Emulsified sunscreen composition

Abstract

To provide an emulsified sunscreen composition that can maintain high UV protection for a long time and offers good user experience and good stability over time; specifically, a composition that exhibits high UV protection, long-lasting makeup, secondary attachment prevention, and good user experience; and furthermore, an emulsified sunscreen composition that delivers high-temperature stability, capable of solving storage problems in the market.SOLUTION: An emulsified sunscreen composition contains (A) polyurethane-79 gel composition composed of (A-1) polyurethane-79 and (A-2) liquid oil solution, (B) silicone-based surfactant and (C) UV protection agent.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to an emulsified sunscreen composition. More specifically, by containing specific components, it can maintain a high UV protection effect for a long time, has good stability over time such as high-temperature stability, has good makeup retention, has an anti-secondary adhesion effect, and has a good usability composition.

Background Art

[0002] Protecting the skin from ultraviolet rays is an important issue in skin care and body care, and various sunscreen compositions have been developed to minimize the adverse effects of ultraviolet rays on the skin. Sunscreen compositions protect the skin from harmful UVA and UVB by blending UV protectants such as UV absorbers and UV scatterers. In recent years, it is considered important to protect the skin from ultraviolet rays not only under harsh ultraviolet conditions in outdoor activities but also in daily life. As the performance required for sunscreen compositions, it is important not only to have a high UV protection effect but also to maintain that effect for a long time. Furthermore, good usability and sufficient storage stability in the market are also required.

[0003] UV absorbers blended as UV protectants have a maximum absorption wavelength in the UVA and UVB regions and generally have unfavorable aspects in terms of skin safety such as having skin irritation. UV scatterers are powders that physically block ultraviolet rays by reflection or scattering and have little skin irritation, but the whiteness during application and the peculiar squeaking feeling have sometimes been problems.

[0004] Sunscreen cosmetics having excellent UV protection ability have been reported by using a combination of a UV absorber and a surface-treated UV scatterer to exhibit a high UV protection effect (Patent Document 1). However, since the blending amount of the UV protectant itself is large, as described above, skin irritation, whiteness during application, and the peculiar squeaking feeling are problems.

[0005] Therefore, technologies that increase the SPF value by using a substance that does not exhibit UV protection on its own but is used in combination with a UV protection agent have been investigated with the aim of reducing the amount of UV protection agent used and improving skin irritation and feel. For example, it has been reported that the UV protection effect is increased when a cosmetic composition is created by using a lipoamino acid alkyl ester in combination with a UV protection agent (Patent Document 2). Furthermore, it has been reported that the SPF value can be improved by incorporating alkyl silicone waxes with a melting point of 60°C or higher, which similarly do not have UV absorption effects on their own (Patent Document 3). However, when these waxes are used, the feel tends to become heavy, and there are also issues with the feel because it is not possible to suppress the squeaky and sticky feeling of UV scattering agents and UV absorbing agents.

[0006] Polyurethane is a polymer containing urethane bonds in its structure, and is known for its excellent elasticity, flexibility, adhesion, and impact resistance. In recent years, its gelling ability in various solvents has attracted attention, and it is being incorporated into various cosmetics. It is supplied in various forms, such as a powder or lump close to its pure form, a gel pre-dissolved in a solvent, or a solution. Furthermore, there are various molecular structures and compositions, and their properties vary accordingly. Naturally, its solubility in each solvent and its gelling characteristics also differ, ranging from water-soluble types to those soluble in polar oils, non-polar oils, and silicone oils. Dozens of types of polyurethane are known to be under consideration for use in cosmetics (Patent Document 4).

[0007] A water-in-oil composition has been disclosed that incorporates oil-soluble polyurethane into an emulsified sunscreen composition to create a composition with excellent usability and feel, such as spreadability during application, glossiness, adhesion to the skin, and non-stickiness of the film after formation. This composition involves creating a powder by coating the surface of an oil-soluble polyurethane that exhibits high gel strength when dissolved in oil, specifically "(i) a polyurethane obtained by the reaction of (a) hydrogenated polybutadiene having an isocyanate group at the terminus and (b) a linear or branched C2-C6 glycol, or (ii) an oil-soluble polyurethane synthesized by the reaction of (c) hydrogenated polybutadiene having a hydroxyl group at the terminus, (d) a diisocyanate compound, and (b) a glycol represented by HO-R-OH (linear or branched C2-C6 alkylene group)," with an oil-based agent to pre-dilute it with an oil-based agent, and then incorporating a volatile oil-based agent and a fluorine-modified silicone resin. Furthermore, it has been stated that an oil with low polarity is preferable to further increase gel strength (Patent Document 5). However, the oil-soluble polyurethane described in Patent Document 5 is used as a surface treatment agent for powders, and its high gel strength makes it difficult to incorporate in large quantities into formulations, thus presenting a problem in its application to improve the long-term stability of compositions.

