Method for producing film

Abstract

To provide a composition for forming a film having high sebum resistance on the skin or the like by electrostatic spraying and to provide a method for producing a film having high sebum resistance.SOLUTION: There is provided a composition for forming a film which is used for directly forming a film composed of a deposit containing a fiber on the skin by electrostatic spraying and comprises the following components (A), (B) and (C): (A) one or two or more volatile substances selected from water, an alcohol and a ketone, (B) a water-insoluble polymer having fiber-forming ability and (C) one or two or more selected from polyols, wherein the composition comprises (B1) the polymer having a molecular weight of 1×105 or more as the component (B), the mass content ratio ((B1) / (B)) of the component (B1) to the component (B) is 0.5 or more and the mass content ratio ((B) / (C)) of the component (B) to the component (C) is 1 or more.SELECTED DRAWING: None

Description

[Technical Field]

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

[0002] Various methods for forming a film on the skin or the like by electrostatic spraying are known. For example, Patent Documents 1 to 3 describe methods for forming a film on the skin by electrostatically spraying a composition onto the skin. The composition used in this method contains a volatile substance, a polymer having film-forming ability, etc. By electrostatic spraying, the volatile substance volatilizes, forming a film on the skin or the like, which is made of a polymer having film-forming ability, etc. Devices for carrying out these electrostatic sprays have also been reported (Patent Documents 4 and 5). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2006-104211 [Patent Document 2] Japanese Patent Application Publication No. 2018-177797 [Patent Document 3] Japanese Patent Application Publication No. 2018-177803 [Patent Document 4] Special Publication No. 2003-507165 [Patent Document 5] Japanese Patent Application Publication No. 2019-210558 Summary of the Invention [Problem to be solved by the invention]

[0004] However, it has been found that the coating obtained by electrostatically spraying a composition containing the above-mentioned volatile substance and a polymer capable of forming a coating may cause problems such as noticeable pores, breakage of the coating, reduced coating removability, etc., depending on the site and person to which it is applied. When the sites and people on which these symptoms occur were investigated, it was found that they occur in people with a lot of sebum or in sites with a lot of sebum. Accordingly, the present invention provides a composition for forming a highly sebum-resistant coating on the skin or the like by electrostatic spraying, and a method for producing a highly sebum-resistant coating. [Means for solving the problem]

[0005] Therefore, the present inventors have conducted extensive research into the composition of spray compositions used in electrostatic spraying and have found that by blending a certain amount of polyol in addition to a fiber-forming polymer with a specific molecular weight distribution and a volatile substance, the film formed will not break even in the presence of a large amount of sebum and will have a good feel to the touch.Furthermore, they have also found that when a film formed in an area with a large amount of sebum is peeled off and removed, the film can be easily and cleanly removed, thereby completing the present invention.

[0006] That is, the present invention provides a composition comprising the following components (A), (B) and (C): (A) one or more volatile substances selected from water, alcohols, and ketones; (B) a water-insoluble polymer having fiber-forming properties, and (C) Contains one or more polyols selected from the group consisting of polyols, As component (B), (B1) molecular weight 1 × 10 5 Contains the above polymer, the mass ratio of component (B1) to component (B) ((B1) / (B)) is 0.5 or more, The mass ratio of component (B) to component (C) ((B) / (C)) is 1 or more. The present invention provides a film-forming composition for forming a film consisting of a fibrous deposit directly on the skin by electrostatic spraying. The present invention also provides a composition comprising the following components (A), (B) and (C): (A) one or more volatile substances selected from water, alcohols, and ketones; (B) a water-insoluble polymer having fiber-forming properties, and (C) Contains one or more polyols selected from the group consisting of polyols, The number average molecular weight of component (B) is 4.5 x 10 4 That's all, The mass ratio of component (B) to component (C) ((B) / (C)) is 1 or more. The present invention provides a film-forming composition for forming a film consisting of a fibrous deposit directly on the skin by electrostatic spraying.

