Water-based sunscreen cosmetic and sheet-type water-based sunscreen cosmetic

Abstract

To provide aqueous sunscreen cosmetics that suppress squeakiness due to UV scattering agents, offer a moist feel while leaving no squeakiness on the skin, and remain non-sticky and easily washable even with repeated applications.SOLUTION: Aqueous sunscreen cosmetics include (A) UV scattering agent of 5-20%, (B) water-soluble polymer of 0.001-1%, (C) spherical powder of polymethyl methacrylate or methyl methacrylate crosspolymer of 0.1-5%, and (D) alkylene oxide derivative of the following formula (1) of 0.1-10%. (In the formula (1), AO denotes a C3-4 oxyalkylene group, EO denotes an oxyethylene group, "a" denotes the molar addition number of AO, "b" denotes the molar addition number of EO, "a" denotes a number selected from 0 to 50, "b" denotes a number selected from 1 to 50, a+b≥10, and 0≤a / b≤2).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an aqueous sunscreen cosmetic and a sheet-type aqueous sunscreen cosmetic. [Background technology]

[0002] With growing awareness of UV protection, an increasing number of people are using sunscreen cosmetics on a daily basis. In this context, there is growing demand for water-based sunscreen cosmetics, which offer a comfortable feel and high usability that can be used daily without stress.

[0003] Water-based suntan cosmetics are characterized by a refreshing feeling when used due to the large amount of water they contain. However, after the water evaporates after application, the UV scattering agent, which acts as a UV protection agent, can easily cause a dry, squeaky feeling, which can make the skin feel dry and less moist.

[0004] Patent Document 1 reports an oil-in-water type external skin preparation that contains a specific polyglycerin derivative, hydrophobized powder, etc., and has a moist feeling and is not sticky.

[0005] Patent Document 2 reports an oil-in-water emulsion composition that contains a specific polyoxyethylene alkyl ether, liquid oil, and hydrophobically treated fine particle metal oxide powder, and that has a moisturizing feel and is not squeaky. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Laid-Open No. 2007-31337 [Patent Document 2] Japanese Patent Application Laid-Open No. 2014-114274 Summary of the Invention [Problem to be solved by the invention]

[0007] Patent Document 1 reports an oil-in-water topical skin preparation that is moisturizing and non-sticky. However, the oil-in-water topical skin preparation described in Patent Document 1 does not sufficiently improve the squeaky feeling of UV scattering agents. Patent Document 2 reports an oil-in-water emulsion composition that is moisturizing and non-squeaky. However, when the oil-in-water emulsion composition described in Patent Document 2 is designed to increase the moist feeling while suppressing the squeaky feeling, reapplication to maintain the effect causes stickiness and reduced cleansing properties.

[0008] Therefore, there is a demand for a water-based sunscreen cosmetic that is not rough, has a moist feeling, is not sticky even when applied in layers, and is easy to wash off.

[0009] Recently, sunscreen cosmetic formulations have become more diverse, allowing consumers to select the appropriate formulation based on their intended use and purpose. Among these, sheet-type sunscreen cosmetic formulations, in which sunscreen cosmetic formulations are impregnated into sheets, are recognized as sunscreens for everyday use due to their ease of portability and application. However, when attempting to impregnate a sheet with a sunscreen containing an ultraviolet scattering agent, polymers and the like incorporated to improve the dispersibility of the ultraviolet scattering agent can inhibit the ease of penetration and spread of the sunscreen onto the sheet. Furthermore, powders and the like incorporated to reduce the squeaky feeling can cause the sheet to fluff upon application, reducing usability. Therefore, when impregnating a sheet with a sunscreen cosmetic formulation, there is a demand for a sheet that is easy to penetrate and spread onto the sheet and that is less likely to fluff during use.

[0010] The present invention aims to provide an aqueous sunscreen cosmetic composition that suppresses the squeaky feeling caused by an ultraviolet scattering agent, provides a moist feeling without leaving a squeaky feeling on the skin, is non-sticky even when reapplied, and is easy to wash off even after reapplication. Additionally, the present invention aims to provide an aqueous sunscreen cosmetic composition in sheet form that easily penetrates and spreads throughout the sheet when applied to a sheet, and is suppressed from fuzzing during use of the sheet. [Means for solving the problem]

[0011] As a result of intensive research conducted in light of the above-mentioned problems, the present inventors have discovered that an aqueous sunscreen cosmetic that can solve the above-mentioned problems can be obtained by combining an ultraviolet scattering agent, a water-soluble polymer, a spherical powder of polymethyl methacrylate or methyl methacrylate crosspolymer, and an alkylene oxide derivative having a specific structure in specified blending amounts, and have thus completed the present invention.

[0012] That is, the present invention provides an aqueous sunscreen cosmetic composition having the following characteristics:

[0013] <1> An aqueous sunscreen cosmetic comprising (A) 5 to 20% of an ultraviolet scattering agent, component (B) 0.001 to 1% of a water-soluble polymer derived from cellulose or polysaccharide, component (C) 0.1 to 5% of a spherical powder of polymethyl methacrylate or methyl methacrylate crosspolymer, and (D) 0.1 to 10% of an alkylene oxide derivative represented by the following formula (1):

[0014] [ka]

[0015] In formula (1), AO represents an oxyalkylene group having 3 to 4 carbon atoms, EO represents an oxyethylene group, a represents the number of moles of the oxyalkylene group having 3 to 4 carbon atoms added, b represents the number of moles of the oxyethylene group EO added, a represents a number from 0 to 50, b represents a number from 1 to 50, and a+b≧10. The oxyalkylene groups having 3 to 4 carbon atoms and the oxyethylene groups are added in a random or block manner, and in the case of block addition, the order of arrangement does not matter and 0≦a / b≦2.

