Method for producing coating film on skin

Abstract

To provide a method that can form an ultraviolet protection film on the skin by selecting a cosmetic containing an ultraviolet protection agent according to one's preference without worrying about rough skin or environmental load (pollution).SOLUTION: Provided is a method for producing a coating film on the skin, comprising: a process (1) for applying to the skin an oil-in-water emulsion composition X containing components (a) and (b), (a) 0.5 mass% or more and less than 5 mass% of an adhesive polymer, and (b) a cationic polymer; a process (2-1) for transcripting nanofibers mainly composed of a water-insoluble polymer to the skin after application in step (1), or a process (2-2) for electrostatically spraying a volatile medium solution containing a water-insoluble polymer directly onto the skin after application in step (1) to form a nanofiber sheet formed by deposition of nanofibers; and subsequently a process (3) for applying to the formed coating film a cosmetic composition Y containing one or more components selected from an ester oil and a fine powder.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a method for producing a coating on the skin. [Background technology]

[0002] Conventionally, methods for producing a film on the skin have been provided. For example, as described in Patent Document 1, a film with high adhesion to the skin can be formed by applying a cosmetic and applying a nanofiber sheet. In addition, as described in Patent Document 2, a method for producing an ultraviolet protection film on the skin is disclosed, which comprises applying a composition containing an ultraviolet absorbing agent to the skin and electrostatically spraying the composition directly onto the skin. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2020-26398 A [Patent Document 2] JP 2018-177795 A Summary of the Invention [Problem to be solved by the invention]

[0004] Cosmetics contain ester oils for moisturizing and various other functions, and fine powders for improving texture and scattering ultraviolet rays. Although the degree of oxidation varies depending on the type and treatment, ester oils are known to oxidize due to ultraviolet rays, and may be a burden on the skin if they are in contact with the skin for a long period of time. Although fine powders have a high adhesion to the skin due to their fineness, they may be a burden on the skin when washing, etc., depending on the person. [Means for solving the problem]

[0005] Therefore, the present inventors have conducted research to reduce the burden on the skin to a higher level and improve the convenience during use, and as a result, have found that a coating containing a cosmetic containing the useful ingredient is formed on the skin by (1) applying an oil-in-water emulsion composition containing a specific adhesive polymer and a cationic polymer to the skin, (2) transferring a nanofiber sheet mainly composed of a water-insoluble polymer to the skin to form a coating on the skin, or electrostatically spraying a volatile medium solution containing a water-insoluble polymer directly onto the skin to form a nanofiber sheet formed by deposition of nanofibers, and then (3) applying a cosmetic composition containing one or more ingredients selected from ester oil and fine powder to the formed coating. The obtained coating can be efficiently removed by peeling off the coating after use, since the composition containing the adhesive polymer can improve the adsorption of the cosmetic composition to the nanofiber sheet, and as a result, the burden on the skin can be reduced even if the ester oil in the cosmetic composition is oxidized, or the fine powder in the cosmetic composition is prevented from coming into contact with the skin grooves and pores of the skin, thereby improving the convenience when washing the skin. Therefore, the present inventors have found that it is possible to select a cosmetic composition according to one's preference without worrying about the burden on the skin, and to form a coating containing the cosmetic composition on the skin, thereby completing the present invention.

[0006] That is, the present invention provides 1) Step (1) of applying an oil-in-water emulsion composition X containing components (a) and (b) to the skin; (a) 0.5% by mass or more and less than 5% by mass of adhesive polymers having a maximum tensile shear load of 1 N or more and 90 N or less, as measured with reference to JIS K6850, selected from rubber-based adhesive polymers, silicone-based adhesive polymers, acrylic-based adhesive polymers, urethane-based adhesive polymers, and nonionic polymers; (b) Cationic polymer 2) a step (2-1) of transferring a nanofiber sheet formed on a substrate, the nanofiber sheet being formed by deposition of nanofibers mainly composed of a water-insoluble polymer, to the skin after application of the step (1); or a step (2-2) of electrostatically spraying a volatile medium solution containing a water-insoluble polymer directly onto the skin after application of the step (1) to form a nanofiber sheet formed by deposition of nanofibers; and 3) Step (3) of applying a cosmetic composition containing one or more selected from an ester oil and a fine powder to the formed coating film; The present invention provides a method for producing a coating on the skin, which comprises the steps of:

[0007] The present invention also provides a skin protection kit comprising the following (A) and (B): (A) an oil-in-water emulsion composition X containing the components (a) and (b); (a) 0.5% by mass or more and less than 5% by mass of adhesive polymers having a maximum tensile shear load of 1 N or more and 90 N or less, as measured with reference to JIS K6850, selected from rubber-based adhesive polymers, silicone-based adhesive polymers, acrylic-based adhesive polymers, urethane-based adhesive polymers, and nonionic polymers; (b) a cationic polymer, (B) A nanofiber sheet formed on a substrate, the nanofiber sheet being formed by deposition of nanofibers comprised primarily of a water-insoluble polymer. Effect of the Invention

[0008] According to the present invention, the composition containing an adhesive polymer can improve the adsorption of the ester oil or fine powder in the cosmetic composition to the nanofiber sheet, thereby improving the burden on the skin when the ester oil is oxidized by ultraviolet light, etc., and the convenience of washing and removing the fine powder that has adhered to the skin grooves and pores can be improved. Therefore, it becomes possible to select a cosmetic composition according to one's preference and form a coating containing the cosmetic composition on the skin without worrying about the burden on the skin or the effort of washing. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] The present invention is a method for producing a coating on skin, one aspect of which comprises: 1) Step (1) of applying an oil-in-water emulsion composition X containing components (a) and (b) to the skin; (a) 0.5% by mass or more and less than 5% by mass of adhesive polymers having a maximum tensile shear load of 1 N or more and 90 N or less, as measured with reference to JIS K6850, selected from rubber-based adhesive polymers, silicone-based adhesive polymers, acrylic-based adhesive polymers, urethane-based adhesive polymers, and nonionic polymers; (b) Cationic polymer 2) a step (2-1) of transferring a nanofiber sheet formed on a substrate, the nanofiber sheet being formed by deposition of nanofibers mainly composed of a water-insoluble polymer, to the skin after application of the step (1); or a step (2-2) of electrostatically spraying a volatile solvent solution containing a water-insoluble polymer directly onto the skin after application of the step (1) to form a nanofiber sheet formed by deposition of nanofibers mainly composed of a water-insoluble polymer; and 3) Step (3) of applying a cosmetic composition containing one or more selected from an ester oil and a fine powder to the formed coating film; The present invention relates to a method for producing a coating on the skin, the method comprising the steps of: Step (1), step (2) (step (2-1) and step (2-2) are collectively referred to as step (2)), and step (3) will be described below.

[0010] [Process (1)] Step (1) is a step of applying an oil-in-water emulsion composition X containing components (a) and (b) to the skin. (a) 0.5% by mass or more and less than 5% by mass of adhesive polymers having a maximum tensile shear load of 1 N or more and 90 N or less, as measured with reference to JIS K6850, selected from rubber-based adhesive polymers, silicone-based adhesive polymers, acrylic-based adhesive polymers, urethane-based adhesive polymers, and nonionic polymers; (b) Cationic polymer Examples of the adhesive polymer contained in component (a) used in the oil-in-water emulsion composition X include rubber-based adhesive polymers, silicone-based adhesive polymers, acrylic-based adhesive polymers, and urethane-based adhesive polymers, and one or more types selected from these can be used.

[0011] Examples of rubber-based adhesive polymers include rubber-based adhesive polymers based on synthetic rubbers such as natural rubber, polyisoprene rubber, styrene-butadiene (SB) rubber, styrene-isoprene (SI) rubber, styrene-isoprene-styrene block copolymer (SIS) rubber, styrene-butadiene-styrene block copolymer (SBS) rubber, styrene-ethylene-butylene-styrene block copolymer (SEBS) rubber, styrene-ethylene-propylene-styrene block copolymer (SEPS) rubber, styrene-ethylene-propylene block copolymer (SEP) rubber, reclaimed rubber, butyl rubber, polyisobutylene, and modified versions of these synthetic rubbers. Among these rubber-based adhesive polymers, at least one selected from styrene-isoprene-styrene block copolymer, styrene-butadiene-styrene block copolymer, styrene-butadiene rubber, polyisobutylene, isoprene rubber, and silicone rubber is more preferable. An example of a commercially available rubber-based adhesive polymer is Yodosol GH41F (manufactured by Akzo Nobel).

[0012] Examples of the acrylic adhesive polymer include an acrylic adhesive polymer having as a base polymer an acrylic polymer (homopolymer or copolymer) using one or more (meth)acrylic acid alkyl esters as monomer components. Specific examples of the (meth)acrylic acid alkyl ester include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, s-butyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, and (meth)acrylate. Examples of (meth)acrylic acid C1-20 alkyl esters include nonyl acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, tridecyl (meth)acrylate, tetradecyl (meth)acrylate, pentadecyl (meth)acrylate, hexadecyl (meth)acrylate, heptadecyl (meth)acrylate, octadecyl (meth)acrylate, nonadecyl (meth)acrylate, and eicosyl (meth)acrylate. Examples of the secondary monomers used together with these base polymers include N-vinylpyrrolidone, methylvinylpyrrolidone, (meth)acrylic acid, vinyl acetate, etc. Examples of commercially available acrylic polymers include Amphomer 28-4910 (Akzo Nobel), Yodozol GH256F (particle size 20 to 40 nm; Akzo Nobel), Yodozol GH800F (Akzo Nobel), Yodozol GH810F (Akzo Nobel), Daitosol 5000AD (Daito Chemical Industry Co., Ltd.), Daitosol 5000SJ (Daito Chemical Industry Co., Ltd.), etc.

[0013] As the silicone adhesive polymer, for example, a silicone adhesive polymer having a silicone rubber or silicone resin containing organopolysiloxane as a base polymer is preferably used. As the base polymer constituting the silicone adhesive polymer, a base polymer obtained by crosslinking the above-mentioned silicone rubber or silicone resin may be used. As the silicone rubber, for example, an organopolysiloxane containing dimethylsiloxane as a constituent unit may be mentioned. In the organopolysiloxane, a functional group (for example, a vinyl group) may be introduced as necessary. As the silicone resin, for example, R3SiO 1 / 2 Building block, SiO2 building block, RSiO 3 / 2 Examples of the silicone adhesive polymer include organopolysiloxanes containing at least one type of structural unit selected from the structural unit and the R2SiO structural unit. The silicone adhesive polymer may contain a crosslinking agent. Examples of the crosslinking agent include siloxane-based crosslinking agents and peroxide-based crosslinking agents. Any appropriate crosslinking agent can be used as the peroxide-based crosslinking agent. Examples of the peroxide-based crosslinking agent include benzoyl peroxide, t-butyl peroxybenzoate, and dicumyl peroxite. Examples of the siloxane-based crosslinking agent include polyorganohydrogensiloxane.

[0014] As the organopolysiloxane, the following poly(N-acylalkyleneimine)-modified organopolysiloxane (hereinafter also simply referred to as "modified organopolysiloxane") can be used.

[0015] The modified organopolysiloxane has at least two silicon atoms of the organopolysiloxane segment constituting the main chain connected, via an alkylene group containing a heteroatom, to a compound represented by the following general formula (1):

[0016] [ka]

[0017] [In the formula, R 1represents a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, an aralkyl group, or an aryl group, and n represents 2 or 3. The modified organopolysiloxane is formed by bonding poly(N-acylalkyleneimine) segments composed of repeating units represented by the following formula: wherein the mass ratio (α / β) of the organopolysiloxane segment (α) constituting the main chain to the poly(N-acylalkyleneimine) segment (β) is 40 / 60 or more and 98 / 2 or less, and the weight average molecular weight of the organopolysiloxane segment constituting the main chain is 30,000 or more and 100,000 or less.

[0018] The mass ratio (α / β) of the organopolysiloxane segment (α) to the poly(N-acylalkyleneimine) segment (β) of the modified organopolysiloxane is preferably 40 / 60 or more, more preferably 55 / 45 or more, and even more preferably 65 / 35 or more, from the viewpoint of improving the abrasion resistance and durability of the coating obtained by steps (2) and (3). From the same viewpoint, it is preferably 98 / 2 or less, more preferably 90 / 10 or less, and even more preferably 82 / 18 or less.

[0019] In the modified organopolysiloxane, at least two poly(N-acylalkyleneimine) segments can be bonded to any silicon atom constituting the organopolysiloxane segment via an alkylene group containing a heteroatom, but it is preferable that the poly(N-acylalkyleneimine) segment is bonded to one or more silicon atoms excluding both terminals via the alkylene group, and it is more preferable that the poly(N-acylalkyleneimine) segment is bonded to two or more silicon atoms excluding both terminals via the alkylene group.