[0007] The present invention also provides a composition comprising the following components (A), (B) and (C): (A) one or more volatile substances selected from water, alcohols, and ketones; (B) a water-insoluble polymer having fiber-forming properties, and (C) Contains one or more polyols selected from the group consisting of polyols, As component (B), (B1) molecular weight 1 × 10 5 Contains the above polymer, the mass ratio of component (B1) to component (B) ((B1) / (B)) is 0.5 or more, The present invention provides a method for producing a coating, which uses a composition in which the mass ratio of component (B) to component (C) ((B) / (C)) is 1 or more to form a coating consisting of a deposit containing fibers on the surface of an object to be coated. The present invention further provides a composition comprising the following components (A), (B) and (C): (A) one or more volatile substances selected from water, alcohols, and ketones; (B) a water-insoluble polymer having fiber-forming properties, and (C) Contains one or more polyols selected from the group consisting of polyols, The number average molecular weight of component (B) is 4.5 x 10 4 That's all, The present invention provides a method for producing a coating, which uses a composition in which the mass ratio of component (B) to component (C) ((B) / (C)) is 1 or more to form a coating consisting of a deposit containing fibers on the surface of an object to be coated. [Effects of the Invention]

[0008] According to the present invention, even on surfaces such as skin where a large amount of sebum is present, it is possible to form a coating made of deposits including fibers, which is uniform, has high adhesion and transparency, does not break or lift, and has a pleasant feel. Furthermore, when a coating formed on an area with a large amount of sebum is peeled off and removed, the coating can be easily and cleanly removed. [Brief explanation of the drawings]

[0009] [Figure 1] FIG. 1 is a schematic diagram showing the configuration of an electrostatic spray device that is preferably used in the present invention. [Figure 2] FIG. 2 is a schematic diagram showing how the electrostatic spraying method is carried out using an electrostatic spraying device. DETAILED DESCRIPTION OF THE INVENTION

[0010] The present invention will now be described based on preferred embodiments thereof with reference to the drawings. The coating manufacturing method of the present invention is a method for forming a coating consisting of fiber-containing deposits on the surface of an object to be coated, such as skin. In an embodiment of the present invention, a composition containing predetermined components is applied to the object to be coated, such as skin, to form a coating. The present invention employs an electrostatic spray method as a coating formation method. The electrostatic spray method involves applying a positive or negative high voltage to a composition to charge the composition, and then spraying the charged composition toward the object to be coated, such as skin. The sprayed composition spreads into space while repeatedly atomizing due to Coulomb repulsion, and during this process, or after adhesion to the skin, the volatile solvent dries, forming a coating consisting of fiber-containing deposits on the surface of the skin. Note that electrostatic spinning is a preferred electrostatic spray method. The composition used for electrostatic spraying is also called a "spray composition" or a "spinning composition."

[0011] The composition used in the present invention (hereinafter also referred to as the "spray composition") is liquid in the environment in which the electrostatic spray method is performed. This composition contains the following components (A), (B), and (C). (A) one or more volatile substances selected from water, alcohols, and ketones; (B) a water-insoluble polymer having fiber-forming ability; (C) One or more polyols selected from the group consisting of polyols;

[0012] In addition, in an embodiment of the present invention, from the viewpoint of imparting excellent sebum resistance and a good feel to the resulting film containing fiber deposits, component (B) is preferably one of the following (1) to (4): (1) As component (B), (B1) molecular weight 1×10 5 The composition contains the above polymers, and the mass ratio of component (B1) to component (B) ((B1) / (B)) is 0.5 or more, and the mass ratio of component (B) to component (C) ((B) / (C)) is 1 or more. (2) The number average molecular weight of component (B) is 4.5 × 10 4 If it is more than or equal to: (3) The composition is obtained by adding components (A), (B), and (C), and the number average molecular weight of component (B) is 4.5 × 10 4 If it is more than or equal to: (4) The peak of the molecular weight distribution of component (B) is 9.0 × 10 4 If the polymer is more than Each component will be described below.

[0013] The volatile substance of component (A) is a substance that is volatile in a liquid state. In the spray composition, component (A) is added to the spray composition by sufficiently charging the spray composition in an electric field and then ejecting it from the tip of a nozzle toward the target for fiber formation, such as skin. As component (A) evaporates, the charge density of the spray composition becomes excessive, causing further evaporation of component (A) while further breaking down the particles due to Coulomb repulsion, ultimately forming a coating containing a dry fiber deposit. 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.