[0008] Sunscreen compositions are desirable to maintain their UV protection effect for a long period of time without reapplication, in order to protect the skin from sunlight during the day. Physical contact in daily life can cause UV protection agents to transfer to the object they come into contact with, preventing the coating from being maintained and reducing the UV protection ability. Therefore, enhancing the secondary adhesion-free effect is an effective means of maintaining the UV protection effect of sunscreen compositions. Techniques to enhance the secondary adhesion-free effect include incorporating large amounts of components that evaporate at room temperature, such as volatile silicone oils, volatile hydrocarbon oils, volatile hydrofluoroethers, and water, and combining them with oily film-forming agents such as hard, non-transferable silicone resins. For example, it has been disclosed that a water-in-oil composition is formulated by combining cyclic silicone oil or light liquid isoparaffin and volatile hydrofluoroether with an oil-soluble silicone resin (Patent Document 6). As the volatile components in the composition evaporate and the silicone resin used forms a rigid oily film, a hard film is created, resulting in a secondary adhesion-free effect. However, because it lacks flexibility, it may wrinkle or crack due to changes in skin condition throughout the day, resulting in an unsatisfactory effect. Furthermore, volatile components in the composition evaporate, and the moisturizing effect is also diminished. For the reasons stated above, there was an urgent need to develop a sunscreen composition that offers high UV protection, good makeup retention, prevents secondary adhesion, has a pleasant feel, and exhibits good stability over time. [Prior art documents] [Patent Documents]

[0009] [Patent Document 1] Japanese Patent Publication No. 2017-066137 [Patent Document 2] Japanese Patent Publication No. 2022-091735 [Patent Document 3] Japanese Patent Publication No. 2020-111542 [Patent Document 4] Japanese Patent Publication No. 2022-152038 [Patent Document 5] Japanese Patent Publication No. 2020-029444 [Patent Document 6] Japanese Patent Publication No. 2005-225806 [Overview of the project] [Problems that the invention aims to solve]

[0010] The present invention has been made in view of the above-mentioned prior art, and aims to provide a sunscreen composition that has a high UV protection effect, good makeup retention, prevents secondary adhesion, and has a good feel when used. In addition, it has good high temperature stability and solves the problems of storage in the market. [Means for solving the problem]

[0011] As a result of diligent research and development, the inventors have discovered an emulsified sunscreen composition that can solve the above problems by combining (A) a polyurethane-79 gel composition, in which polyurethane-79 obtained by the reaction of 1,6-hexamethylene diisocyanate (HDI), 1,4-butanediol, hydrogenated dilinoleyl alcohol, and hydrogenated polybutanediol has both ends blocked with stearyl alcohol, with (B) a silicone-based surfactant and (C) a UV protection agent, and have completed the present invention.

[0012] In other words, the present invention consists of the following components (A) to (C) [1] (A) Polyurethane-79 gelling composition comprising (A-1) Polyurethane-79 and (A-2) liquid oil (B) Silicone-based surfactants (C) UV protection agent This is an emulsified sunscreen composition containing [ingredient name]. [2] The above component (C) UV protection agent is a hydrophobized fine particle metal oxide The emulsified sunscreen composition described in [1] above. [3] The emulsified sunscreen composition according to [1], wherein the component (B) silicone-based surfactant is a polyglycerin-modified silicone. 〔4〕The emulsion sunscreen composition according to any one of 〔1〕to 〔3〕above, wherein the content ratio of the above (A-1) and the above (B) is a mass ratio, and (A-1) / (B)=0.05 to 5.

Advantages of the Invention

[0013] According to the present invention, there is provided an emulsion sunscreen composition having a high ultraviolet protection effect, good makeup retention, an anti-secondary adhesion effect, and good usability. In addition, it has good high-temperature stability and can solve the problems during storage in the market.

Best Mode for Carrying Out the Invention

[0014] Next, preferred embodiments of the present invention will be described in detail. However, the present invention is not limited to the following preferred embodiments and can be freely changed within the scope of the present invention. In addition, in this specification, percentages are expressed by mass unless otherwise specified. In this specification, when representing a numerical range using ~, the range includes the numerical values at both ends.

[0015] The (A) polyurethane-79 gel composition contained in the emulsion sunscreen composition of the present invention is a gelled composition composed of (A-1) polyurethane-79 and (A-2) a liquid oil agent.

[0016] (A-1) Polyurethane-79 is a polyurethane in which 1,6-hexamethylene diisocyanate (HDI), a linear aliphatic diisocyanate, and 1,4-butanediol, a linear extender dihydric alcohol, form a block of a hard segment that becomes a polyurethane through urethane bonds, and a block of a soft segment of hydrogenated dilinoleyl alcohol and hydrogenated polybutanediol, with both ends blocked with stearyl alcohol. Due to the polarity of the polyurethane block, an association via hydrogen bonds between polymer-polymer and polymer-oil forms a physical network in the oil. It is considered that gelation occurs by incorporating an oil agent into this three-dimensional network structure. Polyurethane-79 has higher alcohol residues at its ends, improving its solubility in various oil agents and thus enhancing the stability of the emulsifying sunscreen composition. Preferably, the (A-1) polyurethane-79 used in the present invention can be easily and uniformly dissolved by dissolving it in the (A-2) liquid oil agent to form a gel-like composition.