[0016] <2> (E) A (meth)acrylic copolymer containing a structural unit represented by the following formula (I) and a structural unit represented by the following formula (II), in which the molar ratio (I / II) of the two structural units is 90 / 10 to 30 / 70.

[0017] [ka]

[0018] In formula (I), R 1 represents a hydrogen atom or a methyl group, and R 2 Ha-(CH2) n represents -, and n is an integer of 1 to 4. * represents a bonding site to another structural unit.

[0019] [ka]

[0020] In formula (II), R 3 represents a hydrogen atom or a methyl group, and L 1 represents a divalent linking group selected from the group consisting of a phenylene group, a cyclohexylene group, -C(=O)-O-, -O-, -C(=O)-NH-, -OC(=O)-, and -OC(=O)-O-; L 2 represents a linear or branched alkyl group having 10 to 22 carbon atoms. * represents a bonding site with other structural units.

[0021] Contains 0.001 to 1% of <1> The aqueous sunscreen cosmetic composition according to claim 1.

[0022] <3> <1> or <2> 1. A sheet-like water-based sunscreen cosmetic, comprising a sheet base impregnated with the water-based sunscreen cosmetic according to claim 1. [Effects of the Invention]

[0023] The present invention can provide an aqueous sunscreen cosmetic composition that is free from a squeaky feeling, has a moist feeling, is not sticky even when reapplied, and is easily washable even after reapplication.In addition, it can provide a sheet-type aqueous sunscreen cosmetic composition that easily soaks into and spreads throughout the sheet when applied to a sheet, and is suppressed from pilling during sheet use. DETAILED DESCRIPTION OF THE INVENTION

[0024] (A) UV scattering agent Component (A) is an ultraviolet scattering agent. An ultraviolet scattering agent refers to a substance that can reflect and scatter ultraviolet rays to protect the skin and the like from ultraviolet rays. Examples of materials for the ultraviolet scattering agent of component (A) include titanium oxide, zinc oxide, iron oxide, zirconium oxide, and aluminum oxide. Examples of ultraviolet scattering agents include those obtained by microparticulating these materials or by compounding them. The ultraviolet scattering agent preferably contains one or two types selected from titanium oxide and zinc oxide.

[0025] The titanium oxide and zinc oxide used as the UV scattering agent may be titanium oxide and zinc oxide that are commonly used in cosmetics. Preferably, titanium oxide and zinc oxide with better dispersibility, for example, titanium oxide and zinc oxide that have been surface-treated, specifically hydrophobized, by a known method as needed, can be contained in the skin composition.

[0026] Examples of surface treatment methods include silicone treatment with methylhydrogenpolysiloxane, methylpolysiloxane, or the like; fluorine treatment with perfluoroalkyl phosphate ester, perfluoroalcohol, or the like; amino acid treatment with N-acylglutamic acid, or the like; alkylalkoxysilane treatment with octyltriethoxysilane, octyltrimethoxysilane, or the like; lecithin treatment; silica treatment; metal soap treatment; fatty acid treatment; and alkyl phosphate ester treatment.

[0027] Component (A) is preferably microparticulated to an average primary particle diameter of 8 to 80 nm, more preferably 10 to 50 nm. The average primary particle diameter can be measured by observing with a transmission electron microscope (TEM), measuring the diameters of any 20 primary particles, and calculating the average value.

[0028] The concentration of the UV scattering agent (A) added is 5 to 20% by mass, preferably 5 to 18% by mass, and more preferably 5 to 15% by mass, relative to the total mass of the aqueous sunscreen cosmetic. By increasing the content of component (A), the UV protection effect can be sufficiently enhanced. By not including an excessive amount of component (A), the squeaky feeling and stickiness after multiple applications can be reduced, and a decrease in cleanability after multiple applications and fluffing of the sheet can be suppressed.

[0029] (B) Water-soluble polymer Component (B) is a water-soluble polymer derived from cellulose or polysaccharides. The cellulose- or polysaccharide-derived water-soluble polymer of component (B) may be a natural water-soluble polymer, a semi-synthetic water-soluble polymer, or any polymer that is typically incorporated into cosmetics.

[0030] Specific examples include water-soluble polymers derived from cellulose such as carboxymethyl cellulose and hydroxyethyl cellulose, and water-soluble polymers derived from polysaccharides such as gum arabic extract, tragacanth gum extract, guar gum, quince seed extract, agar, xanthan gum, fructan, pullulan, sodium hyaluronate, and sodium chondroitin sulfate.

[0031] The (B) cellulose- or polysaccharide-derived water-soluble polymers may be used alone or in combination of two or more. In the present invention, it is preferable to use a polysaccharide-derived water-soluble polymer from the viewpoints of reducing stickiness during reapplication and facilitating spreading of the polymer onto a sheet.

[0032] Among these, in the present invention, it is preferable to use one or more water-soluble polymers selected from gum arabic extract and quince seed (marmelo seed) extract. Commercially available water-soluble polymers derived from gum arabic extract include, for example, "Proteoglycan (Plant)" manufactured by NOF Corporation. Commercially available water-soluble polymers derived from quince seed (marmelo seed) extract include, for example, "Quince Seed G," "Quince Seed 2S," and "Quince Seed 2SP" manufactured by Dai Nippon Chemical Industry Co., Ltd.

[0033] The concentration of the water-soluble polymer (B) added is 0.001 to 1% by mass, preferably 0.003 to 1% by mass, and more preferably 0.005 to 1% by mass, relative to the total mass of the aqueous sunscreen cosmetic. By increasing the content of component (B), it is possible to reduce the squeaky feeling and improve the moist feeling. By not including an excessive amount of component (B), it is possible to reduce the sticky feeling after multiple applications and to prevent a decrease in cleanability after multiple applications and a decrease in the ease with which the product spreads onto the sheet.