[0020] The alkylene group containing a heteroatom present in the bond between the organopolysiloxane segment and the poly(N-acylalkyleneimine) may be an alkylene group having 2 to 20 carbon atoms and containing 1 to 3 nitrogen atoms, oxygen atoms, and / or sulfur atoms. Specific examples thereof include the following.

[0021] [ka]

[0022] The N-acylalkyleneimine unit constituting the poly(N-acylalkyleneimine) segment is represented by the above general formula (1). In general formula (1), R 1 Examples of the alkyl group having 1 to 22 carbon atoms include linear, branched, or cyclic alkyl groups having 1 to 22 carbon atoms. Specific examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, an octadecyl group, a nonadecyl group, an eicosyl group, and a docosyl group.

[0023] Examples of the aralkyl group include aralkyl groups having 7 to 15 carbon atoms, and specific examples thereof include a benzyl group, a phenethyl group, a trityl group, a naphthylmethyl group, and an anthracenylmethyl group.

[0024] Examples of the aryl group include aryl groups having 6 to 14 carbon atoms, and specific examples include a phenyl group, a tolyl group, a xylyl group, a naphthyl group, a biphenyl group, an anthryl group, and a phenanthryl group.

[0025] In this specification, the mass ratio (α / β) refers to a value determined by dissolving 5% by mass of organopolysiloxane in deuterated chloroform and analyzing it by nuclear magnetic resonance (H-NMR) to determine the integral ratio of alkyl groups or phenyl groups in the organopolysiloxane segment to methylene groups in the poly(N-acylalkyleneimine) segment.

[0026] In the modified organopolysiloxane, the weight average molecular weight (MWg) of the organopolysiloxane segment between adjacent poly(N-acylalkyleneimine) segments is preferably 1,300 or more, more preferably 1,500 or more, even more preferably 1,800 or more, and is preferably 32,000 or less, more preferably 10,000 or less, even more preferably 5,000 or less.

[0027] In this specification, the term "organopolysiloxane segment between adjacent poly(N-acylalkyleneimine) segments" refers to a portion surrounded by a dashed line between the two points from the bonding point (bonding point A) of the poly(N-acylalkyleneimine) segment to the organopolysiloxane segment to the bonding point (bonding point B) of the adjacent poly(N-acylalkyleneimine) segment, as shown in the following formula (2), and is a region in which one R 2 SiO unit and one R 6 and y+1 R 2 2SiO units. Also, the term "poly(N-acylalkyleneimine) segment" refers to a segment composed of the above R 6 -ZR binds to 7 This refers to.

[0028] [ka]

[0029] In the above general formula (2), R 2 each independently represents an alkyl group having 1 to 22 carbon atoms or a phenyl group; R 6 represents an alkylene group containing a heteroatom, and R 7 represents the residue of a polymerization initiator, and -ZR 7 represents a poly(N-acylalkyleneimine) segment, and y represents a positive number.

[0030] MWg is the molecular weight of the portion enclosed by the dashed line in the above general formula (2), and can be interpreted as the mass (g / mol) of organopolysiloxane segment per mole of poly(N-acylalkyleneimine) segment. When the functional groups of the organopolysiloxane raw material compound are 100% substituted with poly(N-acylalkyleneimine), this coincides with the functional group equivalent (g / mol) of the modified organopolysiloxane.

[0031] Furthermore, when the functional group equivalent weight (g / mol) of the raw material organopolysiloxane is known, MWg can be calculated using the following formula even if the functional groups are not 100% substituted with poly(N-acylalkyleneimine).

[0032] MWg = [functional group equivalent of organopolysiloxane (g / mol)] ÷ [substitution rate (%) / 100 (%)]

[0033] Furthermore, when the functional group equivalent of the organopolysiloxane is unknown, MWg can be calculated from the content (Csi) of the organopolysiloxane segment constituting the main chain and the molecular weight (MWox) of the poly(N-acylalkyleneimine) segment according to the following formula.

[0034]

number

[0035] The molecular weight (MWox) of the poly(N-acylalkyleneimine) segment can be measured by a method of calculation from the molecular weight and degree of polymerization of the N-acylalkyleneimine unit or by a gel permeation chromatography (GPC) measurement method described below, but in the present invention, it refers to the number average molecular weight measured by the GPC measurement method. The MWox of the modified organopolysiloxane is preferably 500 or more, more preferably 600 or more, and even more preferably 700 or more, from the viewpoint of excellent abrasion resistance and durability of the coating obtained by steps (2) and (3), and is preferably 5,500 or less, more preferably 3,500 or less, and even more preferably 3,000 or less.

[0036] The weight average molecular weight (MWsi) of the organopolysiloxane segment constituting the main chain is 7,000 or more, preferably 10,000 or more, more preferably 20,000 or more, and 120,000 or less, preferably 80,000 or less, more preferably 60,000 or less, from the viewpoint of excellent abrasion resistance and durability of the coating obtained by step (2) and step (3). Since the organopolysiloxane segment constituting the main chain has a common skeleton with the organopolysiloxane as the raw material compound, the MWsi is approximately the same as the weight average molecular weight of the organopolysiloxane as the raw material compound. The weight average molecular weight of the organopolysiloxane as the raw material compound is measured by GPC under the following measurement conditions and converted into polystyrene.

[0037] Column: Super HZ4000+Super HZ2000 (Tosoh Corporation) Eluent: 1mM triethylamine / THF Flow rate: 0.35mL / min Column temperature: 40℃ Detector: UV Sample: 50μL

[0038] The weight average molecular weight (MWt) of the modified organopolysiloxane is preferably 10,000 or more, more preferably 12,000 or more, more preferably 24,000 or more, and is preferably 200,000 or less, more preferably 150,000 or less, more preferably 120,000 or less, more preferably 92,000 or less, and more preferably 80,000 or less. This allows the coating obtained in step (2) and step (3) to have sufficient coating strength and excellent abrasion resistance and durability. In this specification, MWt can be determined from the weight average molecular weight of the modified organopolysiloxane, which is the raw material compound, and the above-mentioned mass ratio (α / β).

[0039] The modified organopolysiloxane can be produced by known production methods such as the methods disclosed in JP-A-2009-024114 and WO-A-2011 / 062210.

[0040] The urethane adhesive polymer may be made of a urethane resin obtained by reacting a polyol with a polyisocyanate compound. The polyol may be, for example, a polyether polyol, a polyester polyol, a polycarbonate polyol, or a polycaprolactone polyol. The polyisocyanate compound may be, for example, diphenylmethane diisocyanate, tolylene diisocyanate, or hexamethylene diisocyanate. A commercially available urethane adhesive polymer may be Baycusan C2000 (COVESTRO).

[0041] The nonionic polymer is not particularly limited, and any nonionic polymer commonly used in the field of cosmetics can be used. Examples of nonionic polymers include (meth)acrylic water-soluble nonionic polymers, (meth)acrylic water-insoluble nonionic polymers, polyvinylpyrrolidone, polyacrylamide, low-saponification polyvinyl alcohol (saponification degree 60 mol% or less), neutral polysaccharides and their derivatives (ethers, esters, etc.). Examples of neutral sugars and their derivatives include neutral gums (guar gum, hydroxypropyl guar, etc.), cellulose ethers (hydroxyethyl cellulose (HEC), methyl hydroxyethyl cellulose (MHEC), ethyl hydroxyethyl cellulose (EHEC), methyl ethyl hydroxyethyl cellulose (MEHEC), hydroxypropyl cellulose (HPC), hydroxypropyl methyl cellulose (HPMC), and hydrophobized derivatives thereof (HM-EHEC, etc.)), starch and its derivatives (dextrin, etc.).

[0042] Examples of compounds having an ethylenically unsaturated bond capable of constituting a nonionic polymer such as the (meth)acrylic water-soluble nonionic polymer, the (meth)acrylic water-insoluble nonionic polymer, polyvinylpyrrolidone, polyacrylamide, low-saponification polyvinyl alcohol (saponification degree 60 mol % or less) are given below, but the present invention is not limited in any way by the following specific examples. Examples of nonionic monomers include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and nonionic (meth)acrylate. (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, phenyl (meth)acrylate, toluyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, stearyl (meth)acrylate, glycidyl (meth)acrylate, 2-aminoethyl (meth)acrylate, γ-((meth)acryloyloxypropyl) (meth)trimethoxysilane, γ-((meth)acryloyloxypropyl)dimethoxymethylsilane, ethylene oxide adduct of (meth)acrylic acid, trifluoromethylmethyl (meth)acrylate, 2-trifluoromethylethyl (meth)acrylate, 2-perfluoroethylethyl (meth)acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth)acrylate, 2-perfluoroethyl (meth)acrylate, perfluoromethyl (meth)acrylate, diperfluoromethylmethyl (meth)acrylate (Meth)acrylic acid esters such as 2-perfluoromethyl-2-perfluoroethylmethyl (meth)acrylate, 2-perfluorohexylethyl (meth)acrylate, 2-perfluorodecylethyl (meth)acrylate, and 2-perfluorohexadecylethyl (meth)acrylate; aromatic alkenyl compounds such as styrene, α-methylstyrene, p-methylstyrene, and p-methoxystyrene; vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; conjugated diene compounds such as butadiene and isoprene;Halogen-containing unsaturated compounds such as vinyl chloride, vinylidene chloride, perfluoroethylene, perfluoropropylene, and vinylidene fluoride; silicon-containing unsaturated compounds such as vinyltrimethoxysilane and vinyltriethoxysilane; unsaturated carboxylic anhydrides such as maleic anhydride; unsaturated dicarboxylic acid diesters such as dialkyl maleates and dialkyl fumarate; vinyl ester compounds such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, and vinyl cinnamate; maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-butylmaleimide, N-hexylmaleimide, N-octylmaleimide, and Examples of the monomers include maleimide-based compounds such as N-dodecylmaleimide, N-stearylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide; monomers derived from (meth)acrylic acid or (meth)acrylamide and an alkylene oxide having 2 to 4 carbon atoms, such as polyethylene glycol (meth)acrylate, methoxypoly(ethylene glycol / propylene glycol) mono(meth)acrylate, polyethylene glycol di(meth)acrylate, and N-polyalkyleneoxy(meth)acrylamide; and hydrophilic nonionic monomers such as N-vinylpyrrolidone, N-(meth)acryloylmorpholine, and acrylamide.

[0043] Among these, one or more selected from the group consisting of (meth)acrylic water-insoluble nonionic polymers, polyvinylpyrrolidone, and low-saponification polyvinyl alcohol (saponification degree 60 mol% or less) are preferred. Commercially available products include, for example, MAS683 (manufactured by Cosmedy Pharmaceuticals), polyvinylpyrrolidone K-90 (manufactured by BASF), and JMR-150L (manufactured by Nippon Vinegar Vinyl Co., Ltd.).

[0044] In this specification, the term "(meth)acrylic" means "acrylic or methacrylic".

[0045] The (a) adhesive polymer is selected from the viewpoint of improving the abrasion resistance and durability of the coating obtained by steps (2) and (3) after a long time has elapsed. As the adhesive polymer, a polymer having a maximum tensile shear load of 1N or more, more preferably 3N or more, and even more preferably 5N or more, measured with reference to JISK6850 is preferably a polymer having a maximum tensile shear load of 90N or less, more preferably 60N or less, and even more preferably 30N or less, measured with reference to JISK6850. Specifically, it is preferable to use one or more types selected from rubber-based adhesive polymers, silicone-based adhesive polymers, acrylic-based adhesive polymers, and urethane-based adhesive polymers.

[0046] The adhesiveness (maximum tensile shear load) of the polymer can be measured as follows: 20 mg of polymer solution (10% ethanol solution) is applied to an area of ​​1.25 cm x 2.5 cm at the edge of one polycarbonate substrate, and then it is laminated to another polycarbonate substrate (Standard Test Piece, Carbon Glass Polish Clear, 10 cm x 2.5 cm x 2.0 mm) and dried for more than 12 hours. Both ends of the polycarbonate substrate are pulled at a pulling speed of 5 mm / min using an Orientec Tensilon UTC-100W, and the maximum tensile shear load is measured.

[0047] The content of the adhesive polymer (a) in the oil-in-water emulsion composition is 0.5% by mass or more and less than 5% by mass from the viewpoint of durability against tearing and peeling of the coating obtained by steps (2) and (3) after a long time has elapsed. It is more preferably 0.6% by mass or more, and even more preferably 0.8% by mass or more. It is more preferably 4% by mass or less, even more preferably 3% by mass or less, and even more preferably 2% by mass or less. Specifically, it is preferably 0.6% by mass or more and 4% by mass or less, more preferably 0.8% by mass or more and 3% by mass or less, and even more preferably 0.8% by mass or more and 2% by mass or less.