[0017] For the polyurethane-79 gel composition of (A) of the present invention, commercially available OILKEMIA 5S CC (manufactured by LUBRIZOL) can be used. Its composition is a (A) polyurethane-79 gel composition containing 30% of (A-1) polyurethane-79 and 70% of glyceryl tri(caprylate / caprate) as the (A-2) liquid oil agent. When formulated in cosmetics in Japan, when indicating the formulation ingredients, it is common to indicate 70% of glyceryl tri(caprylate / caprate), 25% of hydrogenated polyolefin (C6-20), and 5% of (HDI / trimethylolhexyl lactone) cross-polymer.

[0018] The content of (A-1) polyurethane-79 in the (A) polyurethane-79 gel composition is not particularly limited, but is preferably 10 to 50% by mass, more preferably 20 to 40% by mass. The content of liquid oil (A-2) in the polyurethane-79 gel composition (A) is not particularly limited, but is preferably 50 to 90% by mass, and more preferably 60 to 80% by mass. This range is preferable because it facilitates uniform dissolution during manufacturing, makes it easy to adjust the blending concentration, and allows the effects of the invention to be significantly achieved.

[0019] The liquid oil (A-2) used in the polyurethane-79 gel composition of (A) is not particularly limited as long as it is commonly used in cosmetics. While its properties are not particularly limited, it is preferably a liquid oil at 25°C. Examples of liquid oils (A-2) used in the polyurethane-79 gel composition of (A) include hydrocarbon oils, ester oils, fatty acids, and silicone oils, regardless of their origin, such as animal oils, vegetable oils, or synthetic oils. It is preferable to use one or more of these in the liquid oil (A-2).

[0020] The content of (A) polyurethane-79 gel composition in the emulsified sunscreen composition of the present invention is not particularly limited. The content of (A-1) polyurethane-79 in the emulsified sunscreen composition of the present invention is not limited, but it is very preferable to be 0.1 to 10.0% by mass, preferably 0.2 to 5.0% by mass, and more preferably 0.3 to 2.0% by mass. This range is preferable in that it provides excellent makeup retention and prevents secondary adhesion. Furthermore, it is preferable in terms of the uniformity of the makeup film, and a high UV protection effect can be obtained in combination with component (C).

[0021] In the present invention, any silicone-based surfactant commonly used in emulsified sunscreen compositions can be used as (B), but polyether-modified silicones are preferred. Specifically, examples include polyoxyalkylene-modified silicones, polyglycerin-modified silicones, polyoxyalkylene-alkyl copolymer-modified silicones, polyglycerin-alkyl copolymer-modified silicones, and linear copolymer-type polyether-modified silicones. The silicone main chain can be a linear type, a branched type, or a cross-linked type. Furthermore, the silicone chains branched from the silicone main chain can be linear or further branched.

[0022] (B) As for silicone-based surfactants, polyglycerin-modified silicones and polyglycerin-alkyl copolymerized silicones are preferred from the viewpoint of emulsification, long-term storage stability, and adjusting to a suitable viscosity, as well as from the viewpoint of providing a good moisturizing feel when applied to the skin. The silicone chain may be linear, branched, or partially crosslinked. One or more of these can be used from the viewpoint of improving emulsification and long-term storage stability, maintaining excellent moisture-clotting properties, and providing a good feel without stickiness or discomfort.

[0023] Examples of commercially available (B) silicone-based surfactants include KF-6100 (Polyglyceryl-3 Disiloxane Dimethicone) (manufactured by Shin-Etsu Chemical Co., Ltd.), KF-6104 (Polyglyceryl-3 Polydimethylsiloxyethyl Dimethicone) (manufactured by Shin-Etsu Chemical Co., Ltd.), KF-6106 (Polyglyceryl-3 Polydimethylsiloxyethyl Dimethicone) (manufactured by Shin-Etsu Chemical Co., Ltd.), KF-6105 (Lauryl Polyglyceryl-3 Polydimethylsiloxyethyl Dimethicone) (manufactured by Shin-Etsu Chemical Co., Ltd.), KF-6011 (PEG-11 Methyl Ether Dimethicone) (manufactured by Shin-Etsu Chemical Co., Ltd.), and KF-6012 (PEG / PPG-20 / 22-butyl ether dimethicone) (manufactured by Shin-Etsu Chemical Co., Ltd.), KF-6015 (PEG-3 dimethicone) (manufactured by Shin-Etsu Chemical Co., Ltd.), KF-6017 (PEG-10 dimethicone) (manufactured by Shin-Etsu Chemical Co., Ltd.), KF-6028 (PEG-9 polydimethylsiloxyethyl dimethicone) (manufactured by Shin-Etsu Chemical Co., Ltd.), KF-6038 (lauryl PEG-9 polydimethylsiloxyethyl dimethicone) (manufactured by Shin-Etsu Chemical Co., Ltd.), KF-6043 (PEG-10 dimethicone) (manufactured by Shin-Etsu Chemical Co., Ltd.), KSG-210 ((dimethicone / (PEG-10 / 15)) crosspolymer / dimethicone mixture) (manufactured by Shin-Etsu Chemical Co., Ltd.), DOWSIL BY11-030 (PEG / PPG-19 / 19 Dimethicone / Cyclopentasiloxane mixture) (manufactured by Toray Dow Corning), DOWSIL BY25-337 (PEG / PPG-19 / 19 Dimethicone / Light Liquid Isoparaffin mixture) (manufactured by Toray Dow Corning), DOWSIL SH 3775 M Fluid (PEG-12 Dimethicone) (manufactured by Toray Dow Corning), DOWSIL FZ-2233 (Polysilicone 13) (manufactured by Toray Dow Corning), DOWSIL ES-5300 Formulation Aid (Lauryl PEG-10 Tris(trimethylsiloxy)silylethyl dimethicone) (manufactured by Toray Dow Corning), DOWSIL ES-5600 Silicone Glycerol Emulsifier (Cetyl diglyceryl Examples include polyether-modified silicones such as Tris(trimethylsiloxy)silylethyldimethicone (manufactured by Toray Dow Corning).