[0034] (C) Spherical powder of polymethyl methacrylate or methyl methacrylate crosspolymer Component (C) is a polymethyl methacrylate powder or a methyl methacrylate crosspolymer spherical powder. The polymethyl methacrylate powder or methyl methacrylate crosspolymer spherical powder of component (C) can be any of those typically used in cosmetics, and one or more of these can be used. The crosslinking agent for the methyl methacrylate crosspolymer powder is not particularly limited, but examples thereof include ethylene glycol dimethacrylate. Furthermore, component (C) may be subjected to a surface treatment, a composite treatment, or may contain a powder or oil such as a colorant. Examples of the treatment agent include, but are not limited to, an oil, a fluorine compound, a powder, a colorant, a gelling agent, a synthetic polymer, a surfactant, and the like.

[0035] Commercially available products of component (C) include Matsumoto Microsphere M, Matsumoto Microsphere M-100, Matsumoto Microsphere M-101, Matsumoto Microsphere M-305, Matsumoto Microsphere M-306, Matsumoto Microsphere M-600, Matsumoto Microsphere MHB-R, Matsumoto Microsphere M-310, Matsumoto Microsphere M-311 (all manufactured by Matsumoto Yushi Pharmaceutical Co., Ltd.), Ganz Pearl GM-2800, Ganz Pearl GMI-0804 (all manufactured by Aica Kogyo Co., Ltd.), and the like.

[0036] The average particle size of component (C) is preferably 1 to 40 μm, and more preferably 5 to 20 μm. By setting the average particle size to 1 μm or more, it is possible to sufficiently reduce the squeaky feeling. By setting the average particle size to 40 μm or less, it is possible to prevent a decrease in moist feeling. The average particle size of the spherical powder can be measured as the volume average particle size (D50) using, for example, a laser scattering particle size distribution analyzer (manufactured by HORIBA Corporation).

[0037] The concentration of the spherical powder of (C) polymethyl methacrylate or methyl methacrylate crosspolymer added is 0.1 to 5%, preferably 0.1 to 3%, and more preferably 0.1 to 1%. Increasing the content of component (C) can reduce the squeaky feeling and stickiness after reapplication. Not increasing the content of component (C) can reduce the decrease in moist feeling, the decrease in cleanability after reapplication, and the occurrence of fluffing of the sheet.

[0038] (D) Alkylene oxide derivatives Component (D) is an alkylene oxide derivative represented by formula (1). [ka]

[0039] In formula (1), AO represents an oxyalkylene group having 3 to 4 carbon atoms, EO represents an oxyethylene group, a represents the number of moles of the oxyalkylene group having 3 to 4 carbon atoms added, b represents the number of moles of the oxyethylene group EO added, a represents a number from 0 to 50, b represents a number from 1 to 50, a+b≧10, and 0≦a / b≦2. The oxyalkylene group having 3 to 4 carbon atoms and the oxyethylene group are added in a random or block manner, and in the case of block addition, the order of arrangement is not important.

[0040] By setting a to 50 or less, it is possible to suppress the squeaking of the ultraviolet scattering agent and further improve the cleanability after recoating. Therefore, a is set to 0 to 50, preferably 0 to 40, and most preferably 0 to 30.

[0041] By making b 1 or more, the squeaky feeling is suppressed, the moist feeling is increased, and the washability after reapplication is improved. Also, by making b 50 or less, the sticky feeling after reapplication can be reduced. Therefore, b is set to 1 to 50, preferably 10 to 40, and most preferably 10 to 30.

[0042] By making a+b 10 or more, it is possible to suppress the squeaky feeling and improve the moist feeling. Therefore, a+b is set to 10 or more, and most preferably 20 or more. There is no particular upper limit for a+b, but it is preferably 50 or less.

[0043] When a is greater than 0, the oxyalkylene groups and oxyethylene groups having 3 to 4 carbon atoms are added randomly or in a block form. When added in a block form, the order of arrangement is not important.

[0044] By setting the ratio a / b to 2 or less, the squeaky feeling can be reduced, the moist feeling can be improved, and the fuzzing of the sheet can be suppressed. Therefore, the ratio a / b is set to 2 or less, and 1.2 or less is most preferable. The lower limit of the ratio a / b is 0, but it may be set to 0.3 or more.

[0045] Examples of the oxyalkylene group having 3 to 4 carbon atoms include an oxypropylene group and an oxybutylene group, with an oxypropylene group being the most preferred. The alkylene oxide derivative represented by formula (1) may have either an oxypropylene group or an oxybutylene group, or both. When both are present, the oxypropylene group and the oxybutylene group may be in either a random or block form. When added in a block form, the order of arrangement is not important.

[0046] Component (D) of the present invention has a monoether structure in which an alkylene oxide is added to the first hydroxyl group of the three hydroxyl groups of glycerin. The monoether purity is 80% or more, preferably 90% or more, and more preferably 95% or more. There is no particular upper limit to the monoether purity, but it can be 100% or less.

[0047] Monoether purity is 1 It can be calculated from the following formula using the peak integral value obtained by H-NMR measurement.

number

[0048] x represents the peak integral of approximately 2.4 ppm derived from the methylene groups at 1,3-positions of glycerin to which ethylene oxide has been added, when the peak integral of approximately 3.3 ppm derived from the methine group at 2-position of glycerin, which is detected only in the monoether form, is set to 1. However, if the peak integral of approximately 3.3 ppm derived from the methine group at 2-position of glycerin of the monoether form cannot be detected, the purity of the monoether form is set to 0.