[0014] Among the volatile substances of component (A), the alcohols preferably include, for example, monohydric chain aliphatic alcohols, monohydric cyclic aliphatic alcohols, and monohydric aromatic alcohols. Examples of monohydric chain aliphatic alcohols include C1-C6 alcohols, monohydric cyclic alcohols include C4-C6 cyclic alcohols, and monohydric aromatic alcohols include benzyl alcohol and phenylethyl alcohol. Specific examples include ethanol, isopropyl alcohol, butyl alcohol, phenylethyl alcohol, n-propanol, and n-pentanol. One or more of these alcohols can be used. Among the volatile substances of component (A), the alcohols do not include polyols, which are polyhydric alcohols, but are alcohols other than component (C), which will be described later.

[0015] Among the volatile substances of component (A), 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.

[0016] Water can also be contained in component (A). When water is contained, it is preferable to use water in combination with an alcohol and / or a ketone. The content of water in component (A) is preferably 0.01% by mass or more and 5% by mass or less, from the viewpoints of the volatility of component (A) and the adhesion of the coating to the skin.

[0017] The volatile substance of component (A) 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.

[0018] The content of component (A) in the spray composition is preferably 45% by mass or more, more preferably 50% by mass or more, and even more preferably 55% by mass or more. It is also preferably 95% by mass or less, more preferably 94% by mass or less, and even more preferably 93% by mass or less. The content of component (A) in the spray composition is preferably 45% by mass or more and 95% by mass or less, more preferably 50% by mass or more and 94% by mass or less, and even more preferably 55% by mass or more and 93% by mass or less. By including component (A) in the spray composition in this proportion, the spray composition can be sufficiently volatilized when electrostatic spraying is performed, even in the presence of component (C). 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 in component (A). It is also 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 in component (A).

[0019] The water-insoluble polymer having fiber-forming ability, component (B), is generally a substance that can be dissolved in the volatile substance, component (A). Here, "dissolved" means that the polymer is in a dispersed state at 20°C, and that the dispersed state is visually uniform, preferably visually transparent or translucent.

[0020] The water-insoluble polymer having fiber-forming ability is selected appropriately depending on the properties of the volatile substance of component (A). In this specification, the term "water-insoluble polymer" refers to a polymer that, when weighed at 1 atmosphere and 23°C, is immersed in 10 g of ion-exchanged water for 24 hours, does not dissolve more than 0.5 g of the immersed polymer.

[0021] Examples of water-insoluble, fiber-forming polymers (B) include fully saponified polyvinyl alcohol, which can be insolubilized after fiber formation; partially saponified polyvinyl alcohol, which can be crosslinked after fiber formation by using a crosslinking agent; low-saponified polyvinyl alcohol; oxazoline-modified silicones such as poly(N-propanoylethyleneimine) graft-dimethylsiloxane / γ-aminopropylmethylsiloxane copolymers; polyvinyl acetal diethylaminoacetate; zein (a major component of corn protein); polyesters; polylactic acid (PLA); acrylic resins such as polyacrylonitrile resins and polymethacrylic acid resins; polystyrene resins; polyvinyl butyral resins; polyethylene terephthalate resins; polybutylene terephthalate resins; polyurethane resins; polyamide resins; polyimide resins; and polyamideimide resins. These water-insoluble polymers can be used alone or in combination of two or more. Of these water-insoluble polymers, it is preferable to use one or more selected from fully saponified polyvinyl alcohol, partially saponified polyvinyl alcohol, low-saponified polyvinyl alcohol, polyvinyl butyral resin, polyurethane resin, polymethacrylic acid resin, oxazoline-modified silicone, polyvinyl acetal diethylaminoacetate, and polylactic acid, more preferably to use one or more selected from polyvinyl butyral resin, polylactic acid, and polyurethane resin, even more preferably to contain polyvinyl butyral resin, and even more preferably to use polyvinyl butyral resin as the main component.

[0022] In the present invention, it is preferable that component (B) has a specific molecular weight or molecular weight distribution from the viewpoint of imparting excellent sebum resistance to a coating containing fiber deposits. Furthermore, by having component (B) have such a specific molecular weight or molecular weight distribution, the peelability of a coating containing sebum is significantly improved. The molecular weight of component (B) is determined by preparing a calibration curve using standard polystyrene using gel permeation chromatography (GPC). First, in one embodiment, component (B) is (B1) molecular weight 1 × 10 5It is preferable that the above polymers are contained, and the mass ratio of component (B1) to component (B) ((B1) / (B)) is 0.5 or more. That is, it is preferable that component (B) contains a (B1) having a molecular weight of 1×10 5 The content of the above polymers is preferably 50% by mass or more. The mass ratio of component (B1) to component (B) ((B1) / (B)) is preferably 0.51 or more, more preferably 0.53 or more, and even more preferably 0.55 or more, from the viewpoints of imparting excellent sebum resistance to the coating containing fiber deposits, improving the feel of the coating, and improving the peelability of the sebum-containing coating. Here, the upper limit of (B1) / (B) is preferably 1 or less, more preferably 0.95 or less, and even more preferably 0.9 or less, from the same viewpoints.