[0048] (b) Examples of the cationic polymer include poly(dimethyldiallylammonium halide) type cationic polymers, cationic copolymer polymers of dimethyldiallylammonium halide and acrylamide, quaternary nitrogen-containing cellulose ethers, polyethylene glycol, epichlorohydrin, condensation products of tallow amine or cocoyl amine obtained from propyleneamine and beef tallow fatty acid, cationized vinylpyrrolidone-dimethylaminoethyl methacrylate copolymers, and N,N-dimethylaminoethyl diethyl methacrylate sulfate-N,N-dimethylacrylamide-polyethylene glycol dimethacrylate copolymers (polyquaternium-52), of which N,N-dimethylaminoethyl diethyl methacrylate sulfate-N,N-dimethylacrylamide-polyethylene glycol dimethacrylate copolymers (polyquaternium-52) are more preferred.

[0049] Examples of poly(dimethyldiallylammonium halide) type cationic polymers include Merquat 100 (Nalco). Examples of copolymer type cationic polymers of dimethyldiallylammonium halide and acrylamide include Merquat 550 (Nalco). Examples of quaternary nitrogen-containing cellulose include Polymer JR-400, Polymer JR-125, and Polymer JR-30M (Union Carbide). Examples of condensation products of polyethylene glycol, epichlorohydrin, propyleneamine, and tallowylamine or cocoylamine include Polyquat H (Henkel). Examples of cationic vinylpyrrolidone-dimethylaminoethyl methacrylate copolymers include Gafquat 755 and Gafquat 734 (GAF). Examples of N,N-dimethylaminoethyl diethyl methacrylate sulfate-N,N-dimethylacrylamide-polyethylene glycol dimethacrylate copolymers include Sofcare KG-301W (Kao). Other examples include the HC Polymer series sold by Osaka Organic Chemical Industry Co., Ltd. and the Jaguar series by Rhodia.

[0050] The content of the (b) cationic polymer in the oil-in-water emulsion composition X is preferably 0.05% by mass or more, more preferably 0.07% by mass or more, and even more preferably 0.08% by mass or more, from the viewpoints of the performance of the ester oil and fine powder of the coating obtained by steps (2) and (3), their removability, the appearance of the peeling film, and suppression of burden on the skin. Also, it is preferably 3% by mass or less, more preferably 2% by mass or less, and even more preferably 1% by mass or less. Specifically, it is preferably 0.05% by mass or more and 3% by mass or less, more preferably 0.07% by mass or more and 2% by mass or less, and even more preferably 0.08% by mass or more and 1% by mass or less. The mass ratio (a / b) of the adhesive polymer (a) to the cationic polymer (b) in the oil-in-water emulsion composition X is preferably 5 or more and 18 or less, more preferably 6 or more and 14 or less, and even more preferably 7 or more and 10 or less, from the viewpoints of the performance of the ester oil and fine powder in the coating obtained in steps (2) and (3), their removability, the appearance of the release film, and suppression of burden on the skin.

[0051] The emulsion composition X is an oil-in-water emulsion composition, and preferably contains an oil and water in addition to the components (a) and (b), and more preferably contains a polyol, a liquid oil (liquid at 20° C.), a surfactant, and water in addition to the components (a) and (b).

[0052] Examples of polyols include alkylene glycols such as ethylene glycol, propylene glycol, 1,3-propanediol, and 1,3-butylene glycol; polyalkylene glycols such as diethylene glycol, dipropylene glycol, polyethylene glycols having a molecular weight of 1000 or less, and polypropylene glycol; and glycerins such as glycerin, diglycerin, and triglycerin. Among these, from the viewpoints of usability such as smoothness when applied and durability of the coating film obtained in step (2) and step (3) after a long period of time, ethylene glycol, propylene glycol, 1,3-butylene glycol, dipropylene glycol, polyethylene glycols having a molecular weight of 1000 or less, glycerin, and diglycerin are preferred, propylene glycol, 1,3-butanediol, and glycerin are more preferred, and it is even more preferred that the coating contains at least glycerin.

[0053] The liquid oil in the present invention is an oil that is liquid at 20°C, and includes semi-solid oils with flowability. Examples of liquid oils include hydrocarbon oils, higher alcohols, silicone oils, and fatty acids. Among these, hydrocarbon oils and silicone oils are preferred in terms of smoothness during application, adhesion and abrasion resistance of the coating film obtained in steps (2) and (3) after a long time. In addition, one or more types selected from these liquid oils can be used in combination.

[0054] Examples of the liquid hydrocarbon oil include liquid paraffin, squalane, squalene, n-octane, n-heptane, cyclohexane, light isoparaffin, liquid isoparaffin, hydrogenated polyisobutene, polybutene, polyisobutene, etc., and from the viewpoint of usability, liquid paraffin, light isoparaffin, liquid isoparaffin, squalane, squalene, n-octane, n-heptane, and cyclohexane are preferred, and liquid paraffin and squalane are more preferred. In addition, from the viewpoint of the adhesion and abrasion resistance of the coating obtained in steps (2) and (3), the viscosity of the hydrocarbon oil at 30°C is preferably 1 mPa s or more, more preferably 3 mPa s or more. From the viewpoint of adhesion and abrasion resistance of the coating film obtained in step (2) and step (3), the total content of isododecane, isohexadecane, and hydrogenated polyisobutene in the oil-in-water emulsion composition X is preferably 10 mass % or less, more preferably 5 mass % or less, even more preferably 1 mass % or less, and still more preferably 0.5 mass % or less, and may not be contained at all. Similarly, from the viewpoint of the adhesion and abrasion resistance of the coatings obtained in steps (2) and (3), the viscosity of the silicone oil at 30°C is preferably 1 mPa·s or more, and more preferably 3 mPa·s or more. The viscosity here is measured at 30° C. using a BM type viscometer (manufactured by Tokimec Co., Ltd., measurement conditions: rotor No. 1, 60 rpm, 1 minute). From the same viewpoint, the total content of ether oils such as cetyl-1,3-dimethylbutyl ether, dicapryl ether, dilauryl ether, diisostearyl ether, etc. in the oil-in-water emulsion composition X is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 1% by mass or less.

[0055] The higher alcohol may be a liquid higher alcohol having 12 to 20 carbon atoms, and is preferably a higher alcohol having a branched fatty acid as a constituent element, specifically, isostearyl alcohol, oleyl alcohol, etc.

[0056] Examples of liquid silicone oils include linear silicones, cyclic lysines, and modified silicones, such as dimethylpolysiloxane, dimethylcyclopolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, phenyl-modified silicones, and higher alcohol-modified organopolysiloxanes. From the viewpoint of the adhesion of the coating obtained in steps (2) and (3), the content of silicone oil in oil-in-water emulsion composition X is preferably 35% by mass or less, and from the viewpoint of improving the releasability of the coating obtained in steps (2) and (3), the content is more preferably 10% by mass or less, even more preferably 7% by mass or less, and even more preferably 5% by mass or less. The kinetic viscosity of the silicone oil at 25°C is set to 3 mm from the viewpoint of adhesion and abrasion resistance of the coating film obtained in steps (2) and (3). 2 / s or more is preferable, 4mm 2 / s or more is preferable, and 5mm 2 / s or more is more preferable, and 30 mm 2 / s or less is preferable, 20 mm 2 / s or less is preferable, and 10 mm 2 / s or less is even more preferable. Among these, from the viewpoints of adhesion and abrasion resistance of the coatings obtained in steps (2) and (3), it is preferable that the silicone oil contains dimethylpolysiloxane.

[0057] In addition, oils that are solid at 20°C (solid oils) can also be used. Oils that are solid at 20°C are preferably solid at 20°C and have a melting point of 40°C or higher. Examples of oils that are solid at 20°C include hydrocarbon waxes, ester waxes, higher alcohols, silicone waxes, etc., and one or more selected from these can be contained. Such waxes are not limited as long as they are used in ordinary cosmetics, and include, for example, mineral waxes such as ozokerite and ceresin; petroleum waxes such as paraffin, microcrystalline wax, and petrolatum; synthetic hydrocarbon waxes such as Fischer-Tropsch wax and polyethylene wax; vegetable waxes such as carnauba wax, candelilla wax, rice wax, wood wax, sunflower wax, and hydrogenated jojoba oil; animal waxes such as beeswax and whale wax; synthetic waxes such as silicone wax, fluorine-based wax, and synthetic beeswax; fatty acids, higher alcohols, and derivatives thereof.

[0058] The content of one or more components selected from polyols and liquid oils in the oil-in-water emulsion composition X is preferably from 1 to 40% by mass, more preferably from 2 to 25% by mass, even more preferably from 4 to 20% by mass, and still more preferably from 10 to 20% by mass, from the viewpoints of improving the adhesion, feel, and durability after long-term use of the coating film obtained in steps (2) and (3).

[0059] A nonionic surfactant, an anionic surfactant, or a cationic surfactant can be used as the surfactant to be incorporated in the oil-in-water emulsion composition X. More preferably, one or more surfactants selected from a nonionic surfactant, an anionic surfactant, and a cationic surfactant are used. Furthermore, the oil-in-water emulsion composition X may contain, in addition to the above-mentioned components, water-soluble polymers, fragrances, colorants, pH adjusters, blood circulation promoters, cooling agents, antiperspirants, disinfectants, skin activators, moisturizers, cooling agents, etc.

[0060] In step (1), the oil-in-water emulsion composition X is applied to the skin. The composition can be applied to the skin in the same manner as ordinary cosmetics are applied to the skin. For example, the composition can be applied to the skin by a method such as finger application, and the step of spreading the composition can be included, so that the composition can be blended with the skin and a thin layer of the composition can be formed.

[0061] Step (2) includes a step (2-1) of transferring a nanofiber sheet formed on a substrate by deposition of nanofibers mainly composed of a water-insoluble polymer to the skin after application in step (1); Alternatively, a volatile solvent solution containing a water-insoluble polymer is electrostatically sprayed directly onto the skin after application in step (1) to form a nanofiber sheet formed by deposition of nanofibers mainly composed of the water-insoluble polymer (step (2-2)). Step (2-1) and then step (2-2) will be described.

[0062] [Process (2-1)] Step (2-1) is a step of transferring a nanofiber sheet formed on a substrate by deposition of nanofibers mainly composed of a water-insoluble polymer to the skin after application in step (1). The nanofiber sheet in step (2-1) is a nanofiber sheet formed in advance on a substrate other than the skin, and is a nanofiber sheet formed by depositing nanofibers whose main component is a water-insoluble polymer.

[0063] A nanofiber sheet is a sheet formed of nanofibers. The nanofiber sheet is preferably composed only of nanofibers, but this does not preclude the nanofiber sheet from containing other components in addition to nanofibers. The thickness of nanofibers, expressed as a circle equivalent diameter, is generally 10 to 3000 nm, particularly 10 to 1000 nm. The thickness of nanofibers can be measured, for example, by scanning electron microscope (SEM) observation. Specifically, the nanofibers are observed at a magnification of 10,000 times by SEM observation, defects (lumps of nanofibers, intersections of nanofibers, droplets) are removed from the two-dimensional image, 10 nanofibers are arbitrarily selected, a line perpendicular to the longitudinal direction of the nanofibers is drawn, and the diameter is directly read to measure the thickness. The length of the nanofiber is not particularly limited, but is preferably 100 times or more the diameter. When the nanofiber sheet is produced, for example, by an electrospinning method, it has a structure in which nanofibers are accumulated to form a sheet, and such a structure in which nanofibers are accumulated is preferred from the viewpoints of adhesion, homogeneity, durability, etc. of the coating formed by the transferred nanofiber sheet, oil-in-water emulsion composition X, and the cosmetic composition applied in step (3).

[0064] When the nanofiber sheet is used by being transferred to the skin, from the viewpoint of making the transferred nanofiber sheet difficult to see (transparent), the thickness of the nanofiber sheet is preferably 0.1 μm or more, more preferably 5.1 μm or more, and even more preferably 10 μm or more. Furthermore, when the nanofiber sheet is used by being transferred to the skin, from the viewpoint of obtaining a good feeling of use and ultraviolet protection effect, the thickness of the nanofiber sheet is preferably 500 μm or less, more preferably 400 μm or less, and even more preferably 100 μm or less. The thickness of the nanofiber sheet is preferably 5.1 μm or more and 500 μm or less, more preferably 10 μm or more and 400 μm or less, and even more preferably 10 μm or more and 100 μm or less. The thickness of the nanofiber sheet is the maximum thickness measured by peeling off only the nanofiber sheet from the substrate and using a contact-type film thickness gauge (Mitutoyo Litematic VL-50A (R5 mm superhard spherical probe)). The load applied to the measurement object during measurement is 0.01 Pa.