[0024] The content of (B) silicone-based surfactant in the emulsified sunscreen composition of the present invention is not particularly limited, but is preferably 0.5 to 10.0% by mass, more preferably 1.0 to 8.0% by mass, and even more preferably 2.0 to 6.0% by mass. This range is preferable in terms of the stability of the emulsified sunscreen composition, the effect of preventing drying, and a good feel during use.

[0025] The content ratio of (A-1) and (B) in the emulsified sunscreen composition of the present invention is not particularly limited, but it is preferable that (A-1) / (B) be contained in a mass ratio of (A-1) / (B) = 0.05 to 5. Within this range, stability and a good feel of the emulsified sunscreen composition can be obtained. Furthermore, it is preferable to obtain excellent makeup retention and a secondary adhesion prevention effect.

[0026] In the present invention, component (C) UV protection agent corresponds to (C-1) UV scattering agent or (C-2) UV absorbing agent, and it is acceptable to use one of these alone or to combine two or more of them.

[0027] The component (C-1) ultraviolet scattering agent in this invention is not particularly limited, and those commonly used in cosmetics can be used, but hydrophobized metal oxides are preferably used. Hydrophobized metal oxides are metal oxides whose surface has been hydrophobized. The type of metal oxide is not particularly limited as long as it is within the range commonly used in cosmetics, but fine particle metal oxides such as titanium dioxide, zinc oxide, zirconium oxide, and cerium oxide are particularly preferred. Among these, zinc oxide and titanium dioxide are powders that block ultraviolet rays, and their shape is not particularly limited, but if a high sunscreen effect is desired, fine particles with an average particle size of 10 to 100 nm are preferable. The particle size or average particle size of the powder particles shall be the value provided by the raw material manufacturer. Alternatively, it may be calculated by measuring with a laser diffraction / scattering particle size distribution analyzer (e.g., LA-920, manufactured by Horiba, Ltd.) using ethanol as the dispersion medium. In this case, the average particle size refers to the 50% diameter obtained from the volume distribution of the particle size distribution.

[0028] In the present invention, hydrophobic treatment means treating the surface of the raw inorganic powder with a hydrophobic organic surface treatment agent. The hydrophobic treatment agent can be any agent commonly used in cosmetics, such as silicones, alkylsilanes, metal soaps, fatty acids, phospholipids, fluorine compounds, silylation agents, and acyl amino acids. Silicone treatment and alkylsilane treatment are particularly preferred from the viewpoint of composition stability and usability. Examples of silicones used in silicone treatment include methicone, dimethicone, and hydrogen dimethicone, but the type of silicone is not particularly limited. Examples of alkylsilanes used in alkylsilane treatment include trialkoxyalkylsilanes such as trimethoxyhexylsilane, trimethoxycaprylylsilane, trimethoxydecylsilane, trimethoxyoctadecylsilane, triethoxyhexylsilane, triethoxycaprylylsilane, triethoxydecylsilane, and triethoxyoctadecylsilane, but the type is not particularly limited. In addition, inorganic compounds such as silica and alumina may be coated simultaneously with the hydrophobic treatment. In the present invention, component (C-1) is subjected to surface coating treatment using a hydrophobic treatment agent, thereby improving its dispersibility in the oil phase.

[0029] In the present invention, the component (C-2) UV absorber can be one that is commonly used in cosmetics, but an oil-soluble UV absorber is preferably used.