[0049] The alkylene oxide derivative of the present invention represented by formula (1) can be produced by known methods. An alkylene oxide is addition-polymerized with an alkyl alcohol, for example, isopropylidene glycol in which all but the primary hydroxyl group of glycerin have been protected, in the presence of an alkali catalyst at 50 to 160°C and 0.5 MPa (gauge pressure) or less. When using two or more alkylene oxides, in the case of a random alkylene oxide, the two or more alkylene oxides are mixed together before addition polymerization. In the case of a block alkylene oxide, AO may be polymerized first, followed by EO, or EO may be polymerized first, followed by AO. Subsequently, an acid such as hydrochloric acid, phosphoric acid, or acetic acid is added to deacetalize the mixture. The excess acid is neutralized with a base such as potassium hydroxide or sodium hydroxide, and the water and neutralization salt are then removed to obtain the alkylene oxide derivative.

[0050] The concentration of component (D) used in the present invention is preferably 0.1 to 10%, more preferably 0.5 to 8%, and particularly preferably 1 to 5%. Increasing the content of component (D) can reduce squeaky sensation, prevent a decrease in cleanability after recoating, and make the sheet less likely to fluff. Not increasing the content of component (D) excessively can make it less likely to reduce stickiness after recoating.

[0051] (E) (Meth)acrylic copolymer The component (E) is a (meth)acrylic copolymer containing a structural unit represented by the following formula (I) and a structural unit represented by the following formula (II).

[0052] [ka]

[0053] In formula (I), R 1 R represents a hydrogen atom or a methyl group, and a methyl group is preferred from the viewpoint of the stability of the copolymer. 2 Ha-(CH2) n represents -, and n is an integer of 1 to 4. That is, R2 is any of -(CH2)-, -(CH2)2-, -(CH2)3-, and -(CH2)4-, with -(CH2)2- being preferred in terms of ease of availability and synthesis.

[0054] Specific examples of the monomer that forms the structural unit of formula (I) include glycerol-1-methacryloyloxyethylene urethane, glycerol-1-methacryloyloxypropylene urethane, etc. Glycerol-1-methacryloyloxyethylene urethane is preferred because of its availability and ease of synthesis.

[0055] The monomer forming the structural unit of formula (I) can be synthesized by a known method. For example, it can be synthesized by the method described in JP 2007-119374 A or a method equivalent thereto. Specific examples of the synthesis method include a method in which a compound obtained by a urethanization reaction between a cyclic acetal and a (meth)acryloyloxyalkylene isocyanate is subjected to a hydrolysis ring-opening reaction in a water-containing solvent in the presence of a urethanization catalyst.

[0056] [ka]

[0057] In formula (II), R 3 represents a hydrogen atom or a methyl group, and from the viewpoint of the stability of the copolymer, a methyl group is preferred. 1 represents phenylene, cyclohexylene, -C(=O)-O-, -O-, -C(=O)-NH-, -OC(=O)-, or -OC(=O)-O-, and among these, -O- is preferred. 2 represents a linear or branched alkyl group having 10 to 22 carbon atoms, preferably 15 to 20 carbon atoms, and examples thereof include a hexadecyl group, a heptadecyl group, and a stearyl group.

[0058] Specific examples of the monomer that forms the structural unit of formula (II) include hexadecyl (meth)acrylate, heptadecyl (meth)acrylate, and stearyl (meth)acrylate, and among these, stearyl (meth)acrylate is preferred.

[0059] The molar ratio (I / II) of the structural units of formula (I) to the structural units of formula (II) in component (E) is 90 / 10 to 30 / 70. By reducing the proportion of the structural units of formula (I) below this range, the sticky feeling after reapplication of the aqueous sunscreen cosmetic can be reduced and pilling of the sheet-type sunscreen cosmetic can be suppressed. By reducing the proportion of the structural units of formula (II) below this range, the solubility of component (E) in water can be improved, making it easier to impregnate the sheet. From these points of view, the molar ratio (I / II) is preferably 80 / 20 to 40 / 60, and more preferably 70 / 30 to 50 / 50.

[0060] The (meth)acrylic copolymer of component (E) can contain other structural units in addition to the structural units of formula (I) and formula (II). Examples of monomers that form such other structural units include isobornyl methacrylate and ethyl methacrylate trimethylammonium chloride. The content of other structural units in the (meth)acrylic copolymer of component (E) is preferably 10 mol% or less, more preferably 0 mol% or more and 10 mol% or less, based on the total amount of the structural units of formula (I) and formula (II). When the copolymer contains other structural units in addition to the structural units of formula (I) and formula (II), the content is preferably more than 0 mol% and 10 mol% or less.

[0061] The (meth)acrylic copolymer of component (E) may be a random copolymer or a block copolymer, but is preferably a random copolymer.

[0062] The weight-average molecular weight (Mw) of the copolymer of component (E) is preferably 5,000 to 500,000, more preferably 10,000 to 200,000, from the viewpoints of ease of spreading and blending into a sheet. To facilitate handling, component (E) can be diluted with a polyhydric alcohol such as glycerin or 1,3-butylene glycol when preparing the aqueous sunscreen cosmetic. These polyhydric alcohols may be included directly in the aqueous sunscreen cosmetic.

[0063] The weight-average molecular weight (Mw) of the copolymer is measured by gel permeation chromatography (GPC) (converted to polyethylene glycol). The weight-average molecular weight by GPC can be calculated by preparing a sample solution using a methanol / chloroform mixed solvent (6 / 4 (volume ratio)) containing 0.5% by mass of lithium bromide, and using a calibration curve of standard polyethylene glycol.

[0064] Component (E) can be prepared by polymerizing a monomer composition containing at least a monomer that forms the structural unit of formula (I) and a monomer that forms the structural unit of formula (II) by a known method. For example, it can be prepared by preparing a monomer composition that satisfies the molar ratio (I / II) of the structural units described above, and then conducting solution polymerization in an inert gas atmosphere such as nitrogen in the presence of a radical polymerization initiator.

[0065] Alternatively, instead of preparing component (E), a commercially available product may be used, such as "CERACUTE-L" manufactured by NOF Corporation.