[0023] In another embodiment, the number average molecular weight of component (B) is 4.5×10 4 The number average molecular weight of component (B) is preferably 4.6 × 10 or more from the viewpoint of imparting excellent sebum resistance to a coating containing fiber deposits, improving the feel of the coating, and removability of a coating containing sebum. 4 It is preferable that the value is equal to or greater than 4.7×10 4 More preferably, it is 4.8×10 or more. 4 From the same viewpoint, the upper limit of the number average molecular weight of component (B) is 3×10 5 Less than 2 x 10 is preferable. 5 Less than 1.7×10 is preferable. 5 The following is even more preferred:

[0024] In another embodiment, the composition is obtained by adding component (A), component (B), and component (C), and the number average molecular weight of component (B) is 4.5×10 4 The number average molecular weight of component (B) in the composition obtained by adding component (B) is preferably 4.6 × 10 or more from the viewpoints of imparting excellent sebum resistance to a coating containing fiber deposits, improving the feel of the coating, and removability of a coating containing sebum. 4 It is preferable that the value is equal to or greater than 4.7×10 4More preferably, it is 4.8×10 or more. 4 From the same viewpoint, the upper limit of the number average molecular weight of component (B) is 3×10 5 Less than 2 x 10 is preferable. 5 Less than 1.7×10 is preferable. 5 The following is even more preferred:

[0025] In another embodiment, the molecular weight distribution peak of component (B) is 9.0 × 10 4 From the viewpoints of imparting excellent sebum resistance to a coating containing fiber deposits, improving the feel of the coating, and improving the peelability of a coating containing sebum, it is preferable that the peak of the molecular weight distribution of component (B) is 9.5 × 10 4 It is preferable that the value is equal to or greater than 1.0×10 5 More preferably, it is 1.1×10 5 From the same viewpoint, the upper limit of the peak of the molecular weight distribution of component (B) is preferably 1.0×10 6 The following is preferable: 7.0 x 10 5 Less than 5.0 x 10 is preferable. 5 Even better: 3.5 x 10 5 Even more preferred are the following:

[0026] When component (B) is a polymer whose main chain is modified with a functional group, such as a polyvinyl butyral resin, if the modification rate of the functional group is too high, the sebum resistance tends to decrease, so the modification rate of the functional group is preferably 75% or less. For example, in the case of a polyvinyl butyral resin, the acetalization rate (butyralization rate) is preferably 75% or less.

[0027] The content of component (B) in the spray composition is preferably 2% by mass or more, more preferably 4% by mass or more, and even more preferably 5% by mass or more, from the viewpoints of forming a coating containing fiber deposits on an object to be coated, such as skin, that is resistant to sebum, and of releasability of the sebum-containing coating. The content is also preferably 30% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less. The content of component (B) in the spray composition is preferably 2% by mass or more and 30% by mass or less, more preferably 4% by mass or more and 20% by mass or less, and even more preferably 5% by mass or more and 15% by mass or less. By including component (B) in the spray composition in this proportion, the desired coating containing fiber deposits can be efficiently formed.

[0028] The mass ratio of component (B) to component (A) in the spray composition ((B) / (A)) is preferably 0.03 or more and 0.5 or less, more preferably 0.04 or more and 0.4 or less, and even more preferably 0.055 or more and 0.3 or less, from the viewpoint of being able to sufficiently volatilize component (A) when performing the electrostatic spray method and to form the desired coating. Furthermore, the mass ratio of ethanol (A) to component (B) in the spray composition ((B) / (A)) is preferably 0.03 or more and 0.5 or less, more preferably 0.04 or more and 0.4 or less, and even more preferably 0.055 or more and 0.3 or less, from the viewpoint of being able to sufficiently volatilize ethanol (A) when performing the electrostatic spray method and to form the desired coating.