[0065] The nanofiber sheet used in the present invention is a nanofiber sheet formed by deposition of nanofibers mainly composed of a water-insoluble polymer, and is obtained by discharging and depositing nanofibers on a substrate by electrostatic spraying or melt-blowing a liquid mainly composed of a water-insoluble polymer. As an example of electrostatic spraying, it is preferable to produce the nanofiber sheet by discharging a volatile medium solution containing a water-insoluble polymer on a substrate by electrospinning to form a deposit. Water-insoluble refers to a nanofiber sheet that has the property that, when 1 g of the nanofiber sheet is weighed out and immersed in 10 g of deionized water in an environment of 1 atmosphere and 23°C, after 24 hours, more than 0.5 g of the immersed nanofiber sheet does not dissolve, and preferably more than 0.8 g of the immersed nanofiber sheet does not dissolve.

[0066] The nanofiber sheet is formed by depositing nanofibers containing a fiber-formable polymer. From the viewpoint of making the nanofiber sheet water-insoluble, the nanofiber sheet preferably contains nanofibers of a water-insoluble polymer as the fiber-formable polymer. Examples of water-insoluble polymers include fully saponified polyvinyl alcohol that can be insolubilized after nanofiber formation, partially saponified polyvinyl alcohol that can be crosslinked after nanofiber formation by using a crosslinking agent in combination, oxazoline-modified silicones such as poly(N-propanoylethyleneimine) graft-dimethylsiloxane / γ-aminopropylmethylsiloxane copolymers, zein (a major component of corn protein), polyester resins such as polylactic acid, polyethylene terephthalate resin, and polybutylene terephthalate resin, acrylic resins such as polyacrylonitrile resin and polymethacrylic acid resin, polystyrene resin, polyvinyl butyral resin, polyurethane resin, polyamide resins such as nylon, polyimide resin, polyamideimide resin, etc. These water-insoluble polymers can be used alone or in combination of two or more.

[0067] Of these water-insoluble polymers, from the viewpoint of obtaining a nanofiber sheet that has excellent transferability and can easily maintain good quality even in the usage environment, particularly in a hot and humid environment, it is preferable that the moisture absorption in a hot and humid environment (left to stand for 24 hours at 40°C and 90 RH%) is 1% or less, more preferably 0.9% or less. From the same viewpoint, it is preferable that the moisture absorption is 0.1% or more, more preferably 0.6% or more.

[0068] In this specification, the moisture absorption of a polymer in a hot and humid environment is measured by a constant rate method described below. 1 g of the polymer to be measured is placed in an incubator at 40°C and 90% RH (high temperature and humidity environment) for 24 hours to apply a high temperature and humidity load to the polymer to be measured. The weight of the polymer to be measured before the high temperature and humidity load is measured immediately after it is placed in an environment of 25°C and 50% RH for 1 minute is defined as the "initial weight", and the weight of the polymer to be measured after the high temperature and humidity load is measured immediately after it is taken out of the incubator and placed in an environment of 25°C and 50% RH for 1 minute is defined as the "weight after high temperature and humidity load". The moisture absorption of the polymer to be measured is calculated using the following formula (1). Moisture absorption = (weight after high temperature and humidity load - initial weight) / initial weight x 100 (%) ... (1) In this specification, unless otherwise specified, "hygroscopicity" means "hygroscopicity under a high temperature and high humidity environment."

[0069] Of the water-insoluble polymers, from the viewpoint of obtaining a nanofiber sheet that has excellent transferability and is easy to maintain good quality, it is more preferable to use one or more polymers selected from polyvinyl butyral resin, polyurethane resin, and polylactic acid, and it is even more preferable to use polyvinyl butyral resin.

[0070] Furthermore, when a nanofiber sheet is formed using only a water-insoluble polymer, the transferability is good, but the compatibility of the nanofiber sheet with the skin may not be sufficient. On the other hand, when a water-soluble polymer is added to the nanofiber sheet in order to improve the compatibility with the skin, the compatibility with the skin is improved, but the nanofiber sheet may absorb moisture, dissolve, and adhere to the substrate, making it difficult to transfer. In addition, such dissolution of the nanofiber sheet tends to occur particularly under conditions such as high temperature or high humidity, and there is room for improvement in nanofiber sheets that are transferred to the skin and used. Therefore, as a result of investigations to develop a nanofiber sheet that has excellent transferability and good skin compatibility even when stored under conditions such as high temperature or high humidity, it was found that if an adhesive polymer is used in combination with the water-insoluble polymer that forms the nanofiber structure, the adhesive polymer contributes to the modification of the nanofiber surface, and a nanofiber sheet that has excellent transferability and good compatibility can be obtained even when stored under high temperature or high humidity conditions. As such an adhesive polymer, a polymer having a moisture absorption of more than 1% and not more than 40% in a high temperature and high humidity environment (left to stand for 24 hours at 40°C and 90% RH) is preferred. That is, from the viewpoint of good skin compatibility, excellent transferability, and reducing wrinkling of the nanofiber sheet attached to the skin and the inclusion of air bubbles, the moisture absorption is more than 1%, preferably 3% or more, more preferably 5% or more, and even more preferably 8% or more, and from the same viewpoint, it is 40% or less, preferably 32% or less, more preferably 29% or less, and even more preferably 18% or less. The moisture absorption of the adhesive polymer is more than 1% and not more than 40%, preferably 3% or more and not more than 32%, more preferably 5% or more and not more than 29%, and even more preferably 8% or more and not more than 18%.

[0071] The adhesive polymer may contain one or more polymers selected from polyvinylpyrrolidone, polyvinylpyrrolidone copolymers, polyalkylene glycols, and silicone structure-containing copolymers. From the viewpoint of improving the skin compatibility of the nanofiber sheet adhered to the skin and from the viewpoint of excellent transferability, it is preferable to use one or more polymers selected from polyvinylpyrrolidone copolymers and polyalkylene glycols.

[0072] Examples of polyvinylpyrrolidone copolymers include vinyl acetate-vinylpyrrolidone copolymer, vinylpyrrolidone-dimethylaminoethyl methacrylate copolymer diethyl sulfate, and vinylcaprolactam-vinylpyrrolidone-dimethylaminopropyl methacrylamide-methacryloylaminopropyl lauryldimonium chloride copolymer. From the viewpoints of improving the compatibility of the nanofiber sheet attached to the skin and of excellent transferability, it is preferable to use a vinyl acetate-vinylpyrrolidone copolymer. From the viewpoint of improving the compatibility of the nanofiber sheet with the skin, the content of one or more polymers selected from polyvinylpyrrolidone, polyvinylpyrrolidone copolymers, polyalkylene glycols, and silicone structure-containing copolymers relative to the total amount of adhesive polymers is preferably 70% by mass or more, more preferably 80% by mass or more, and even more preferably 95% by mass or more.

[0073] Vinyl acetate-vinylpyrrolidone copolymer is a copolymer obtained by polymerization of vinyl acetate and vinylpyrrolidone, and has a structure based on vinyl acetate and a structure based on vinylpyrrolidone in the polymer. Here, assuming that the structure based on vinyl acetate is VP and the structure based on vinylpyrrolidone is VA, the ratio of VP to VA (VP:VA) in the vinyl acetate-vinylpyrrolidone copolymer in the present invention is preferably in the range of VP:VA=20:80 to 80:20, more preferably in the range of VP:VA=25:75 to 65:35, from the viewpoint of improving the compatibility of the nanofiber sheet attached to the skin and from the viewpoint of excellent transferability. The ratio in this item refers to the molar ratio, and the amount of remaining monomers relative to the charged monomer composition can be calculated by gas chromatography.

[0074] More specifically, the following commercially available products can be used as polyvinylpyrrolidone and copolymers of polyvinylpyrrolidone. Product name: Rubiscol K30 (BASF Ltd.) Product name: PVA / VA E735 (Ashland Japan Co., Ltd.) Product name: PVP / VA S-630 (Ashland Japan Co., Ltd.) Product name: PVA / VA E535 (Ashland Japan Co., Ltd.) Product name: PVA / VA E335 (Ashland Japan Co., Ltd.) Product name: Gafquat (registered trademark) 734 (Ashland Japan Co., Ltd.) Product name: Aquastyle300N (Ashland Japan Co., Ltd.)

[0075] Examples of polyalkylene glycols include polyethylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, and polyoxyethylene polyoxypropylene glycol. From the viewpoint of improving the compatibility of the nanofiber sheet attached to the skin and from the viewpoint of excellent transferability, it is preferable to use polyoxyethylene polyoxypropylene glycol.

[0076] From the viewpoints of good skin compatibility, excellent transferability, and reducing wrinkling of the nanofiber sheet attached to the skin and the inclusion of air bubbles, the average number of moles of ethylene oxide added in polyoxyethylene polyoxypropylene glycol is preferably 5 to 200, more preferably 10 to 30. From the similar viewpoints, the average number of moles of propylene oxide added is preferably 5 to 100, more preferably 10 to 30. The average number of moles of ethylene oxide added can be calculated, for example, by the method described in "JIS K 0070-1992 7.1 Neutralization titration method," and the average number of moles of propylene oxide added can be determined using 1H-NMR.

[0077] As more specific examples, the following commercially available products can be used as the polyethylene glycol adduct. Product name: Pronon (registered trademark) 124P (NOF Corporation) Product name: Pronon (registered trademark) 237P (NOF Corporation) Product name: Pronon (registered trademark) 407P (NOF Corporation)

[0078] As more specific examples, the following commercially available products can be used as the silicone structure-containing copolymer. Product name: OS-88TE-E (Kao Corporation) Product name: Silicone KF-6011 (Shin-Etsu Chemical Co., Ltd.)

[0079] In addition, the following commercially available adhesive polymers can be used. Product name: Gantrez (registered trademark)-es225 (Ashland Japan Co., Ltd.)

[0080] In the nanofiber sheet used in the present invention, the content of the water-insoluble polymer is preferably 55% by mass or more, more preferably 60% by mass or more, even more preferably 65% ​​by mass or more, and even more preferably 68% by mass or more, from the viewpoints of good skin compatibility, excellent transferability, and reducing wrinkling of the nanofiber sheet attached to the skin and the inclusion of air bubbles, and from the same viewpoints, it is preferably 96% by mass or less, more preferably 85% by mass or less, even more preferably 80% by mass or less, and even more preferably 75% by mass or less. The content of the water-insoluble polymer is preferably 55% by mass or more and 96% by mass or less, more preferably 60% by mass or more and 85% by mass or less, even more preferably 65% ​​by mass or more and 80% by mass or less, and even more preferably 68% by mass or more and 75% by mass or less.

[0081] In the nanofiber sheet used in the present invention, from the viewpoints of good skin compatibility, excellent transferability, and reducing wrinkling and air bubble inclusion in the nanofiber sheet adhered to the skin, the content of the adhesive polymer is preferably 2% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, even more preferably 20% by mass or more, and even more preferably 25% by mass or more, and from the same viewpoints, it is preferably 45% by mass or less, more preferably 40% by mass or less, even more preferably 35% by mass or less, even more preferably 33% by mass or less, and even more preferably 31% by mass or less. The content of the adhesive polymer is preferably 2% by mass or more and 45% by mass or less, more preferably 10% by mass or more and 40% by mass or less, even more preferably 15% by mass or more and 35% by mass or less, still more preferably 20% by mass or more and 33% by mass or less, and even more preferably 25% by mass or more and 31% by mass or less.

[0082] From the viewpoint of further improving both the transferability and compatibility of the nanofiber sheet, it is preferable to specify the blending ratio of the water-insoluble polymer with relatively low moisture absorption in a high temperature and high humidity environment and the relatively high adhesive polymer as follows. In the nanofiber sheet used in the present invention, the proportion of adhesive polymer in the total polymer, including the water-insoluble polymer and adhesive polymer (hereinafter sometimes simply referred to as the proportion of adhesive polymer), from the viewpoints of good skin compatibility, excellent transferability, and reducing wrinkling of the nanofiber sheet adhered to the skin and the inclusion of air bubbles, is preferably 0.05 or more, more preferably 0.11 or more, even more preferably 0.15 or more, even more preferably 0.18 or more, even more preferably 0.21 or more, and from the same viewpoints, it is preferably 0.60 or less, more preferably 0.52 or less, even more preferably 0.46 or less, even more preferably 0.40 or less, even more preferably 0.38 or less, and even more preferably 0.34 or less. The ratio of the adhesive polymer to the total polymer, including the water-insoluble polymer and the adhesive polymer, is preferably 0.05 to 0.60, more preferably 0.11 to 0.52, even more preferably 0.15 to 0.46, still more preferably 0.18 to 0.40, still more preferably 0.21 to 0.38, and still more preferably 0.21 to 0.34. The ratio of the adhesive polymer is calculated by the following formula (2), where the mass (content) of the water-insoluble polymer in the nanofiber sheet is M1 and the mass (content) of the adhesive polymer is M2. Ratio of adhesive polymer = M2 / (M1+M2) ... (2)

[0083] In the nanofiber sheet used in the present invention, the water-insoluble polymer and the adhesive polymer are combined, and the nanofiber sheet is composed of a water-insoluble polymer with relatively low moisture absorption and a highly adhesive polymer in the above-mentioned blending ratio, thereby improving the moisture resistance of the nanofiber sheet, and even in a storage environment or a use environment of the nanofiber sheet, such as a high temperature and humidity environment, the occurrence of an event in which the nanofiber sheet dissolves due to moisture absorption and remains on the base layer is suppressed. This makes it possible to improve the transferability of the nanofiber sheet. In addition, even when the skin to which the nanofiber sheet is attached is exposed to a high temperature and humidity condition such as a bathroom or a dressing room for a long time, the nanofiber sheet is difficult to dissolve, and the nanofiber sheet can be made to have a stable film shape and maintain quality. In addition, the good compatibility with the skin makes it difficult for the nanofiber sheet to become twisted or have air bubbles mixed in, and the boundary between the skin to which the nanofiber sheet is attached and the skin to which the nanofiber sheet is not attached is difficult to distinguish, making it possible to achieve a natural appearance that does not feel the presence of the nanofiber sheet.