[0066] This commercially available product (trade name "CERACUTE-L") is a product in which component (A) is diluted with glycerin and 1,3-butylene glycol, and contains component (E) which is glyceryl-N-(2-methacryloyloxyethyl)carbamate·stearyl methacrylate copolymer.

[0067] The content of component (E) in the aqueous sunscreen cosmetic of the present invention is 0.001 to 1% by mass, preferably 0.005 to 0.1% by mass, and more preferably 0.01 to 0.05% by mass. From the viewpoints of reducing the squeaky feeling of the aqueous sunscreen cosmetic, improving the moist feeling, and improving washability after reapplication, as well as suppressing pilling of the sheet-type sunscreen cosmetic, it is preferable that component (E) be in this range.

[0068] Furthermore, the aqueous sunscreen cosmetic of the present invention may contain additives used in cosmetics, quasi-drugs, pharmaceuticals, etc., as needed, as long as they do not impair the effects of the present invention. For example, natural fragrances and synthetic fragrances can be added to enhance palatability. Natural fragrances are essential oils obtained by steam distillation or other methods from the flowers, stems, leaves, fruits, peels, and roots of plants, and the separated water can also be used as aromatic perfumes. Synthetic fragrances include esters, ethers, aldehydes, ketones, aromatic alcohols, hydrocarbons, and the like, without any particular limitations. Examples of additives include glycols such as dipropylene glycol, 1,3-butylene glycol, and polyethylene glycol; glycerins such as diglycerin and polyglycerin; sugar alcohols such as sorbitol and maltitol; oils such as hydrocarbon oils, ester oils, silicone oils, and vegetable oils; lower alcohols such as ethanol and isopropanol; sugars such as lactose and sucrose; anionic surfactants such as acylmethyl taurine salts, alkyl ether sulfate ester salts, and amide ether sulfate ester salts; organic or inorganic salts such as citrate, malate, and salt; acids and alkalis used as pH adjusters; parabens; preservatives; extracts derived from plants and animals; vitamins; amino acids; colorings; pigments (excluding component (A)); and ultraviolet absorbers. If any of these components fall under components (B) to (E), those components are treated as components (B) to (E).

[0069] The aqueous sunscreen cosmetic of the present invention comprises the above-mentioned components dissolved or dispersed in water. Examples of water include purified water, tap water, industrial water, and deionized water. The water content in the present invention is typically 30 to 95% by mass, preferably 35 to 93% by mass, and more preferably 40 to 90% by mass, based on the total mass of the aqueous sunscreen cosmetic.

[0070] [Sheet-type sunscreen cosmetics] The aqueous sunscreen cosmetic of the present invention can also be suitably used as a sheet-type sunscreen cosmetic by impregnating it into a sheet substrate w. Recently, sheet-type sunscreen cosmetics in which a nonwoven fabric or the like is impregnated with the sunscreen cosmetic have been attracting attention because of their portability and their ease of application without staining the hands, even in areas that are difficult to apply, such as the ears and the nape of the neck.

[0071] In sheet-type sunscreen cosmetics, unless the entire sheet is sufficiently impregnated with a sunscreen cosmetic containing uniformly dispersed UV scattering agents, the UV protection effect cannot be fully achieved. However, polymers added to improve the dispersibility of the UV scattering agents can sometimes inhibit the ease with which the UV scattering agents spread across the sheet. Furthermore, the UV scattering agents and texture-improving powders added to reduce the squeaky feeling can easily cause the sheet to fluff during application, reducing usability.

[0072] The aqueous sunscreen cosmetic of the present invention has no squeaky feeling, gives a moist feeling, is less sticky even when applied in multiple layers, and is easy to wash off after multiple applications. In addition, it easily penetrates and spreads on an impregnated sheet, and can suppress pilling during application.

[0073] The sunscreen cosmetic of the present invention can be prepared as a sheet-type sunscreen cosmetic by impregnating a sheet substrate with the sunscreen cosmetic of the present invention. In other words, the sheet-type sunscreen cosmetic of the present invention comprises a sheet substrate and the aqueous sunscreen cosmetic of the present invention impregnated into the sheet substrate.

[0074] As the sheet substrate, cosmetic cotton or various other materials are used, for example, cotton, paper, nonwoven fabric, and woven fabric. The sheet substrate may be a laminate, for example, a woven fabric laminate, a nonwoven fabric laminate, or a woven and nonwoven fabric laminate. From the viewpoints of usability, ease of processing, etc., the sheet substrate is preferably a sheet containing nonwoven fabric, and more preferably a sheet prepared from nonwoven fabric.

[0075] Examples of nonwoven fabrics include spunbond nonwoven fabrics, spunlace nonwoven fabrics, thermal bond nonwoven fabrics, needle-punched nonwoven fabrics, stitch-bond nonwoven fabrics, etc. Examples of fibers that make up nonwoven fabrics and woven fabrics include natural fibers such as wood fibers, synthetic fibers such as acrylic, rayon, polyester, cellulose, and acetate, and semi-synthetic fibers such as Promix.

[0076] The basis weight of the sheet substrate is, for example, 20 to 100 g / m 2 and preferably 25 to 80 g / m 2 When the basis weight is within the above range, the sheet substrate does not curl when wiping the skin, providing an excellent feel when used. Furthermore, the amount of aqueous sunscreen cosmetic impregnated per unit area is increased. This ensures sufficient effectiveness even when applied over a wide area of ​​the skin, and further improves usability when used as a sheet-type sunscreen cosmetic for the body.

[0077] The sheet substrate can be produced by a known or conventional production method depending on the type of woven fabric, nonwoven fabric, etc. Alternatively, a commercially available product can be used as the sheet substrate.

