows the evaluation results.

From the above, (A) an ultraviolet protective agent, (B) at least one selected from the group consisting of a polymer containing structural units derived from hydrophobically modified polyurethane and acrylamide, and (C) a polyoxyalkylene glyceryl ether , and the content ratio of the component (B) to the component (C) is 0.18 or more and 1 or less.

The details of each component with the display name in Tables 1 to 5 are shown below.
- Ethylhexyl methoxycinnamate: UVINUL (registered trademark) MC 80 (BASF Japan Ltd.)
- Bisethylhexyloxyphenol methoxyphenyl triazine: TINOSORB (registered trademark) S (BASF Japan Ltd.)
Dodecane: PARAFOL® 12 RSPO-MB (SASOL Germany GmbH)
・Cetanol: Calcoal 6870 (Kao Corporation)
・ Tocopherol: Tocopherol 100 (Nissin OilliO Group Co., Ltd.)
・Hydrogen dimethicone-treated zinc oxide (60%), hydrogenated polyisobutene, polyhydroxystearic acid: ZDB-300 (Titanium Kogyo Co., Ltd.)
・ Sorbitan stearate: Rheodor SP-S10V (Kao Corporation)
・Phenoxyethanol: Phenoxyethanol-S (Yokkaichi Synthetic Co., Ltd.)
- (PEG-240/decyltetradeceth-20/HDI) copolymer (90%), trideceth-6: Avalue ^™ Flex-6 CC Polymer (Lubrizol)
・ Polyurethane-62 (90%), Trideceth-6: Avalue ^TM Flex-6 Polymer (Lubrizol)
・ PEG / PPG / polybutylene glycol-8/5/3 glycerin: Willbride (registered trademark) S-753D (NOF Corporation)
・ Silicic acid (Al/Mg): Sumecton SA (Kunimine Industry Co., Ltd.)
・Agar, xanthan gum: Nomucort AG (Nissin OilliO Group Inc.)
・Silica: Sunsphere NP-100 (AGC Si Tech Co., Ltd.)
Propanediol: Zemea® Select Propanediol (Dupont Tate & Lyle Bio Products Company LLC)
- (Acrylates/alkyl acrylate (C10-30)) crosspolymer: Pemulen ^™ EZ-4U Polymeric Emulsifier (Lubrizol)
- Polyacrylamide (40%), (C13, 14) isoparaffin, laureth-7, water: SEPIGEL 305 (SEPPIC SA)
- (Sodium acrylate/Na acryloyldimethyltaurate) copolymer (40%), isohexadecane, polysorbate 80, water: SIMULGEL EG (SEPPIC SA)
- Hexyl diethylaminohydroxybenzoylbenzoate: UVINUL (registered trademark) A Plus Granular (BASF Japan Ltd.)
・ t-butyl methoxydibenzoylmethane: Parsol 1789 (DSM Corporation)
・ Polyoxypropylene glyceryl ether: Uniol (registered trademark) SGP-65 (NOF Corporation)
- Polyoxyethylene polyoxypropylene glyceryl ether (24E.O.) (24P.O.): Unilube (registered trademark) 50TG-32 (NOF Corporation)

Claims (9)

(A1) an ultraviolet absorber and (A2) an ultraviolet light scattering agent containing at least one selected from the group consisting of (A) an ultraviolet protective agent, and a polymer containing structural units derived from hydrophobically modified polyurethane and acrylamide. (B) component containing at least one selected from the group and (C) component containing polyoxyalkylene glyceryl ether,
The component (B) contains at least one of a polyurethane-62, polyacrylamide, and at least one of acrylamide and acryloyldimethyltaurine as structural units. At least one selected from the group consisting of copolymers comprising
The component (C) contains at least one selected from the group consisting of polyoxypropylene glyceryl ether, polyoxyethylene polyoxypropylene glyceryl ether and polyoxybutylene polyoxyethylene polyoxypropylene glyceryl ether,
The content of the component (A) is 5% by mass or more and 40% by mass or less,
The content of the component (B) is 0.9% by mass or more and 5% by mass or less,
The content of the component (C) is 0.1% by mass or more and 9% by mass or less,
An oil-in-water type UV protection cosmetic, wherein the content ratio of component (B) to component (C) is 0.16 or more and 1.4 or less. (A1) The oil-in-water type UV protective cosmetic composition according to claim 1, wherein the mass ratio of the total content of the components (B) and (C) to the content of the UV absorber is 0.15 or more and 0.7 or less. . (A2) The oil-in-water type UV protective cosmetic composition according to claim 1, wherein the mass ratio of the total content of components (B) and (C) to the content of the UV scattering agent is 0.15 or more and 0.65 or less. . (A1) The oil-in-water type UV protective cosmetic composition according to claim 1, wherein the content of the UV absorber is 20% by mass or less. 2. The oil-in-water type UV protection cosmetic according to claim 1, wherein the content of (A2) UV scattering agent is 20% by mass or less. 2. The oil-in-water type according to claim 1, wherein the hydrophobically modified polyethylene glycol ether of decyltetradecanol of the polyurethane formed from alkylene diisocyanate is a (PEG-240/decyltetradeceth-20/HDI) copolymer. UV protection cosmetics. (A) The UV protection agent contains (A1) an UV absorber and (A2) an UV scattering agent, and the ratio of the total content of components (B) and (C) to the total content of components (A) is 0. The oil-in-water type ultraviolet protective cosmetic composition according to claim 1 , wherein the ratio is 0.05 or more and 0.2 or less. The polymer containing structural units derived from acrylamide includes (Na acrylate/Na acryloyldimethyltaurate) copolymer, (acrylamide/ammonium acrylate) copolymer, (acrylic acid/acryloyldimethyltaurine/dimethylacrylamide) crosspolymer, (acryloyl ammonium dimethyl taurate/vinylpyrrolidone) copolymer, acrylic acid/acrylamide/Na acrylate/Na acryloyl dimethyl taurate) copolymer, (ammonium acryloyl dimethyl taurate/beheneth-25 methacrylate) cross-copolymer and (ammonium acryloyl dimethyl taurate/steareth methacrylate- 25) The oil-in-water type UV protection cosmetic composition according to claim 1, which contains at least one selected from the group consisting of crosspolymers. 2. The oil-in-water type UV protection according to claim 1, wherein the polymer containing structural units derived from acrylamide comprises at least one selected from the group consisting of (Na acrylate/Na acryloyldimethyltaurate) copolymer and polyacrylamide. cosmetics.