[0084] The nanofiber sheet used in the present invention may contain, in addition to the one or more polymers described above, for example, a polyol, a liquid oil, and a surfactant. Examples of polyols that can be contained in the nanofiber sheet include alkylene glycols such as ethylene glycol, propylene glycol, 1,3-propanediol, and 1,3-butylene glycol; polyalkylene glycols such as diethylene glycol, dipropylene glycol, polyethylene glycol and polypropylene glycol having a molecular weight of 1000 or less; and glycerins such as glycerin, diglycerin, and triglycerin. Of these, from the viewpoint of the durability of the coating obtained in steps (2) and (3), the polyol is preferably contained in the nanofiber sheet in an amount of 0.00001% by mass to 5% by mass, more preferably 0.0001% by mass to 4% by mass, and even more preferably 0.001% by mass to 3% by mass.

[0085] The nanofiber sheet used in step (2-1) is a nanofiber sheet formed on a substrate, preferably by, for example, an electrospinning method or a melt flow method. The substrate may be any substrate other than skin, and may be, for example, a film made of a synthetic resin, such as a polyolefin resin or a polyester resin, or a fiber sheet, such as a nonwoven fabric. In addition, from the viewpoint of facilitating peeling of the nanofiber sheet from the skin after it is transferred to the skin, it is preferable that at least the contact surface between the nanofiber sheet and the substrate is breathable. By allowing air to enter between the nanofiber sheet and the substrate, the nanofiber sheet can be easily peeled off. The nanofiber sheet used in step (2-1) does not mean, for example, a nanofiber sheet formed by a user using a handy electrostatic spray device, but preferably means a nanofiber sheet formed on a substrate and stored in a package until use. There are no restrictions on the material of the packaging material, and it can be, for example, a laminated film in which a barrier layer such as an aluminum sheet (aluminum foil) or a silica vapor deposition film is sandwiched between the layers and the front and back of the layer are covered with synthetic resin film layers made of, for example, polyethylene, polyethylene terephthalate, polypropylene, polyester, polyamide, polyvinyl chloride, etc. Furthermore, there is no limitation on the shape of the package, and it can be, for example, a pillow bag, a gusset bag, a pouch, a box, a bottle, a jar, or the like. A single package may contain one nanofiber sheet, or two or more nanofiber sheets. Also, two or more nanofiber sheets may be connected and contained in a single package. In this case, for example, perforations may be provided in the nonwoven fabric, and the sheet-type cosmetic material to be used can be cut along the perforations and used. The nanofiber sheet in this embodiment is preferably contained in a package, and more preferably sealed in a package.

[0086] As the breathable substrate, a fiber sheet or a sponge is preferably used. Specifically, the fiber sheet is various nonwoven fabrics, woven fabrics, knitted fabrics, paper, mesh sheets, and laminates thereof. Examples of nonwoven fabrics include, but are not limited to, meltblown nonwoven fabrics, spunbond nonwoven fabrics, air-through nonwoven fabrics, spunlace nonwoven fabrics, and rayon nonwoven fabrics. The fibers or strands constituting these fiber sheets such as nonwoven fabrics and mesh sheets are preferably thicker than those in the category of nanofiber sheets. In addition, fibers made of fiber-forming synthetic resins and natural cellulose fibers such as cotton and pulp can be used as fibers. Specifically, the sponge is made of a porous material obtained by foaming synthetic resins or natural resins, such as foamed resins. Examples of synthetic resins or natural resins that can be used include, but are not limited to, urethane, polyethylene, melamine, natural rubber, chloroprene rubber, ethylene propylene rubber, nitrile rubber, silicone rubber, and fluororubber. Various materials can be used as the foamed resin as long as they can form a breathable form. From the viewpoint of easily attaching and peeling the nanofiber sheet to the skin after application in step (1), the substrate is more preferably a nonwoven fabric.

[0087] When the substrate layer is laminated to the nanofiber sheet in a peelable manner, it is preferable to apply a release treatment such as coating with a silicone resin or corona discharge treatment to the surface of the substrate facing the nanofiber sheet in order to improve the peelability. Also, when a synthetic resin film or the like is used as the substrate, it is preferable to coat the surface of the film with a release agent by dispersing a powder or granular release agent on the surface of the film. Examples of the release agent include silicone-based, fluorine-based, alkyd-based, olefin-based, and long-chain alkyl-based release agents.

[0088] The operation of step (2) involves attaching the nanofiber sheet formed on the substrate to the skin after application of step (1), together with the substrate, and then peeling off only the substrate. This simple operation allows a homogeneous coating to be formed on the skin.

[0089] [Process (2-2)] Step (2-2) is a step of electrostatically spraying a volatile medium solution containing a water-insoluble polymer directly onto the skin after application in step (1) to form a nanofiber sheet formed by deposition of nanofibers. The water-insoluble polymer used here may be the same as that used in the step (2-1). The adhesive polymer may also be used in combination. The contents and mixing ratios of the water-insoluble polymer and the adhesive polymer in the nanofiber sheet are the same as those in the step (2-1).

[0090] The volatile medium used in the step (2-2) is preferably one or more volatile substances selected from water, alcohols and ketones. These volatile substances are substances that are volatile in a liquid state. In a solution containing a water-insoluble polymer and the volatile substance (also referred to as a spray composition in step (2-2)), the volatile substance is discharged from the nozzle tip toward the skin after the spray composition placed in an electric field is sufficiently charged, and as the volatile substance evaporates, the charge density of the spray composition becomes excessive, and the volatile substance further evaporates while being further finely divided by Coulomb repulsion, and is blended for the purpose of finally forming a dry coating. For this purpose, the vapor pressure of the volatile substance at 20°C is preferably 0.01 kPa or more and 106.66 kPa or less, more preferably 0.13 kPa or more and 66.66 kPa or less, even more preferably 0.67 kPa or more and 40.00 kPa or less, and even more preferably 1.33 kPa or more and 40.00 kPa or less.

[0091] Among the volatile substances, the alcohols preferably include, for example, monohydric chain aliphatic alcohols, monohydric cyclic aliphatic alcohols, and monohydric aromatic alcohols. The monohydric chain aliphatic alcohols include C1-C6 alcohols, the monohydric cyclic alcohols include C4-C6 cyclic alcohols, and the monohydric aromatic alcohols include benzyl alcohol and phenylethyl alcohol. Specific examples of these alcohols include ethanol, isopropyl alcohol, butyl alcohol, phenylethyl alcohol, n-propanol, and n-pentanol. One or more of these alcohols may be used.

[0092] Among the volatile substances, the ketones include di-C1-C4 alkyl ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, etc. These ketones can be used alone or in combination of two or more.

[0093] The volatile substance is more preferably one or more selected from ethanol, isopropyl alcohol, butyl alcohol and water, more preferably one or more selected from ethanol and butyl alcohol, and even more preferably a volatile substance containing ethanol.

[0094] The content of the volatile substance in the spray composition is preferably 50% by mass or more, more preferably 55% by mass or more, and even more preferably 60% by mass or more. It is also preferably 98% by mass or less, more preferably 96% by mass or less, and even more preferably 94% by mass or less. The content of the volatile substance in the spray composition is preferably 50% by mass or more and 98% by mass or less, more preferably 55% by mass or more and 96% by mass or less, and even more preferably 60% by mass or more and 94% by mass or less. By including the volatile substance in the spray composition in this amount, the spray composition can be sufficiently volatilized when performing the electrostatic spray method. Furthermore, the amount of ethanol is preferably 50% by mass or more, more preferably 65% ​​by mass or more, and even more preferably 80% by mass or more, based on the total amount of volatile substances. Also, it is preferably 100% by mass or less. The amount of ethanol is preferably 50% by mass or more and 100% by mass or less, more preferably 65% ​​by mass or more and 100% by mass or less, and even more preferably 80% by mass or more and 100% by mass or less, based on the total amount of volatile substances.

[0095] The content of the water-insoluble polymer, or the water-insoluble polymer and the adhesive polymer in the spray composition is preferably 2% by mass or more, more preferably 4% by mass or more, and even more preferably 6% by mass or more. It is also preferably 50% by mass or less, more preferably 45% by mass or less, and even more preferably 40% by mass or less. The content of the polymer in the spray composition is preferably 2% by mass or more and 50% by mass or less, more preferably 4% by mass or more and 45% by mass or less, and even more preferably 6% by mass or more and 40% by mass or less. By including the polymer in the spray composition in this amount, the desired coating can be efficiently formed.

[0096] The ratio (volatile substance / polymer) of the content of the volatile substance to the polymer (the water-insoluble polymer, or the water-insoluble polymer and the adhesive polymer) in the spray composition is preferably 0.5 or more and 40 or less, more preferably 1 or more and 30 or less, and even more preferably 2 or more and 25 or less, from the viewpoint of sufficiently volatilizing the volatile substance when performing the electrostatic spray method. In addition, the ratio of the ethanol content to the polymer content in the spray composition (ethanol / the polymer) is preferably 0.5 or more and 40 or less, more preferably 1 or more and 30 or less, and even more preferably 2 or more and 25 or less, from the viewpoint of being able to sufficiently volatilize ethanol when performing the electrostatic spray method.

[0097] When performing the electrostatic spray method, the spray composition has a viscosity of preferably 1 mPa·s or more, more preferably 10 mPa·s or more, and even more preferably 50 mPa·s or more at 25°C. The spray composition has a viscosity of preferably 5000 mPa·s or less, more preferably 2000 mPa·s or less, and even more preferably 1500 mPa·s or less at 25°C. The viscosity of the spray composition is preferably 1 mPa·s or more and 5000 mPa·s or less, more preferably 10 mPa·s or more and 2000 mPa·s or less, and even more preferably 50 mPa·s or more and 1500 mPa·s or less at 25°C. By using a spray composition having a viscosity in this range, a porous coating, particularly a nanofiber sheet consisting of a deposit of nanofibers, can be formed by the electrostatic spray method. The viscosity of the spray composition is measured at 25°C using an E-type viscometer. For example, an E-type viscometer manufactured by Tokyo Keiki Co., Ltd. can be used as the E-type viscometer. In this case, rotor No. 43 can be used as the rotor.

[0098] In step (2-2), the spray composition is directly sprayed onto the skin after application in step (1) by electrostatic spraying. The electrostatic spraying includes a step of electrostatically spraying the spray composition onto the skin using an electrostatic spray device. The electrostatic spray device basically has a container for storing the spray composition, a nozzle for ejecting the spray composition, a supply device for supplying the spray composition stored in the container to the nozzle, and a power source for applying a voltage to the nozzle. Specifically, the device described in Patent Document 2 can be used.

[0099] The nanofibers formed on the skin in step (2-2) preferably have the same thickness and length as those obtained in step (2-1), and the nanofiber sheet preferably has the same thickness as those obtained in step (2-1).

[0100] [Process (3)] Step (3) is a step of applying a cosmetic composition containing one or more selected from ester oil and fine powders (hereinafter also referred to as cosmetic composition Y) to the coating film formed in step (2). Cosmetic composition Y is a composition different from the emulsion composition of step (1), and for example, the content of the same type of cationic polymer in the aforementioned emulsion composition is preferably less than the content in the aforementioned emulsion composition, more preferably 50% by mass or less, even more preferably 10% by mass or less, and even more preferably does not contain any cationic polymer.