[0030] Examples of oil-soluble UV absorbers include 2-ethylhexyl paramethoxycinnamate, diethylaminohydroxybenzoyl hexyl benzoate, 2,4-bis-[{4-(2-ethylhexyloxy)-2-hydroxy)-phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine, octocrylene, 2,4,6-tris[4-(2-ethylhexyloxycarbonyl)anilino]-1,3,5-triazine, glyceryl mono-2-ethylhexanoate diparamethoxycinnamate, and 2,5-diisopropyl methyl methyl methyl methyl cinnamate. Methyl cinnamate, isopropyl paramethoxycinnamate / diisopropyl cinnamic acid ester mixture, diethanolamine p-methoxyhydrocinnamate, amyl paradimethylaminobenzoate, 2-ethylhexyl paradimethylaminobenzoate, paraaminobenzoic acid, ethyldihydroxypropyl paraaminobenzoic acid, glyceryl paraaminobenzoic acid, octyldimethyl paraaminobenzoic acid, homomenthyl salicylate, 2-ethylhexyl salicylate, triethanolamine salicylate, dihydroxydimethoxybenzoate Pheno-, dihydroxydimethoxybenzophenone disulfonate sodium, 2,2'-4,4'-tetrahydroxybenzophenone, 4,4'-dihydroxybenzophenone, 4-tert-butyl-4'-methoxydibenzoylmethane, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfate, 2,2'-dihydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2- Examples include hydroxy-4-n-octyloxybenzophenone, 2-phenyl-benzimidazole-5-sulfate, 4-isopropyldibenzoylmethane, 2-ethylhexyl dimethoxybenzylidene dioxoimidazolidinepropionate, 1-(3,4-dimethoxyphenyl)-4,4-dimethyl-1,3-pentanedione, cinoxate, methyl-O-aminobenzoate, 3-(4-methylbenzylidene)camphor, octyltriazone, and methylenebisbenzotriazolyltetramethylbutylphenol. One or more of these can be used.

[0031] Examples of water-soluble UV absorbers that can be used include phenylbenzimidazole sulfonate, hydroxymethoxybenzophenone sulfonate, 4-(2-β-glucopyranosiloxy)propoxy-2-hydroxybenzophenone, phenylene-1,4-bis(2-benzimidazyl)-3,3'-5,5'-tetrasulfonate bis-sodium salt, and terephthalylidene dicamphor sulfonic acid.

[0032] The amount of component (C) used varies depending on the desired UV protection effect, but is not particularly limited as long as the effects of the present invention are obtained. However, it is usually used in an amount of 40% by mass or less, preferably 0.5 to 30% by mass, relative to the total amount of the emulsified sunscreen composition. Within this range, the stability over time and the feel of use are excellent.

[0033] The emulsified sunscreen composition of the present invention may contain as appropriate any components as needed. For example, it may contain solid or semi-solid oils, liquid oils, alcohols, water, water-based gelling agents and thickeners, powders other than component (C), preservatives, etc.

[0034] Examples of solid oils and semi-solid oils include natural animal and vegetable oils, hydrocarbon oils, silicone oils, higher alcohols, higher fatty acids, and ester oils. Examples of solid or semi-solid oils include plant-based oils such as carnauba wax, candelilla wax, hydrogenated oil, and shea butter; hydrocarbons such as ceresin, paraffin wax, microcrystalline wax, petrolatum, polyethylene wax, and Fischer-Tropsch wax; silicones such as stearyl dimethicone and alkyl (C30-45) methicone; higher alcohols such as behenyl alcohol, cetyl alcohol, stearyl alcohol, cholesterol, and phytosterols; higher fatty acids such as stearic acid and behenic acid; and ester-based oils such as dimer dilinoleic acid (phytosteryl / isostearyl / cetyl / stearyl / behenyl), lauroyl glutamate di(phytosteryl / octyldodecyl), and tetra(hydroxystearic acid / isostearic acid) dipentaerythrityl. These can be used individually or in combination of two or more as needed.

[0035] As for surfactants, there are no particular restrictions as long as they are commonly used in cosmetics, and any surfactant other than (B) silicone-based surfactants can be used. Examples of surfactants include anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants. These can be used individually or in combination of two or more as needed.

[0036] Examples of water-soluble thickeners include natural polymers such as agar, plant-derived polymers such as locust bean gum, microbial polymers such as xanthan gum and gellan gum, and cellulosic polymers such as hydroxypropyl methylcellulose and hydroxypropyl methylcellulose stearoxy ether; synthetic polymers such as vinyl polymers such as carboxyvinyl polymer and alkyl-modified carboxyvinyl polymer, polyoxyethylene polymers, acrylic polymers such as acrylic acid / acryloyldimethyltaurate sodium copolymer, sodium polyacrylate, polyethyl acrylate, and polyacrylamide, and water-soluble urethane polymers such as (PEG-240 / decyltetradeceth-20 / HDI) copolymer; and inorganic thickeners such as bentonite, synthetic hectorite, and anhydrous silicic acid. These can be used individually or in combination of two or more as needed.

[0037] Examples of oily gelling agents include dextrin fatty acid esters such as dextrin palmitate and dextrin 2-ethylhexanoate palmitate, amino acid derivatives such as dibutyl lauroyl glutamide, sucrose fatty acid esters such as sucrose stearate, and organically modified clay minerals such as disteardimonium hectorite. These can be used individually or in combination of two or more as needed.

[0038] Examples of preservatives include phenoxyethanol, parahydroxybenzoic acid esters, sodium benzoate, salicylic acid, and iodide propynyl butylcarbamate. Examples of antioxidants include tocopherol and dibutylhydroxytoluene, pH adjusters include lactic acid, citric acid, citrate, sodium bicarbonate, and L-arginine, and chelating agents include sodium edetate, sodium polyphosphate, and sodium metaphosphate. These can be used individually or in combination of two or more as needed.