[0078] In the sheet-form aqueous sunscreen cosmetic, the content of the aqueous sunscreen cosmetic of the present invention impregnated into the sheet substrate is not particularly limited, but is preferably 100 to 1000 parts by mass, more preferably 200 to 800 parts by mass, and even more preferably 200 to 500 parts by mass, per 100 parts by mass of the sheet substrate.

[0079] Examples of the planar shape of the sheet include polygonal shapes such as quadrilaterals (e.g., squares, rectangles, etc.) and triangles; circles, ellipses, semicircles; crescents; barrels; and drum shapes. The sheet may be formed with slits, cutouts, or irregularities. The surface area of ​​one side of the sheet is, for example, 100 to 3000 cm from the viewpoints of usability, portability, packability, etc. 2 and preferably 150 to 1000 cm 2 is.

[0080] The sheet-form sunscreen cosmetic can be produced by impregnating the above-mentioned sheet substrate with the aqueous sunscreen cosmetic of the present invention. Methods for impregnating the sheet substrate with the aqueous sunscreen cosmetic of the present invention include, for example, pouring the aqueous sunscreen cosmetic of the present invention into a folded sheet substrate to impregnate it, spraying the aqueous sunscreen cosmetic of the present invention onto the sheet substrate, impregnating the sheet substrate with the aqueous sunscreen cosmetic of the present invention using a printing method, and immersing the sheet substrate in a solution containing the aqueous sunscreen cosmetic of the present invention.

[0081] In addition, after impregnation into the sheet-type sunscreen cosmetic, a portion of the aqueous sunscreen cosmetic may have volatilized, etc. In this case, too, the composition ratio of the components other than the volatilized liquid components is the same as the composition ratio in the aqueous sunscreen cosmetic. [Example]

[0082] <Synthesis Example 1: Example Compound D-1> 100 g of isopropylidene glycol and 0.5 g of potassium tert-butoxide as a catalyst were charged into an autoclave, and the air in the autoclave was replaced with dry nitrogen. The catalyst was then dissolved at 130°C with stirring. Subsequently, 866 g of ethylene oxide was added dropwise at 130°C and 0.2 to 0.5 MPa (gauge pressure) using a dropping device, and the mixture was stirred for 1 hour. The reaction mixture was then removed from the autoclave, adjusted to pH 3 with hydrochloric acid, and deacetalized. The mixture was then neutralized with potassium hydroxide and treated at 100°C under reduced pressure of -0.095 MPa (gauge pressure) for 3 hours to remove the water content, followed by filtration to obtain Example Compound D-1.

[0083] <Synthesis Examples 2 to 3: Example Compound D-2, Comparative Example Compound D'-1> Example compound D-2 and comparative example compound D'-1 were obtained in the same manner as in Synthesis Example 1, except that the amounts of ethylene oxide, propylene oxide, and butylene oxide added were changed. However, in the case of a blocked adduct such as Example compound A-2, propylene oxide was added dropwise using a dropping device to achieve a predetermined number of moles of addition, followed by the reaction of ethylene oxide added dropwise using a dropping device to achieve a predetermined number of moles of addition. In addition, in the case of a random adduct such as Example compound D'-1, ethylene oxide and propylene oxide were mixed in advance and the mixture was added dropwise using a dropping device to perform the reaction.

[0084] Furthermore, the number average molecular weights of the ethylene oxide, propylene oxide, and butylene oxide adducts were determined from the hydroxyl value obtained by measuring the hydroxyl value in accordance with JIS K1557-1, and the values ​​of a and b in formula (1) were determined from the number average molecular weights. The total average number of moles of ethylene oxide, propylene oxide, and butylene oxide added for example compounds A-1 to A-7 and comparative example compounds A'-1 to A'-4 are shown in Table 1. In Table 1, "AO" indicates the type of oxyalkylene group (AO) possessed by the alkylene oxide derivative shown in formula (1), and "PO" indicates an oxypropylene group.

[0085] [Table 1]

[0086] [Experiments and results on water-based sunscreen cosmetics] Aqueous sunscreen cosmetics of Examples 1 to 10 and Comparative Examples 1 to 5 were prepared and evaluated as follows.

[0087] Components (A) to (D), (D'), (E) and other components were prepared as aqueous sunscreen cosmetics in the compositions shown in Table 2 (Examples), Table 3 (Examples), Table 4 (Comparative Examples) and Table 5 (Common Components). These were evaluated in five categories according to the evaluation criteria set forth below: "UV protection effect," "absence of squeaky feeling," "moist feeling," "absence of stickiness after repeated application," and "cleanability after repeated application."

[0088] UV protection effect The obtained water-based sunscreen cosmetic was applied to a PMMA plate at a concentration of 2 mg / cm 2 After application, the sample was left to stand for 20 minutes under light-shielded conditions, and the SPF was measured using an SPF analyzer (UV-2000S manufactured by Labsphere). 〇: When the SPF value is 10 or higher and the UV protection effect is sufficient. ×: The SPF value is less than 10, and the UV protection effect is insufficient.

[0089] No creaking sensation Twenty women (aged 25-45) were used as panelists, and they applied 0.3 g of an aqueous sunscreen cosmetic to the inside of their arm and evaluated the feeling of squeaking when blending it with their hands, using the following criteria. In detail, a total score of 35 points or more by the 20 people was rated as "◎" (excellent), 25-34 points as "○" (good), 15-24 points as "△" (fair), and 14 points or less as "×" (poor). In this evaluation, "◎" (excellent) and "○" (good) were considered to be pass marks, while "△" (fair) and "×" (poor) were considered to be fail marks. 2 points: If it blends well with the skin and doesn't feel squeaky. 1 point: It blends well with the skin, but feels a bit rough. 0 points: If the product does not blend well with the skin and feels squeaky.