[0101] Examples of the ester oil contained in the cosmetic composition Y include vegetable oils such as jojoba oil and olive oil, animal oils such as liquid lanolin, monoalcohol fatty acid esters, polyhydric alcohol fatty acid esters, and functional ester oils such as ultraviolet absorbers, preservatives such as benzoic acid esters, and antioxidants such as tocopherol, and it is preferable to contain one or more types selected from these ester oils. More preferably, functional ester oils such as ultraviolet absorbers, preservatives, and antioxidants can be used. The functional ester oil is more preferably one or more types selected from ultraviolet absorbers and antioxidants, and even more preferably an ultraviolet absorber. Among these, the ultraviolet absorbing agent is particularly preferably an organic ultraviolet absorbing agent, and examples of the organic ultraviolet absorbing agent that are oil-soluble include a benzoic acid-based ultraviolet absorbing agent, an anthranilic acid-based ultraviolet absorbing agent, a salicylic acid-based ultraviolet absorbing agent, a cinnamic acid-based ultraviolet absorbing agent, a benzophenone-based ultraviolet absorbing agent, and a triazine-based ultraviolet absorbing agent.

[0102] Benzoic acid-based ultraviolet absorbers include para-aminobenzoic acid (hereinafter abbreviated as PABA), glyceryl PABA, ethyl dihydroxypropyl PABA, N-ethoxylate PABA ethyl ester, N-dimethyl PABA ethyl ester, N-dimethyl PABA butyl ester, N-dimethyl PABA amyl ester, octyl dimethyl PABA, diethylaminohydroxybenzoyl hexyl benzoate, etc. From the viewpoint of enhancing the ultraviolet absorbing effect while suppressing stickiness, para-aminobenzoic acid and diethylaminohydroxybenzoyl hexyl benzoate are preferred, and diethylaminohydroxybenzoyl hexyl benzoate is more preferred. Examples of anthranilic acid-based ultraviolet absorbers include homomenthyl-N-acetylanthranilate. Examples of salicylic acid-based ultraviolet absorbers include amyl salicylate, menthyl salicylate, homomenthyl salicylate, octyl salicylate, phenyl salicylate, benzyl salicylate, and p-isopropanol phenyl salicylate. Examples of cinnamic acid-based ultraviolet absorbing agents include ethyl-4-isopropyl cinnamate, ethyl-2,4-diisopropyl cinnamate, methyl-2,4-diisopropyl cinnamate, propyl-p-methoxy cinnamate, isopropyl-p-methoxy cinnamate, isoamyl-p-methoxy cinnamate, 2-ethylhexyl-p-methoxy cinnamate, 2-ethoxyethyl-p-methoxy cinnamate, cyclohexyl-p-methoxy cinnamate, ethyl-α-cyano-β-phenyl cinnamate, 2-ethylhexyl-α-cyano-β-phenyl cinnamate, glyceryl mono-2-ethylhexanoyl di-para-methoxy cinnamate, etc. Among these, from the viewpoint of enhancing the ultraviolet absorbing effect, one or more selected from 2-ethylhexyl-p-methoxy cinnamate are preferred, and 2-ethylhexyl-p-methoxy cinnamate is more preferred. Examples of benzophenone-based ultraviolet absorbers include 2,4-dihydroxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2-hydroxy-4-methoxybenzophenone, 4-phenylbenzophenone, 2-ethylhexyl-4'-phenylbenzophenone-2-carboxylate, 2-hydroxy-4-n-octoxybenzophenone, and 4-hydroxy-3-carboxybenzophenone. As the triazine-based ultraviolet absorber, from the viewpoint of enhancing the ultraviolet absorbing effect, one or more selected from 2,4,6-tris[4-(2-ethylhexyloxycarbonyl)anilino]-1,3,5-triazine, 2,4-bis-[{4-(2-ethylhexyloxy)-2-hydroxy}-phenyl]-6-(4-methoxyphenyl)-1,3,5-triazine, and the like are preferable. Other examples include 3-(4'-methylbenzylidene)-dl-camphor, 3-benzylidene-dl-camphor, urocanic acid ethyl ester, 2-phenyl-5-methylbenzoxazole, 2,2'-hydroxy-5-methylphenylbenzotriazole, 2-(2'-hydroxy-5-t-octylphenyl)benzotriazole, dibenzalazine, dianisoylmethane, 4-methoxy-4'-t-butyldibenzoylmethane, 5-(3,3-dimethyl-2-norbornylidene)-3-pentan-2-one, benzene bis-1,3-diketone derivatives described in JP-A-2-212579, and benzoyl pinacolone derivatives described in JP-A-3-220153.

[0103] As the ultraviolet absorbing agent, from the viewpoint of enhancing the ultraviolet protection effect, it is preferable to contain at least one type selected from benzoic acid-based ultraviolet absorbing agents, benzophenone-based ultraviolet absorbing agents, cinnamic acid-based ultraviolet absorbing agents, and triazine-based ultraviolet absorbing agents, it is more preferable to contain at least one type selected from benzoic acid-based ultraviolet absorbing agents, cinnamic acid-based ultraviolet absorbing agents, and triazine-based ultraviolet absorbing agents, and it is even more preferable to contain at least two types selected from benzoic acid-based ultraviolet absorbing agents, cinnamic acid-based ultraviolet absorbing agents, and triazine-based ultraviolet absorbing agents.

[0104] The ultraviolet absorbent contained in the cosmetic composition Y may be used alone or in combination of two or more, and the combination and content are determined according to the ultraviolet protection effect and other purposes. From the viewpoint of further exerting the ultraviolet protection effect, the content of the ultraviolet absorbent in the cosmetic composition Y is preferably 0.1% by mass or more, more preferably 1% by mass or more, even more preferably 5% by mass or more, and even more preferably 10% by mass or more. In addition, from the viewpoint of suppressing stickiness and imparting a smooth feeling, the content of the ultraviolet absorbent in the cosmetic composition Y is preferably 30% by mass or less, more preferably 25% by mass or less, even more preferably 20% by mass or less, and even more preferably 18% by mass or less.

[0105] Examples of the preservative include paraoxybenzoic acid esters such as methylparaben, ethylparaben, propylparaben, butylparaben, etc. Examples of the antioxidant include ascorbyl dipalmitate, ascorbyl palmitate, tocopherol acetate, propyl gallate, etc.

[0106] The preservatives and antioxidants contained in the cosmetic composition Y may be used alone or in combination of two or more, and the content of the preservative in the cosmetic composition Y is preferably 0.1% by mass or more, more preferably 0.25% by mass or more, even more preferably 0.5% by mass or more, and preferably 4% by mass or less, more preferably 3% by mass or less, and even more preferably 2% by mass or less. The content of the antioxidant in the cosmetic composition Y is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, even more preferably 1% by mass or more, and preferably 10% by mass or less, more preferably 7% by mass or less, and even more preferably 5% by mass or less.

[0107] Examples of ester oils other than the functional ester oils include cholesteryl 12-hydroxystearate, 2-octyldodecyl N-lauroyl-L-glutamate, 2-hexyldecyl adipate, di-2-heptylundecyl adipate, diisobutyl adipate, ethyl laurate, triethyl citrate, di-2-ethylhexyl succinate, di-2-ethylhexyl sebacate, diisopropyl sebacate, diethylhexyl naphthalenedicarboxylate, castor oil fatty acid methyl ester, isopropyl myristate, diisostearyl malate, diisostearyl malate, alkyl benzoate (having 12 to 15 carbon atoms), cetyl lactate, and myristyl lactate.

[0108] Among these, from the viewpoint of adhering a coating formed from the nanofiber sheet and cosmetic composition Y to the skin and from the viewpoint of excellent sensation when applied to the skin, at least one selected from diisobutyl adipate, di-2-ethylhexyl sebacate, isopropyl myristate, diisostearyl malate, diisostearyl malate, alkyl benzoates (having 12 to 15 carbon atoms), cetyl lactate, and myristyl lactate is preferred, and at least one selected from diisostearyl malate, alkyl benzoates (having 12 to 15 carbon atoms), cetyl lactate, and myristyl lactate is more preferred.

[0109] The content of the ester oil other than the functional ester oil in the cosmetic composition Y is preferably 0.1% by mass or more, more preferably 1% by mass or more, and even more preferably 5% by mass or more. Also, it is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less. The content of the ester oil other than the functional ester oil in the cosmetic composition Y is preferably 0.1% by mass or more and 50% by mass or less, more preferably 1% by mass or more and 40% by mass or less, and even more preferably 5% by mass or more and 30% by mass or less.

[0110] The fine powder contained in the cosmetic composition Y preferably has an average particle diameter of 0.01 μm or more and 1 μm or less in the case of a circle equivalent. For example, fine metal powder, fine metal oxide, fine pigment, fine organic powder, fine biodegradable powder, etc. can be mentioned, and the surface treatment of these can be hydrophilic treatment or hydrophobic treatment, and hydrophobic treated powder is more preferable. Furthermore, from the viewpoint of suppressing the burden on the skin of the present invention, fine metal oxide or hydrophobic treated fine metal oxide used as an ultraviolet scattering agent is preferably used as the fine powder.

[0111] As the fine metal oxide particles, from the viewpoint of availability, one or more fine metal oxide particles selected from zinc oxide, titanium oxide, cerium oxide, iron oxide, chromium oxide, cobalt oxide, zirconium oxide, magnesium oxide and aluminum oxide are preferred. Among these fine metal oxide particles, from the viewpoint of ultraviolet protection effect, one or more fine metal oxide particles selected from zinc oxide, titanium oxide and cerium oxide are preferred, and one or more fine metal oxide particles selected from zinc oxide and titanium oxide are more preferred. In addition, these fine metal oxide particles can contain trace elements with a valence of +2 or more, and metals such as iron, zirconium, calcium, manganese, magnesium and yttrium can be contained alone or in combination of two or more. From the viewpoint of ultraviolet protection effect, it is preferable to use at least fine titanium oxide as the fine metal oxide particle, and it is more preferable to use only fine titanium oxide particle or to use a combination of fine titanium oxide particle and fine zinc oxide particle.

[0112] As the fine zinc oxide particles, for example, FINEX-25, FINEX-30, FINEX-50, FINEX-75 (manufactured by Sakai Chemical Industry Co., Ltd.), MZ300 series, MZ500 series, MZ700 series (manufactured by Teika Co., Ltd.), ZnO-350 (manufactured by Sumitomo Osaka Cement Co., Ltd.), etc. are commercially available. As the fine titanium oxide particles, for example, TTO-55 series, TTO-51 series (manufactured by Ishihara Sangyo Kaisha), JR series, JA series (manufactured by Teika Co., Ltd.), etc. are commercially available. As the fine cerium oxide particles, for example, high purity cerium sold by Nikki Co., Ltd. or Seimi Chemical Co., Ltd. may be used.

[0113] Examples of fine particle pigments include color pigments such as red iron oxide, iron hydroxide, iron titanate, yellow iron oxide, carbon black, Prussian blue, ultramarine, manganese violet, cobalt violet, chromium hydroxide, and cobalt titanate; barium sulfate, calcium sulfate, magnesium sulfate, magnesium carbonate, calcium carbonate, talc, mica, kaolin, sericite, silicic acid, silicic acid anhydride, aluminum silicate, magnesium silicate, aluminum magnesium silicate, calcium silicate, barium silicate, strontium silicate, tungstate metal salts, hydroxyapatite, vermiculite, bentonite, montmorillonite, hectorite, smectite, zeolite, ceramic powder, secondary calcium phosphate, alumina, White or extender pigments such as silica, aluminum hydroxide, boron nitride, and synthetic sericite; pearl pigments (shiny powders) such as fish scale foil, titanium oxide-coated mica (titanium mica), bismuth oxychloride, titanium oxide-coated bismuth oxychloride, titanium oxide-coated talc, titanium oxide-coated colored mica, titanium oxide-iron oxide-coated mica, fine particle titanium oxide-coated mica titanium, fine particle zinc oxide-coated mica titanium, organic pigment-treated mica titanium, low-order titanium oxide-coated mica, mica, titanium oxide-coated synthetic mica, titanium oxide-coated plate-like silica, hollow plate-like titanium oxide, iron oxide-coated mica, plate-like iron oxide (MIO), aluminum flakes, stainless steel flakes, titanium oxide-coated plate-like alumina, pearl shell, gold leaf, gold-deposited resin film, and metal-deposited resin film.

[0114] Examples of fine organic powders include organic powders such as silicone resin, polymethylsilsesquioxane, nylon powder, silk powder, urethane powder, and cellulose powder; organic tar-based pigments such as Red No. 104, Red No. 102, Red No. 226, Red No. 201, Red No. 202, Yellow No. 4, and Black No. 401, organic dyes, and their lakes, and these can be used alone or in combination.