[0029] The component (C) used in the present invention is one or more polyols. By combining the component (B) having the specific molecular weight or molecular weight distribution with the component (C), it is possible to impart excellent sebum resistance to a coating containing fiber deposits, and further improve the feel of the coating and the peelability of the sebum-containing coating.

[0030] Examples of polyols of component (C) include alkylene glycols such as ethylene glycol, propylene glycol, 1,3-propanediol, and 1,3-butanediol; polyalkylene glycols such as diethylene glycol, dipropylene glycol, polyethylene glycols with a molecular weight of 1,000 or less, and polypropylene glycol; and glycerins such as glycerin, diglycerin, and triglycerin. Of these, from the viewpoints of being able to impart excellent sebum resistance to a coating containing fiber deposits and improving the feel of the coating and the peelability of a coating containing sebum, ethylene glycol, propylene glycol, 1,3-butanediol, dipropylene glycol, polyethylene glycols with a molecular weight of 1,000 or less, glycerin, and diglycerin are preferred, and polyethylene glycols, propylene glycol, 1,3-butanediol, and glycerin with a molecular weight of 1,000 or less are more preferred, and polyethylene glycols and 1,3-butanediol are even more preferred.

[0031] The content of component (C) in the spray composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, even more preferably 1% by mass, and is preferably 30% by mass or less, more preferably 25% by mass or less, and even more preferably 20% by mass or less, from the viewpoint of being able to impart excellent sebum resistance to a coating containing fiber deposits, improving the feel of the coating, and improving the peelability of the sebum-containing coating. Specifically, the content is preferably 0.1% by mass or more and 30% by mass or less, more preferably 0.5% by mass or more and 25% by mass or less, and even more preferably 1% by mass or more and 20% by mass or less.

[0032] Fibers formed by electrostatic spraying, preferably electrospinning, using the spray composition of the present invention can form a coating as a deposit of fibers containing component (B) as the main component and component (C) present. The presence of component (C) refers to a state in which component (C) is carried inside the fiber, on the surface of the fiber, or between the fibers.

[0033] In the spray composition of the present invention, from the viewpoints of imparting excellent sebum resistance to a coating containing fiber deposits and improving the feel of the coating and the removability of the sebum-containing coating, the mass ratio of component (B) to component (C) ((B) / (C)) is preferably at least 1. By setting the ratio at such a level, it is possible to impart excellent sebum resistance to a coating containing fiber deposits, improve the feel of the coating, and improve the removability of the sebum-containing coating. From the same viewpoint, the ratio ((B) / (C)) is more preferably 1.1 or more, and even more preferably 1.2 or more. From the same viewpoint, the upper limit of the ratio ((B) / (C)) is preferably 30 or less, more preferably 25 or less, and even more preferably 20 or less. Specifically, it is preferably 1 or more and 30 or less, more preferably 1.1 or more and 25 or less, and even more preferably 1.2 or more and 20 or less.

[0034] The spray composition of the present invention may further contain component (D) oil. (D) oil is an oil that is liquid overall (liquid at 20°C), and may contain semi-solid oils and solid oils in addition to oils that are liquid at 20°C (liquid oils). Examples of liquid oils include hydrocarbon oils, ester oils, higher alcohols, silicone oils, and fatty acids. Among these, hydrocarbon oils, ester oils, and silicone oils are preferred from the viewpoint of imparting excellent sebum resistance to a coating containing fiber deposits and improving the feel of the coating. Furthermore, one or more types selected from these liquid oils can be used in combination.

[0035] Examples of the liquid hydrocarbon oil include liquid paraffin, squalane, squalene, n-octane, n-heptane, cyclohexane, light isoparaffin, liquid isoparaffin, hydrogenated polyisobutene, polybutene, and polyisobutene. These oils can impart excellent sebum resistance to a coating containing fiber deposits, and from the viewpoint of improving the feel of the coating, liquid paraffin, light isoparaffin, liquid isoparaffin, squalane, squalene, n-octane, n-heptane, and cyclohexane are preferred, with liquid paraffin and squalane being more preferred. Furthermore, from the viewpoints of being able to impart excellent sebum resistance to a coating containing fiber deposits and improving the feel of the coating, the viscosity of the hydrocarbon oil at 30°C is preferably 1 mPa·s or more, and more preferably 3 mPa·s or more. Furthermore, from the viewpoints of being able to impart excellent sebum resistance to a coating containing fiber deposits and improving the feel of the coating, the total content of isododecane, isohexadecane, and hydrogenated polyisobutene in the liquid 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 at all. Similarly, from the viewpoints of imparting excellent sebum resistance to a coating containing fiber deposits and improving the feel of the coating, the viscosity of the ester oil and 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, and diisostearyl ether in component (D) is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 1% by mass or less.