[0090] Moisturizing Twenty women (aged 25-45) were used as panelists, who applied 0.3 g of an aqueous sunscreen cosmetic to the inside of their arms and evaluated the moisturizing feeling after rubbing it in with their hands according to the following criteria. In detail, a total score of 35 points or more by the 20 panelists was rated as "◎" (excellent), 25-34 points as "○" (good), 15-24 points as "△" (fair), and 14 points or less as "×" (poor). In this evaluation, "◎" (excellent) and "○" (good) were considered to be acceptable, while "△" (fair) and "×" (poor) were considered to be unacceptable. 2 points: No dryness and sufficient moisturizing. 1 point: No dryness, but the moistness is slightly lacking. 0 points: If your skin feels dry and not moisturized.

[0091] No sticky feeling after applying multiple coats Twenty women (aged 25-45) served as panelists. They spread 2g of the aqueous sunscreen cosmetic from their elbows to their wrists, allowed it to dry naturally (approximately 5 minutes), then reapplied another layer of the aqueous sunscreen cosmetic. After repeating this process three times, the stickiness was evaluated according to the following criteria. In detail, a total score of 35 points or more by the 20 panelists was evaluated as "◎" (excellent), 25-34 points as "○" (good), 15-24 points as "△" (fair), and 14 points or less as "×" (poor). In this evaluation, "◎" (excellent) and "○" (good) were considered pass, while "△" (fair) and "×" (poor) were considered fail. 2 points: If you feel a moist feeling and no unpleasant stickiness. 1 point: The skin feels moist, but there is also a slightly unpleasant stickiness. 0 points: If you feel an unpleasant sticky feeling.

[0092] - Easy to clean after recoating Twenty women (aged 25-45) served as panelists. They spread 2 g of the water-based sunscreen cosmetic from their elbows to their wrists, allowed it to dry naturally (approximately 5 minutes), and then reapplied another layer of the water-based sunscreen cosmetic, repeating this process three times. The applied area was then scrubbed with body soap, rinsed with water, and dried. The cleansing properties were evaluated based on the skin condition after scrubbing using the following criteria. Specifically, a total score of 35 or more by the 20 panelists was rated as "Excellent," 25-34 as "Good," 15-24 as "Fair," and 14 or less as "Poor." In this evaluation, "Excellent" and "Good" were considered pass marks, while "Fair" and "Poor" were considered fail marks. 2 points: No sticky feeling on skin after washing. 1 point: If your skin feels slightly sticky after washing. 0 points: If your skin feels sticky after washing.

[0093] The compositions and evaluation results of Examples 1 to 10 and Comparative Examples 1 to 5 are shown in Tables 2 to 4. The compositions shown in Tables 2 to 4 indicate the ratio (% by mass) of each component to the total mass. The compositions of components common to all aqueous sunscreen cosmetics are shown in Table 5. The compositions shown in Table 5 indicate the ratio (% by mass) of each component to the total mass of the compositions shown in Tables 2 to 4.

[0094] The ingredients used in the sunscreen cosmetics are as follows: Hydrogen dimethicone / silica-treated zinc oxide: (average primary particle size 35 nm) Triethoxycaprylylsilane-isostearate treated zinc oxide: (average primary particle size 35 nm) Aluminum hydroxide / stearic acid-treated titanium dioxide: (average primary particle size 15 nm) Hydrogen dimethicone / silica-treated titanium dioxide: (average primary particle size 15 nm) Polyglyceryl stearate / silica-treated titanium dioxide: (average primary particle size 15 nm) Quince seed extract: (Dainippon Kasei Co., Ltd. "Quince Seed 2SP") Water-soluble proteoglycan (derived from gum arabic. NOF Corporation "Proteoglycan (Plant)") Polymethyl methacrylate spherical powder (Matsumoto Microsphere (registered trademark)-M, manufactured by Matsumoto Yushi Pharmaceutical Co., Ltd., average particle size 5-20 nm) Methyl methacrylate crosspolymer spherical powder (Matsumoto Yushi Pharmaceutical Co., Ltd. "Matsumoto Microsphere (registered trademark) - M305", average particle size 5-20 nm) Glyceryl-N-(2-methacryloyloxyethyl)carbamate-stearyl methacrylate copolymer (NOF Corporation, "Ceracute (registered trademark)-L"; molar ratio (I / II) is 60 / 40)

[0095] [Table 2]

[0096] [Table 3]

[0097] [Table 4]

[0098] [Table 5]

[0099] All of the samples of Examples 1 to 10 were aqueous sunscreen cosmetics that had no squeaky feeling, a moist feeling, were not sticky even when applied in multiple layers, and were easy to wash off after application.

[0100] On the other hand, in Comparative Examples 1 to 6, sufficient effects were not obtained.

[0101] That is, in Comparative Example 1, component (A) was contained in a large amount and component (B) was blended in at more than 1%, so the SPF was sufficient, but the skin felt squeaky and dry, and the moisturizing feeling was insufficient. Furthermore, a sticky feeling occurred after reapplication, and the cleanability after reapplication was insufficient. In Comparative Example 2, component (B) was not blended, and component (D) was blended in at more than 10%, so a squeaky feeling occurred, the moisturizing feeling decreased, and a sticky feeling occurred after reapplication. In Comparative Example 3, component (C) was not blended, so a squeaky feeling occurred, and a sticky feeling occurred after reapplication. In Comparative Example 4, component (C) was blended in at more than 5% and the content of component (D) was low, so the moisturizing feeling decreased, and the cleanability after reapplication was poor. In Comparative Example 5, a different alkylene oxide derivative in which a+b was less than 10 was blended as component (D), resulting in a squeaky feeling and a reduced moist feeling.

[0102] [Experiments and results on sheet-type sunscreen cosmetics] The aqueous sunscreen cosmetics of Examples 11 to 20 and Comparative Examples 6 to 8 were prepared and applied to sheets (KP9340P: material: rayon / pulp, basis weight: 40 g / m 2 The sheet-type sunscreen cosmetic impregnated with the above-mentioned ingredients was evaluated as follows.