[0115] The hydrophobization treatment of the fine powder may be carried out using a known surface treatment agent for hydrophobization, and examples thereof include fluorine compound treatment, silicone treatment, silicone resin treatment, pendant treatment, silane coupling agent treatment, titanium coupling agent treatment, oil treatment, N-acylated lysine treatment, polyacrylic acid treatment, metal soap treatment, amino acid treatment, inorganic compound treatment, plasma treatment, mechanochemical treatment, silane compound treatment, and silazane compound treatment. Of these treatments, treatment with silicone or silicone resin, treatment with a silane compound or silazane compound, and treatment with a metal soap such as aluminum stearate, aluminum isostearate, or aluminum laurate are preferred from the standpoint of dispersion stability, etc.

[0116] The shape of the fine powder is not particularly limited, and examples thereof include spherical, plate-like, rod-like, spindle-like, needle-like, and irregular shapes. The average particle size of the "fine powder" is preferably 0.01 μm or more, more preferably 0.012 μm or more, even more preferably 0.015 μm or more, and is preferably 0.8 μm or less, more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. The specific range of the average particle size is preferably 0.01 μm or more and 0.8 μm or less, more preferably 0.012 μm or more and 0.5 μm or less, and particularly preferably 0.015 μm or more and 0.1 μm or less. When the fine particle metal oxide is used as an ultraviolet absorbing agent, the ultraviolet protection effect and dispersion stability can be improved by setting the average particle size in such a range. The particle size is the size obtained by observation under an electron microscope or by measurement using a particle size distribution analyzer based on the laser diffraction / scattering method, regardless of whether the particles are circular or nearly circular. Specifically, in the case of the laser diffraction / scattering method, ethanol is used as a dispersion medium and measurement is performed using a laser diffraction / scattering type particle size distribution analyzer (e.g., LMS-350, manufactured by Seishin Enterprise Co., Ltd.).

[0117] The fine powder can be used alone or in combination of two or more kinds, and the combination and content are determined according to the purpose of use. In general, the content of the fine powder in the cosmetic composition Y is preferably 0.1% by mass or more, more preferably 1% by mass or more, even more preferably 5% by mass or more, even more preferably 10% by mass or more, and is preferably 60% by mass or less, more preferably 50% by mass or less, even more preferably 40% by mass or less, and even more preferably 30% by mass or less. For example, when a fine powder is used as an ultraviolet scattering agent, the content in cosmetic composition Y is preferably 0.1% by mass or more, more preferably 1% by mass or more, even more preferably 5% by mass or more, and even more preferably 10% by mass or more, and from the viewpoint of suppressing stickiness and imparting a smooth feel, the content of the ultraviolet scattering agent in cosmetic composition Y is preferably 60% by mass or less, more preferably 50% by mass or less, even more preferably 40% by mass or less, and even more preferably 30% by mass or less. Note that when the fine powder is hydrophobized, the particle size and content refer to the particle size and mass including the agent subjected to the hydrophobization treatment.

[0118] Cosmetic composition Y may contain an oil other than the ester oil that is liquid at 20°C for the purpose of dissolving or dispersing the ester oil and fine powder such as an ultraviolet absorber, and for the purpose of improving the adhesion to the skin and durability of a coating formed containing the transferred nanofiber sheet and cosmetic composition Y.

[0119] Examples of oils that are liquid at 20°C other than the ester oils include, from the standpoint of usability such as smoothness when applied, linear or branched hydrocarbon oils such as liquid paraffin, light isoparaffin, liquid isoparaffin, squalane, and squalene, and silicone oils such as dimethylpolysiloxane, dimethylcyclopolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, and higher alcohol-modified organopolysiloxane. These liquid oils can be used alone or in combination of two or more.

[0120] Examples of the hydrocarbon oil include liquid paraffin, squalane, squalene, n-octane, n-heptane, cyclohexane, light isoparaffin, and liquid isoparaffin, and from the viewpoint of usability, liquid paraffin and squalane are preferred.

[0121] Furthermore, from the viewpoint of ensuring that the coating formed by the nanofiber sheet and cosmetic composition Y adheres to the skin, the viscosity of the hydrocarbon oil at 30° C. is preferably 10 mPa·s or more, and more preferably 30 mPa·s or more. From this viewpoint, the total content of isododecane, isohexadecane, and hydrogenated polyisobutene, which have a viscosity of less than 10 mPa·s at 30° C., in cosmetic composition Y is preferably 10% by mass or less, more preferably 5% by mass or less, even more preferably 1% by mass or less, and even more preferably 0.5% by mass or less, and may not be present. The viscosity here is measured at 30° C. using a BM type viscometer (manufactured by Tokimec Co., Ltd., measurement conditions: rotor No. 1, 60 rpm, 1 minute).

[0122] Examples of silicone oils include dimethylpolysiloxane, methylcyclopolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, and higher alcohol-modified organopolysiloxane. The kinetic viscosity of the silicone oil at 25°C is set to 3 mm from the viewpoint of allowing the coating formed by the nanofiber sheet and cosmetic composition Y to adhere to the skin. 2 / s is preferred, 4mm 2 / s is more preferable, 5mm 2 / s or more is more preferable, and 30 mm 2 / s or less is preferable, 20 mm 2 / s or less is preferable, and 10 mm 2 / s or less is even more preferable. Among these, it is preferable that the composition contains methylpolysiloxane, from the viewpoint of adhering the coating formed from the nanofiber sheet and cosmetic composition Y to the skin.

[0123] The content of oil other than the ester oil that is liquid at 20°C in the cosmetic composition Y is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 5% by mass or more. Also, it is preferably 90% by mass or less. The content of liquid oil in the cosmetic composition Y is preferably 0.1% by mass or more and 90% by mass or less, more preferably 0.5% by mass or more and 70% by mass or less, and even more preferably 50% by mass or less.

[0124] Cosmetic composition Y may further contain water and / or a polyol. When cosmetic composition Y contains water or a polyol, the form of the cosmetic composition Y may be an emulsion (O / W emulsion, W / O emulsion) or a two-layer type, but the composition is different from the emulsion composition used in step (1).

[0125] In the case where a polyol is contained, examples of the polyol include alkylene glycols such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butylene glycol, etc.; polyalkylene glycols such as diethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, etc.; glycerins such as glycerin, diglycerin, triglycerin, etc. Among these, from the viewpoint of usability such as smoothness, one or more selected from ethylene glycol, propylene glycol, 1,3-butylene glycol, dipropylene glycol, polyethylene glycol, glycerin, and diglycerin are preferred, further one or more selected from propylene glycol, 1,3-butanediol, and glycerin are more preferred, and one or two selected from propylene glycol and 1,3-butylene glycol are even more preferred.

[0126] Cosmetic composition Y contains functional ester oil, fine powder, and the above-mentioned components, and can be in the form of an oily composition, a water-in-oil type emulsion composition, an oil-in-water type emulsion composition, etc. The form can be liquid, milky, creamy, paste, solid, multi-layered, etc. Components other than ester oil, fine powder, etc. that can be blended in the cosmetic composition include the above-mentioned liquid oil, as well as solid oil, emulsifier, water, polyol, coloring pigment, extender pigment, dye, fragrance, other antioxidant, other preservative, and various other vitamins.

[0127] In particular, when cosmetic composition Y contains a hydrocarbon oil, an ester oil, a vegetable oil containing triglyceride, etc., or a polar oil such as silicone oil, the composition preferably contains water and a polar oil from the viewpoint of improving the adhesion to the skin of the coating formed by the nanofiber sheet and cosmetic composition Y, and preferably contains 40% by mass or more and 100% by mass or less of water and polar oil in total. From the viewpoint of stability, cosmetic composition Y may contain a surfactant, a polymer, or a thickener, and from the viewpoint of improving the adhesion to the skin and the moisturizing performance of the coating, it may contain an oil that is solid at 30° C., such as petrolatum, cetanol, stearyl alcohol, or ceramide. Similarly, when cosmetic composition Y contains a polyol, the composition preferably contains water and a polyol from the viewpoint of improving the adhesion to the skin of the coating formed by the nanofiber sheet and cosmetic composition Y, and preferably contains 40% by mass or more and 100% by mass or less of water and polyol in total. From the viewpoint of stability, cosmetic composition Y may contain a surfactant, a polymer, or a thickener, and from the viewpoint of improving the adhesion to the skin and the moisturizing performance of the coating, it may contain an oil that is solid at 30° C., such as petrolatum, cetanol, stearyl alcohol, or ceramide.

[0128] Cosmetic composition Y preferably has a viscosity of about 100,000 mPa·s or less, preferably 30,000 mPa·s or less, and more preferably about 10,000 mPa·s or less at 25°C, in terms of improving the adhesion between the nanofiber sheet and a coating formed from cosmetic composition Y. The viscosity of cosmetic composition Y is measured using a B-type viscometer (Toki Sangyo Co., Ltd., Model TVB-10, measurement conditions: rotor No. 1, 60 rpm, 1 minute).

[0129] Cosmetic composition Y can be applied to the film formed in steps (1) and (2) by using a method such as finger application to apply the composition to the film, and then by providing a step of spreading the composition, it becomes possible to blend the composition into the film and form a thin layer of the composition. The step of spreading cosmetic composition Y can be performed by, for example, rubbing with the user's own finger or a tool such as an applicator. Alternatively, cosmetic composition Y can be sprayed onto the film by a conventional method to form a thin layer of the composition. In this case, a separate spreading step is not particularly necessary, but the operation of spreading after spraying can be performed.

[0130] The amount of cosmetic composition Y applied onto the coating may be an amount necessary and sufficient to provide the various effects of the functional ester oil or fine powder (e.g., ultraviolet protection effect, etc.) and to improve adhesion between the nanofiber sheet formed in step (2) and the coating formed from the cosmetic composition. From the viewpoint of providing the various effects of the functional ester oil or fine powder and improving durability, the amount of cosmetic composition Y applied to the skin is preferably such that the basis weight of the composition after application is 1 g / m 2 More preferably, 3 g / m 2 More preferably, 5 g / m 2 More preferably, 10 g / m 2 From the viewpoint of the film feel, the amount is preferably 85 g / m 2 More preferably, it is 60 g / m 2 More preferably, it is 40 g / m or less. 2 and even more preferably 35 g / m2 For example, the amount of cosmetic composition Y applied to the skin is preferably such that the basis weight of the composition after application is 5 g / m 2 More than 40g / m 2 Less than 10 g / m 2 More than 35g / m 2 The quantity is as follows:

[0131] [Skin protection kit] Another aspect of the present invention is a skin protection kit comprising the following (A) and (B): (A) an oil-in-water emulsion composition X containing the components (a) and (b); (a) 0.5% by mass or more and less than 5% by mass of adhesive polymers having a maximum tensile shear load of 1 N or more and 90 N or less, as measured with reference to JIS K6850, selected from rubber-based adhesive polymers, silicone-based adhesive polymers, acrylic-based adhesive polymers, urethane-based adhesive polymers, and nonionic polymers; (b) a cationic polymer, (B) A nanofiber sheet formed on a substrate, the nanofiber sheet being formed by deposition of nanofibers whose main component is a water-insoluble polymer. The skin protection kit of the present invention may further comprise (C) a cosmetic composition Y containing one or more components selected from functional ester oils and fine powders. The kit of the present invention may comprise "the oil-in-water emulsion composition X (A)" and "the nanofiber sheet (B)". A release agent and a release sheet may be provided on the opposing surface of the nanofiber sheet formed on the substrate. The kit of the present invention may also include a usage procedure and a protocol.