[0036] Examples of the ester oil include esters of straight-chain or branched-chain fatty acids and straight-chain or branched-chain alcohols or polyhydric alcohols.Specifically, these include isopropyl myristate, cetyl isooctanoate, isocetyl octanoate, octyldodecyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, decyl oleate, octyldodecyl oleate, hexyldecyl dimethyloctanoate, cetyl lactate, myristyl lactate, lanolin acetate, isocetyl stearate, isocetyl isostearate, ethylhexyl isononanoate, isononyl isononanoate, isotridecyl isononanoate, isostearyl isostearate, and 12-hydroxystearyl Cholesteryl diol, ethylene glycol di-2-ethylhexanoate, dipentaerythritol fatty acid ester, N-alkyl glycol monoisostearate, propylene glycol dicaprylate, propylene glycol diisostearate, neopentyl glycol dicaprate, diisostearyl malate, glycerin di-2-heptylundecanoate, trimethylolpropane tri-2-ethylhexanoate, trimethylolpropane triisostearate, pentaerythritol tetra-2-ethylhexanoate, glyceryl tri-2-ethylhexanoate , Trimethylolpropane Triisostearate, Cetyl 2-Ethylhexanoate, 2-Ethylhexyl Palmitate, Diethylhexyl Naphthalenedicarboxylate, Benzoate (C12-15) Alkyl, Cetearyl Isononanoate, Tri(Caprylic / Capric) Glycerin, Butylene Glycol (Dicaprylic / Capric), Propylene Glycol (Dicaprylic / Capric), Glyceryl Triisostearate, Glyceryl Tri-2-Heptylundecanoate, Glyceryl Cocoate, Castor Oil Fatty Acid Methyl Ester, O Examples of suitable alkyl acrylates include oleyl leate, 2-heptylundecyl palmitate, diisobutyl adipate, 2-octyldodecyl N-lauroyl-L-glutamate, di-2-heptylundecyl adipate, ethyl laurate, di-2-ethylhexyl sebacate, 2-hexyldecyl myristate, 2-hexyldecyl palmitate, 2-hexyldecyl adipate, diisopropyl sebacate, di-2-ethylhexyl succinate, triethyl citrate, 2-ethylhexyl paramethoxycinnamate, and tripropylene glycol dipivalate. Among these, from the viewpoint of being able to impart excellent sebum resistance to a coating containing fiber deposits and improving the feel of the coating, octyldodecyl myristate, myristyl myristate, isocetyl stearate, isononyl isononanoate, isocetyl isostearate, cetearyl isononanoate, diisobutyl adipate, di-2-ethylhexyl sebacate, isopropyl myristate, isopropyl palmitate, diisostearyl malate, neopentyl glycol dicaprate, Preferably, at least one selected from isopropyl myristate, isopropyl palmitate, diisostearyl malate, neopentyl glycol dicaprate, alkyl benzoate (having 12 to 15 carbon atoms), and tri(caprylic / capric)glycerin is preferred, more preferably at least one selected from neopentyl glycol dicaprate and tri(caprylic / capric)glycerin, and even more preferably at least one selected from neopentyl glycol dicaprate and tri(caprylic / capric)glycerin.

[0037] Furthermore, as the ester oil, vegetable oils and animal oils containing the above-mentioned ester oils can be used, such as olive oil, jojoba oil, macadamia nut oil, medfoam oil, castor oil, safflower oil, sunflower oil, avocado oil, canola oil, apricot kernel oil, rice germ oil, and rice bran oil.

[0038] Examples of higher alcohols include liquid higher alcohols having 12 to 20 carbon atoms, and higher alcohols containing branched fatty acids as a constituent are preferred, and specific examples include isostearyl alcohol and oleyl alcohol.

[0039] Examples of liquid silicone oils include linear silicones, cyclic silicones, and modified silicones, such as dimethylpolysiloxane, dimethylcyclopolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, phenyl-modified silicones, and higher alcohol-modified organopolysiloxanes.