[0039] Other powders besides component C include inorganic powders, organic powders, inorganic pigments, organic pigments, pearl pigments, natural pigments, etc., and any of them can be used regardless of their particle shape (spherical, needle-shaped, plate-shaped, etc.), particle size, particle structure (porous, non-porous, etc.), or crystalline structure (crystalline, amorphous). These can be used individually or in combination of two or more as needed.

[0040] The emulsified sunscreen composition of the present invention can take the form of a cream, gel, liquid, emulsion, or multilayer separation, and can also take the form of a mousse or spray using a propellant or compressed air. Furthermore, the emulsified sunscreen composition of the present invention can be suitably used in skincare cosmetics such as lotions and creams, makeup cosmetics such as foundations, concealers, BB creams, makeup bases, eye colors, cheek colors, eyebrow products, mascaras, and eyeliners, and sunscreen cosmetics. In particular, it is suitable for makeup cosmetics and sunscreen cosmetics because it does not leave a heavy feeling on the skin, has good staying power, and does not cause secondary adhesion.

[0041] In this invention, HLB is a numerical value that represents the hydrophilic-hydrophobic balance, which is commonly used in the field of surfactants, and commonly used calculation formulas, such as the Kawakami formula, can be used. This invention employs the following Kawakami formula.

number

[0042] The present technology will be described in more detail below with reference to examples and comparative examples. However, these examples do not limit the present invention in any way.

[0043] [Sunscreen effect] <“SPF” measurement method> For the substrate HELIOPLATE HD6 (manufactured by Helio Screen), the emulsified sunscreen composition shown in Table 1 was applied at a concentration of 1.3 mg / cm³. 2 The surface was coated evenly and dried at room temperature for 30 minutes. An SPF analyzer UV-2000S (manufactured by Labsphere) was used to measure the SPF at nine points on the coated surface, and the average SPF value was calculated.

[0044] "Method for evaluating the effect of improving SPF (Specialty Productivity Factor)" For evaluating the SPF value, a reference example without component (A) polyurethane-79 gel composition was used as the standard for SPF improvement, and the SPF relative to the standard was calculated using the following formula.

number

[0045] [Usability] "Sensory evaluation methods" For samples prepared one day prior to preparation, a panel of 20 cosmetic evaluation specialists evaluated "spreadability," "uniformity of the cosmetic film," "non-stickiness," and "moisturizing effect" on a 7-point scale according to the following evaluation criteria. Furthermore, the average score of all panel members was used to make a final judgment according to the following criteria. [Sensory evaluation criteria] (Evaluation result): (Score) Very good: 6 points Good: 5 points Fairly good: 4 points Average: 3 points Slightly poor: 2 points Defective: 1 point Very poor: 0 points [Sensory judgment criteria] (Average score): (Judgment) 5.0 or higher: ◎ 3.5 or higher but less than 5.0: ○ 1.5 or higher but less than 3.5: △ Less than 1.5: ×

[0046] [No makeup transfer] "Method for evaluating secondary adhesion to black paper" Ten minutes after applying the sample to the arm, a piece of black drawing paper was pressed against it, and the state of the sample adhering to the black drawing paper was evaluated. [Secondary adhesion evaluation criteria] ◎: 16-20 people were determined to have no or very little secondary adhesion. ○: 11-15 people were determined to have no or very little secondary adhesion. △: 6-10 people were determined to have no or very little secondary adhesion. ×: Determined that 0-5 people had no or very little secondary adhesion.

[0047] "Method for evaluating makeup longevity" Twenty cosmetic evaluation panel members evaluated the "condition of the sample 6 hours after application" on a 7-point scale according to the following evaluation criteria. The average score of all panel members was then used to make a final judgment according to the following criteria. [Criteria for evaluating makeup longevity] (Evaluation result): (Score) Very good: 6 points Good: 5 points Fairly good: 4 points Average: 3 points Slightly poor: 2 points Defective: 1 point Very poor: 0 points [Criteria for judging makeup longevity] (Average score): (Judgment) 5.0 or higher: ◎ 3.5 or higher but less than 5.0: ○ 1.5 or higher but less than 3.5: △ Less than 1.5: ×

[0048] [Stability] "Method for evaluating stability" 30g of the sample was placed in a transparent PET container (30ml) and left to stand in a 50°C incubator for one month. [Evaluation Criteria] No separation was observed. :〇 Separation was observed: ×

[0049] Reference examples, Examples 1-6, and Comparative Examples 1-6 (Water-in-oil type sunscreens) The water-in-oil type moisturizing creams shown in Table 1 were manufactured using the following manufacturing method. Each sample was evaluated using the evaluation method described above, and the results are also shown in Table 1. [Manufacturing method] (1): Heat components 1-7 and 10-16 until uniformly mixed and dissolved. (2): Add components 8, 9, and 17-16 to (1) and mix and dissolve uniformly. (3) Heat and dissolve components 20-25 uniformly. (4): Add (3) to (2) and emulsify. (5): Process (4) in a homomixer. (6):(5) was defoamed to obtain a water-in-oil sunscreen composition.