[0132] In relation to the above-mentioned embodiments, the present invention further discloses the following methods and kits. <1> 1) Step (1) of applying an oil-in-water emulsion composition X containing components (a) and (b) to the skin; (a) 0.5% by mass or more and less than 5% by mass of adhesive polymers having a maximum tensile shear load of 1 N or more and 90 N or less, as measured with reference to JIS K6850, selected from rubber-based adhesive polymers, silicone-based adhesive polymers, acrylic-based adhesive polymers, urethane-based adhesive polymers, and nonionic polymers; (b) Cationic polymer 2) a step (2-1) of transferring a nanofiber sheet formed on a substrate, the nanofiber sheet being formed by deposition of nanofibers mainly composed of a water-insoluble polymer, to the skin after application of the step (1); or a step (2-2) of electrostatically spraying a volatile medium solution containing a water-insoluble polymer directly onto the skin after application of the step (1) to form a nanofiber sheet formed by deposition of nanofibers; and 3) Step (3) of applying a cosmetic composition Y containing one or more components selected from an ester oil and a fine powder to the formed coating film. A method for producing a coating on the skin, comprising the steps of: <2> The content of the cationic polymer (b) in the oil-in-water emulsion composition X is 0.05% by mass or more and 3% by mass or less. <1> The manufacturing method described above. <3> The content mass ratio (a / b) of the adhesive polymer (a) to the cationic polymer (b) in the oil-in-water emulsion composition X is 5 or more and 18 or less. <1> or <2> The manufacturing method described above. <4> (b) The cationic polymer is one or more selected from the group consisting of poly(dimethyldiallylammonium halide) type cationic polymers, cationic copolymer polymers of dimethyldiallylammonium halide and acrylamide, quaternary nitrogen-containing cellulose ethers, polyethylene glycol, epichlorohydrin, condensation products of tallow amine or cocoyl amine obtained from propyleneamine and beef tallow fatty acid, cationized vinylpyrrolidone-dimethylaminoethyl methacrylate copolymers, and N,N-dimethylaminoethyl diethyl methacrylate sulfate-N,N-dimethylacrylamide-polyethylene glycol dimethacrylate copolymers (polyquaternium-52). <1> ~ <3> 13. The method for producing a semiconductor device according to any one of the preceding claims. <5> The oil-in-water emulsion composition X further contains a polyol and a liquid oil. <1> ~ <4> 13. The method for producing a semiconductor device according to any one of the preceding claims. <6> The oil-in-water emulsion composition X further contains a solid oil. <1> ~ <5> 13. The method for producing a semiconductor device according to any one of the preceding claims. <7> The oil-in-water emulsion composition X further contains a surfactant and water. <1> ~ <6> 13. The method for producing a semiconductor device according to any one of the preceding claims. <8> The nanofiber sheet contains a water-insoluble polymer and an adhesive polymer. <1> ~ <7> 13. The method for producing a semiconductor device according to any one of the preceding claims. <9> When the mass of the water-insoluble polymer in the nanofiber is (M1) and the mass of the adhesive polymer is (M2), the value of M2 / (M1+M2) is 0.05 or more and 0.60 or less. <1> ~ <8> 13. The method for producing a semiconductor device according to any one of the preceding claims. <10> The water-insoluble polymer has a moisture absorption of 1% or less when left standing in a high-temperature and high-humidity environment (40°C, 90% RH for 24 hours). <1> ~ <9> 13. The method for producing a semiconductor device according to any one of the preceding claims. <11> The adhesive polymer has a moisture absorption of more than 1% and not more than 40% when left standing in a high temperature and high humidity environment (40°C, 90% RH for 24 hours). <8> ~ <10> 13. The method for producing a semiconductor device according to any one of the preceding claims. <12> The nanofiber has a thickness, expressed as a circle equivalent diameter, of 10 to 3000 nm, preferably 10 to 1000 nm, and a length of 100 times or more of the diameter. <1> ~ <11> 13. The method for producing a semiconductor device according to any one of the preceding claims. <13> The thickness of the nanofiber sheet is preferably 5.1 μm or more and 500 μm or less, more preferably 10 μm or more and 400 μm or less, and even more preferably 10 μm or more and 100 μm or less. <1> ~ <12> 13. The method for producing a semiconductor device according to any one of the preceding claims. <14> The water-insoluble polymer is one or more selected from the group consisting of polyvinyl butyral resin, polyurethane resin, and polylactic acid. <1> ~ <13> The method for producing according to any one of the preceding claims. <15> The adhesive polymer is one or more selected from polyvinylpyrrolidone, a copolymer of polyvinylpyrrolidone, a polyalkylene glycol, and a copolymer containing a silicone structure. <8> ~ <14> The method for producing according to any one of the preceding claims. <16> The nanofiber sheet further contains one or more selected from the group consisting of polyols, liquid oils, and surfactants. <1> ~ <15> 13. The method for producing a semiconductor device according to any one of the preceding claims. <17> The polyol content in the nanofiber sheet is 0.00001% by mass or more and 5% by mass or less. <16> The manufacturing method described above. <18> The substrate is a fiber sheet. <1> ~ <17> 13. The method for producing a semiconductor device according to any one of the preceding claims. <19> The substrate is a nonwoven fabric. <1> ~ <18> 13. The method for producing a semiconductor device according to any one of the preceding claims. <20> The ester oil contained in the cosmetic composition Y includes one or more ester oils selected from vegetable oils, animal oils, monoalcohol fatty acid esters, polyhydric alcohol fatty acid esters, and functional ester oils. <1> ~ <19> 13. The method for producing a semiconductor device according to any one of the preceding claims. <21> The functional ester oil includes an ester oil selected from an ultraviolet absorber, a preservative, and an antioxidant. <20> The manufacturing method described above. <22> The fine powder contained in the cosmetic composition Y contains an ultraviolet scattering agent, and preferably contains a fine metal oxide or a hydrophobized fine metal oxide. <1> ~ <21> 13. The method for producing a semiconductor device according to any one of the preceding claims. <23> A skin protection kit comprising the following (A) and (B): (A) an oil-in-water emulsion composition X containing the components (a) and (b); (a) 0.5% by mass or more and less than 5% by mass of adhesive polymers having a maximum tensile shear load of 1 N or more and 90 N or less, as measured with reference to JIS K6850, selected from rubber-based adhesive polymers, silicone-based adhesive polymers, acrylic-based adhesive polymers, urethane-based adhesive polymers, and nonionic polymers; (b) a cationic polymer, (B) A nanofiber sheet formed on a substrate, the nanofiber sheet being formed by deposition of nanofibers comprised primarily of a water-insoluble polymer. <24> The cosmetic composition Y further comprises one or more components selected from ester oil and fine powder. <23> The kit described. <25> The content of the cationic polymer (b) in the oil-in-water emulsion composition X is 0.05% by mass or more and 3% by mass or less. <23> or <24> The kit described. <26> The content mass ratio (a / b) of the adhesive polymer (a) to the cationic polymer (b) in the oil-in-water emulsion composition X is 5 or more and 18 or less. <23> ~ <25> 2. The kit according to claim 1 , <27> The substrate is a fiber sheet. <23> ~ <26> 2. The kit according to claim 1 , EXAMPLES

[0133] The present invention will now be described in more detail with reference to examples, but the present invention is not limited to these examples.

[0134] [Manufacturing of nanofiber sheets] A nanofiber sheet was formed on a substrate by electrospinning using an electrostatic spray device and a composition for forming a nanofiber sheet. The substrate was a rayon nonwoven fabric (product name: Omikenshi 45, Omikenshi Co., Ltd.), and the composition for forming a nanofiber sheet shown in Tables 1 and 2 was used. The manufacturing conditions for the nanofiber sheet in each example were as follows. Applied voltage: 27kV, Distance between capillary collectors: 185 mm, Discharge rate of nanofiber sheet forming composition: 1 ml / h, Manufacturing environment: 28℃, 36%RH. The thus obtained nanofiber sheet of each Example had a thickness of 30 μm, and the nanofibers had a thickness of 300 to 600 nm. The polymer content in the nanofiber sheet of each Example produced is shown in Table 3. Furthermore, Table 4 shows the content of the water-insoluble polymer and the adhesive polymer. The nanofiber sheet used for evaluation was a 3 x 3 cm square.

[0135] [Examples 1 to 3, Comparative Examples 1 to 5] The composition shown in Table 8 was applied at 6 mg / cm2 onto a substrate (HD-6 manufactured by Labsphere) or onto the skin. 2 Then, a nanofiber sheet shown in Table 3 was attached. On top of the nanofiber sheet, formulations A to C (Tables 5 to 7) having ultraviolet protection properties were applied at 1.3 mg / cm. 2 The results are shown in Table 8.

[0136] [UV protection measurement] The coating formed on the substrate (HD-6, Labsphere) was measured at five points using the above method, and the average value was taken as the value of UV protection ability. The measurement was performed using an SPF analyzer (UV-2000S, Labsphere) with and without the nanofiber sheet. The evaluation was performed on N=3 coatings. The UV protection ability of the coating (%) = value when nanofiber sheet was used / value when nanofiber sheet was not used × 100, with a being 120% or more, b being 110-119%, and c being less than 110%.

[0137] [Measurement of UV protection agent adsorption and removal ability, appearance evaluation of peeled film] The coating formed on the substrate (HD-6 manufactured by Labsphere) by the above method was measured at five points, and the average value was taken as the value of the UV protection ability. The measurement was performed using an SPF analyzer (UV-2000S manufactured by Labsphere). The coating was then peeled off and attached to another substrate, and the average value of the five points was taken as the value of the UV protection ability of the peeled film. The evaluation was performed on N=3 coatings. UV protection agent adsorption and removal ability (%) = UV protection ability of peelable film / UV protection ability of coating formed on substrate × 100, with values ​​of 91 to 100% being rated as a, 81 to 90% being rated as b, 71 to 80% being rated as c, and 70% or less being rated as d. In addition, five expert panelists evaluated the appearance of the peeled film, rating it as a if no tears or holes were found, b if some tears or holes were found, c if tears or holes were found, and d if many tears or holes were found. The evaluation was performed on N=3 coatings.

[0138] [Evaluation of skin roughness] After step (3), the coating was removed and five sensitive panelists evaluated the "absence of rough skin (itchiness, redness, and itching)" according to the following criteria. The average score for the five panelists is shown. 4: Not at all, 3: Somewhat, 2: Yes, 1: Quite a bit

[0139] [Examples 4 to 6] The composition shown in Table 9 was applied at 6 mg / cm2 onto a substrate (HD-6 manufactured by Labsphere) or onto the skin. 2 Then, a nanofiber sheet shown in Table 4 was attached. On top of the nanofiber sheet, formulations A to C (Tables 5 to 7) having ultraviolet protection properties were applied at 1.3 mg / cm. 2 The results are shown in Table 9.

[0140] [Evaluation of usability after storage at high temperature and humidity] Five expert panelists evaluated the nanofiber sheets after storage at high temperature and humidity for "ease of use (transferability, compatibility)" using the following criteria. For the evaluation, the nanofiber sheets were left to stand in an incubator (EYELA KCL-2000) at 40°C and 90% RH (high temperature and humidity environment) for 24 hours. The average score for the five panelists is shown. 4: good, 3: average, 2: bad, 1: very bad

[0141] [Table 1]

[0142]

Table 2

[0143]

Table 3

[0144]

Table 4

[0145]

Table 5

[0146]

Table 6

[0147]

Table 7

[0148]

Table 8

[0149]

Table 9

Claims

1. 1) Step (1) Applying an oil-in-water emulsion composition X containing component (a) and component (b) to the skin. (a) Adhesive polymers selected from rubber-based adhesive polymers, silicone-based adhesive polymers, acrylic-based adhesive polymers, urethane-based adhesive polymers, and nonionic polymers, with a maximum tensile shear load of 1 N or more and 90 N or less as measured in reference to JIS K6850, 0.5% by mass or more and less than 5% by mass, (b) Cationic polymers 2) A nanofiber sheet formed on a substrate, the nanofiber sheet formed by the deposition of nanofibers mainly composed of a water-insoluble polymer, is transferred to the skin after step (1) is applied (2-1), or a volatile medium solution containing a water-insoluble polymer is electrostatically sprayed directly onto the skin after step (1) is applied to form a nanofiber sheet formed by the deposition of nanofibers (2-2), and then 3) A step (3) to apply a cosmetic composition Y containing one or more components selected from ester oil and fine powder to the formed film. A method for producing a coating on the skin, characterized by having the following characteristics.

2. The method for producing a coating according to claim 1, wherein the oil-in-water emulsion composition X further contains a solid oil.

3. The method for producing a coating according to claim 1 or 2, wherein the oil-in-water emulsion composition X further contains a polyol and a liquid oil.

4. A method for producing a coating according to claim 1 or 2, wherein the water-insoluble polymer is a water-insoluble polymer whose moisture absorption under high temperature and high humidity conditions (standing for 24 hours at 40°C and 90% RH) is 1% or less.

5. A method for producing a nanofiber sheet according to claim 1 or 2, wherein the nanofiber sheet contains a water-insoluble polymer and an adhesive polymer whose moisture absorption is greater than 1% but less than or equal to 40% under high temperature and high humidity conditions (standing for 24 hours at 40°C and 90% RH).

6. A method for producing a film according to claim 1 or 2, wherein the cosmetic composition Y contains one or more selected functional ester oils.

7. The manufacturing method according to claim 1 or 2, wherein the cosmetic composition Y contains one or more selected from fine powders.

8. A skin protection kit comprising the following (A) and (B). (A) Oil-in-water emulsion composition X containing component (a) and component (b), (a) Adhesive polymers selected from rubber-based adhesive polymers, silicone-based adhesive polymers, acrylic-based adhesive polymers, urethane-based adhesive polymers, and nonionic polymers, with a maximum tensile shear load of 1 N or more and 90 N or less as measured in reference to JIS K6850. 0.5 Mass% or more and less than 5% by mass, (b) Cationic polymers, (B) A nanofiber sheet formed on a substrate, the nanofiber sheet formed by depositing nanofibers mainly composed of a water-insoluble polymer.

9. Furthermore, the skin protection kit according to claim 8 comprises (C) a cosmetic composition Y containing one or more selected from functional ester oils and fine powders.