[0103] -Easy spread of stains onto sheets The edge of a sheet cut into a 2 cm x 20 cm strip was immersed in the aqueous sunscreen cosmetic (3.6 g) and left to stand for 5 minutes. The ease of spreading of the aqueous sunscreen cosmetic onto the sheet was evaluated based on the distance (cm) between the top of the soaked area and the liquid surface, using the following criteria. In this evaluation, a score of ◯ was considered to be acceptable. ○: The distance that has penetrated from the end is longer than 5 cm. △: When the distance penetrated from the end is between 3cm and 5cm. ×: The distance that the solution has penetrated from the end is less than 3 cm.

[0104] -Prevents sheet fluffing Twenty women (aged 25-45) were used as panelists. They rubbed a sheet (15cm x 20cm) soaked in an aqueous sunscreen cosmetic (3.6g) from their elbows to their wrists, spreading the aqueous sunscreen cosmetic. After they could no longer feel the impregnated liquid in the sheet, the sheet's pilling suppression was evaluated according to the following criteria. In detail, a total score of 35 points or more by the 20 panelists was evaluated as "◎" (excellent), 25-34 points as "○" (good), 15-24 points as "△" (fair), and 14 points or less as "×" (poor). In this evaluation, "◎" (excellent) and "○" (good) were considered pass, while "△" (fair) and "×" (poor) were considered fail. 2 points: No pilling was observed on the sheet. 1 point: The sheet is slightly fuzzy. 0 points: If the sheet is frayed.

[0105] The compositions and evaluation results of Examples 11 to 20 and Comparative Examples 6 to 8 are shown in Tables 6 to 8. The compositions shown in Tables 6 to 8 indicate the ratio (% by mass) of each component to the total mass. The compositions of components common to all aqueous sunscreen cosmetics are shown in Table 5. The compositions shown in Table 5 indicate the ratio (% by mass) of each component to the total mass of the compositions shown in Tables 6 to 8.

[0106] The materials used in the sunscreen cosmetics are the same as those listed in Tables 2 to 4.

[0107] [Table 6]

[0108] [Table 7]

[0109] [Table 8]

[0110] All of the samples of Examples 11 to 20 were water-based sunscreen cosmetic sheets that easily spread on the sheet and were also inhibited from fuzzing.

[0111] On the other hand, in Comparative Examples 6 to 8, sufficient effects were not obtained.

[0112] That is, in Comparative Example 6, component (A) was contained in a large amount and component (B) was blended in an amount greater than 1%, which made it difficult for the ink to spread onto the sheet and also resulted in an insufficient effect of inhibiting sheet fuzzing. In Comparative Example 7, component (B) was not blended and component (D) was blended in an amount greater than 10%, which resulted in an insufficient effect of inhibiting sheet fuzzing. In Comparative Example 8, component (C) was contained in an amount greater than 5% and component (D) was not blended, which resulted in an insufficient effect of inhibiting sheet fuzzing. [Industrial Applicability]

[0113] The aqueous sunscreen cosmetic of the present invention can be applied to the face, skin, and other skin types, and has unique effects not obtainable with conventional sunscreen cosmetics, specifically, it suppresses the squeaky feeling caused by the UV scattering agent, leaving a moist feeling without a dry feeling, is non-sticky even when applied in layers, and furthermore, it does not leave a squeaky feeling on the skin even after application in layers, and is highly washable. Furthermore, when impregnated into a sheet, the aqueous sunscreen cosmetic of the present invention can provide a sheet-type sunscreen cosmetic that easily spreads onto the sheet and is suppressed from pilling, and is therefore expected to be widely applicable to sunscreen cosmetics.

Claims

1. An aqueous sunscreen cosmetic comprising 5 to 20% of the following component (A), 0.001 to 1% of component (B), 0.1 to 5% of component (C), and 0.1 to 10% of component (D). (A) UV scattering agent (B) Water-soluble polymer derived from cellulose or polysaccharide (C) Spherical powder of polymethyl methacrylate or methyl methacrylate crosspolymer (D) An alkylene oxide derivative represented by the following formula (1): 【Chemistry 1】 (In formula (1), AO represents an oxyalkylene group having 3 to 4 carbon atoms, EO represents an oxyethylene group, a represents the number of moles of the oxyalkylene group having 3 to 4 carbon atoms added, b represents the number of moles of the oxyethylene group EO added, a represents a number from 0 to 50, b represents a number from 1 to 50, and a+b≧10. The oxyalkylene groups having 3 to 4 carbon atoms and the oxyethylene groups are added in a random or block manner, and in the case of block addition, the order of arrangement does not matter, and 0≦a / b≦2.

2. (E) A (meth)acrylic copolymer containing a structural unit represented by the following formula (I) and a structural unit represented by the following formula (II), in which the molar ratio (I / II) of the two structural units is 90 / 10 to 30 / 70: 【Chemistry 2】 (In formula (I), R １ represents a hydrogen atom or a methyl group, R ２ Ha-(CH ２ ) ｎ -, and n is an integer of 1 to 4. * represents a bonding site with other structural units. 【Transformation 3】 (In formula (II), R ３ represents a hydrogen atom or a methyl group, L １ represents a divalent linking group selected from the group consisting of a phenylene group, a cyclohexylene group, —C(═O)—O—, —O—, —C(═O)—NH—, —O—C(═O)—, and —O—C(═O)—O—; L ２ represents a linear or branched alkyl group having 10 to 22 carbon atoms. * represents the bonding site with other structural units.) 2. The aqueous sunscreen cosmetic according to claim 1, comprising 0.001 to 1% of

3. 3. A sheet-like aqueous sunscreen cosmetic, comprising a sheet substrate impregnated with the aqueous sunscreen cosmetic according to claim 1 or 2.

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