[0050] [Table 1] *1 OILKEMIA 5S CC (contains 30% polyurethane-79: manufactured by Lubrizol) *2 Leopard KL2 (manufactured by Chiba Flour Milling Co., Ltd.) *3 KSP-100 (manufactured by Shin-Etsu Chemical Co., Ltd.) *4 Adekanol GT-700 (manufactured by Adeka) *5 KF-6105 (manufactured by Shin-Etsu Chemical Co., Ltd.) Low HLB *6 KF-6028 (manufactured by Shin-Etsu Chemical Co., Ltd.) HLB 4.0 *7 MZX-304OTS (manufactured by Teika Co., Ltd.) *8 MT-100TV (manufactured by Teika Co., Ltd.) *9 NIKKOL DGMIS (manufactured by Nikko Chemicals Co., Ltd.) HLB 5.5 *10 SY Glister CRS-75 (manufactured by Sakamoto Pharmaceutical Co., Ltd.) HLB3.3 *11 KSG-16 (manufactured by Shin-Etsu Chemical Co., Ltd.) *12 Godball SF-16C (manufactured by Suzuki Oil & Fat Industry Co., Ltd.)

[0051] Compared to the reference example water-in-oil sunscreen composition without the polyurethane-79 gel composition, the water-in-oil sunscreen compositions of Examples 1-6 showed enhanced UV protection by incorporating the polyurethane-79 gel composition. Furthermore, these water-in-oil sunscreen compositions had good spreadability, a uniform application film, and a moisturizing feel without stickiness, resulting in a good user experience and good stability. In contrast, the reference example did not yield good results regarding "uniformity of the application film," nor did it yield good results regarding "non-transferability" or "makeup longevity." Moreover, separation was observed at "50°C for 1 month." In Comparative Example 1, the polyurethane-79 gel composition was replaced with dextrin palmitate, a typical oily gelling agent, but good results were not obtained regarding "spreadability" or "uniformity of the application film." Furthermore, it was inferior to the polyurethane-79 gel composition in terms of "non-transferability." In Comparative Example 2, the polyurethane-79 gel composition was replaced with a spherical silicone resin. It was expected that the UV protection effect would be enhanced by diffuse reflection of light, but no enhancement of sunscreen effect was obtained. Furthermore, good results were not obtained for "uniformity of the coated film," nor for "no transfer of makeup." In Comparative Example 3, the polyurethane-79 gel composition was replaced with (PEG-240 / decyltetradeceth-20 / HDI) copolymer, which is the same polyurethane copolymer. Since (PEG-240 / decyltetradeceth-20 / HDI) copolymer is a water-soluble polyurethane, even when heated with an oil, it did not dissolve well and a uniform composition could not be obtained, making evaluation impossible. Therefore, the composition was obtained by heating and dissolving it in 1,3-butylene glycol in the aqueous phase and adding it to the aqueous phase, and evaluation was performed. Separation was observed after "50°C for 1 month," and no improvement in stability was seen, nor were good results obtained for "no transfer of makeup." In Comparative Example 4, the polyurethane-79 gel composition was replaced with ceresin, which has a high thickening effect in the oil phase. However, no improvement in SPF effectiveness was achieved. Furthermore, no favorable results were obtained regarding the absence of makeup transfer. Comparative Example 5 did not contain silicone-based surfactants and increased the amount of polyglycerin-based surfactants, but this resulted in worsening of spreadability and increased stickiness, and separation was observed at 50°C. Comparative Example 6 did not contain any UV protection agents.Therefore, it did not provide any sun protection.

[0052] Formulation Example 1: Sunscreen Gel (Oil-in-Water Sunscreen Composition) Ingredients (mass%) 1: Polyurethane-79 Caprylic / Capric Triglyceride *1 3% 2: Ethylhexyl Methoxycinnamate 8% 3: Diethylaminohydroxybenzoyl hexyl benzoate 2% 4: Octocrylene 2% 5: Behenyl alcohol 1% 6: PEG / PPG / Polybutylene Glycol-8 / 5 / 3 Glycerin 0.5% 7: Glyceryl (ethylhexanoate / stearic acid / adipate) *13 1.5% 8: PEG-10 Dimethicone *14 2% 9: Diphenylsiloxy Phenylen Trimethicone 3% 10:PEG-9 Polydimethylsiloxyethyl Dimethicone *6 1% 11: Silica *15 2% 12: Particulate Zinc Oxide / Triethoxycaprylylsilane *7 5% 13: Purified water (appropriate amount) 14: (Acryloyldimethyltaurate Ammonium / VP) Copolymer 0.3% 15: Cetyl Phosphate K 0.5% 16: Dipropylene glycol 1% 17:1,3-Butylene Glycol 5% 18: Dipotassium glycyrrhizinate 0.1% 19: Acrylates Copolymer *16 5% 20: Ethanol 10% 21: Phenoxyethanol 0.5% 22: Potassium hydroxide 0.05% 23: Nicotinamide 5% 24: Arbutin 2% 25: Betaine 0.5% 26: Polyquaternium-51 0.2% 27: Sodium hyaluronate 0.05% Total 100% *13 Nomucoat LAH (manufactured by Nisshin Oillio Group Co., Ltd.) *14 KF-6043 (manufactured by Shin-Etsu Chemical Co., Ltd.) HLB 14.5 *15 Sunsphere NP-100 (manufactured by AGC SI-TEC) *16 ACULYN 33A, 28% pure content (manufactured by Toray Dow Corning) (Manufacturing method) (1): Mix ingredients 1 to 12 and heat until dissolved. (2): Mix ingredients 13-27 and heat until dissolved. (3): Add (2) to (1) and emulsify. (4): Process in a homomixer. (5):(4) was cooled and degassed to obtain an oil-in-water type sunscreen composition.

[0053] Formulation Example 1 had a high UV protection effect with an SPF of 48 measured by the SPF analyzer UV-2000S, and was a composition with good usability, exhibiting excellent "spreadability," "uniformity of application film," "stickiness," and "moisturizing feel." Furthermore, it was a sunscreen composition with good "makeup longevity," maintaining a clean application even with sweat and sebum, and having a "secondary adhesion prevention effect" that made it resistant to rubbing against clothing, resulting in a high "sunscreen effect." In addition, a stability test was conducted at 50°C for 1 month, and it was confirmed that there was no separation.

[0054] Formulation Example 2: Liquid Foundation (Water-in-Oil Composition) Ingredients (mass%) 1: Polyurethane-79 Caprylic / Capric Triglyceride *1 10% 2: Lauryl PEG-9 Polydimethylsiloxyethyl Dimethicone *17 0.6% 3: Fine particle zinc oxide / decamethylcyclopentasiloxane dispersion (60% pure hydrogen dimethicone-treated zinc oxide) *18 10% 4: Fine particle titanium dioxide / decamethylcyclopentasiloxane dispersion (40% pure isostearic acid-treated titanium dioxide) *19 15% 5: Hydrophobized iron oxide 2% 6: Hydrophobized titanium dioxide (pigment grade) 4% 7: Hydrophobized zinc oxide (pigment grade) 3% 8: Sorbitan sesquioleate 2% 9: Triethylhexanoin 3% 10: Cetyl ethylhexanoate 7% 11: Isotridecyl isononanoate 2% 12: Stearyl glycyrrhetinate 0.05% 13: Polymethylsilsesquioxane (powder) 3% 14: Talc 4% 15: Trifluoroalkyldimethyltrimethylsiloxysilicate / Dimethicone 1% 16: Decamethylcyclopentasiloxane 8% 17: Purified water (appropriate amount) 18:1,3-Butylene Glycol 10% 19: Hydroxypropyl methylcellulose stearoxy ether 0.02% 20: Sodium acetylated hyaluronate 0.05% 21: Glycerin 3% 22: Sodium Chloride 0.5% 23: Sodium metaphosphate 0.01% 24: Hydroxypropyl methylcellulose stearoxy ether 0.05% 25: Ethylhexylglycerin 0.5% 26: Propynyl iodide butylcarbamate 0.01% Total 100% *17 KF-6038 (manufactured by Shin-Etsu Chemical Co., Ltd.) HLB3.0 *18 LZ-014 (manufactured by Teika Co., Ltd.) *19 LT-053 (manufactured by Teika Co., Ltd.) (Manufacturing method) (1): Components 1 to 12 are heated and mixed, then dispersed using a roll mill. (2): Add ingredients 13-16 to (1) and mix until uniform. (3) Mix ingredients 17-26 and heat until dissolved. (4): Process (2) in a homomixer. (5): Add (3) to (4) and emulsify. (6): Process (5) in a homomixer. (7): The foam was removed to obtain a water-in-oil foundation.

[0055] Regarding Formulation Example 2, the SPF Analyzer UV-2000S measured an SPF of 41, indicating a high level of UV protection. The composition exhibited good usability, with excellent spreadability, uniformity of the applied film, low stickiness, and moisturizing properties. Furthermore, it provided good makeup longevity, remaining clean and even with sweat and sebum. It also had a high sun protection effect, being resistant to friction from clothing due to its anti-secondary adhesion properties. In addition, a stability test was conducted at 50°C for one month, confirming that there were no problems.

Claims

1. The following components (A) to (C) (A) Polyurethane-79 gelling composition comprising (A-1) Polyurethane-79 and (A-2) liquid oil (B) Silicone-based surfactants (C) UV protection agent An emulsified sunscreen composition containing the following:

2. The emulsified sunscreen composition according to claim 1, wherein the (C) ultraviolet protection agent is a hydrophobized fine particle metal oxide.

3. The emulsified sunscreen composition according to claim 1, wherein the (B) silicone-based surfactant is a polyglycerin-modified silicone.

4. The emulsified sunscreen composition according to any one of claims 1 to 3, wherein the content ratio of (A-1) to (B) is (A-1) / (B) = 0.05 to 5 by mass.

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