[0040] Component (D) may contain an oil that is solid at 20°C, as long as component (D) as a whole remains liquid. The oil that is solid at 20°C is not particularly limited as long as it is an oil that is commonly used in cosmetics. Examples include waxes, cholesterol derivatives, phytosterol derivatives, dipentaerythritol fatty acid esters, triglycerides, lanolin, lanosterol derivatives, petrolatum, ceramides, higher alcohols, and higher fatty acids.

[0041] The content of component (D) in the spray composition is preferably 0% by mass or more, and preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less, from the viewpoint of imparting excellent sebum resistance to a coating containing fiber deposits and improving the feel of the coating. Specifically, the content is preferably 0% by mass or more and 25% by mass or less, more preferably 0% by mass or more and 20% by mass or less, and even more preferably 0% by mass or more and 15% by mass or less. Note that a content of 0.5% by mass or more is more preferable from the viewpoint of maintaining the transparency of the coating.

[0042] The spray composition may contain only the above-mentioned components (A), (B), and (C), or may contain components (A), (B), (C), and (D), or may contain other components in addition to components (A), (B), (C), and (D). Examples of other components include plasticizers for the fiber-forming polymer of component (B), color pigments, extender pigments, dyes, surfactants, fragrances, repellents, antioxidants, stabilizers, preservatives, and various vitamins. When other components are contained in the spray composition, the content of the other components is preferably 0.1% to 30% by mass, and more preferably 0.5% to 20% by mass.

[0043] In the method for producing a coating of the present invention, the spray composition is electrostatically sprayed onto the surface of an object to be coated, thereby forming a coating consisting of a deposit containing fibers. The object to be coated may be a substrate such as resin, glass, or metal, or may be skin, but skin is preferred. When forming a coating on skin, the spray composition is electrostatically sprayed directly onto the skin surface to form a coating consisting of a deposit containing fibers on the skin surface. Of the electrostatic spray methods, electrospinning is preferably used to efficiently form a deposit containing fibers.

[0044] When performing electrostatic spraying, the spray composition, preferably the spinning composition, has a viscosity at 25°C of preferably 1 mPa·s or more, more preferably 10 mPa·s or more, and even more preferably 50 mPa·s or more. The viscosity at 25°C of the spray composition is preferably 5000 mPa·s or less, more preferably 2000 mPa·s or less, and even more preferably 1500 mPa·s or less. The viscosity of the spray composition at 25°C 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. By using a spray composition having a viscosity within this range, porous coatings, particularly porous coatings consisting of fiber deposits, can be successfully formed by electrostatic spraying. The formation of a porous coating is advantageous from the viewpoints of coating adhesion, coating transparency, suppression of coating sensation, prevention of stuffiness on the skin, etc. The viscosity of the spray composition is measured at 30°C using an E-type viscometer. As the E-type viscometer, for example, an E-type viscometer manufactured by Tokyo Keiki Co., Ltd. can be used. In this case, rotor No. 43 can be used as the rotor.

[0045] The spray composition is sprayed or dispensed by electrostatic spraying directly onto the desired area of ​​the object to be coated, preferably human skin. Here, the skin also includes nails. The electrostatic spray method includes a step of electrostatically spraying a spray composition onto skin using an electrostatic spray device. The electrostatic spray device basically includes a container for containing the composition, a nozzle for discharging the composition, a supply device for supplying the composition contained in the container to the nozzle, and a power source for applying a voltage to the nozzle.

[0046] FIG. 1 shows a schematic diagram illustrating the configuration of an electrostatic spray device suitable for use in the present invention. The electrostatic spray device 10 shown in the figure is equipped with a low-voltage power supply 11. The low-voltage power supply 11 is capable of generating a voltage of several volts to several tens of volts. To enhance the portability of the electrostatic spray device 10, the low-voltage power supply 11 preferably comprises one or more batteries. Another advantage of using a battery as the low-voltage power supply 11 is that it can be easily replaced as needed. Instead of a battery, an AC adapter or the like can also be used as the low-voltage power supply 11.

[0047] The electrostatic spray device 10 also includes a high-voltage power supply 12. The high-voltage power supply 12 is connected to the low-voltage power supply 11 and includes an electric circuit (not shown) that boosts the voltage generated by the low-voltage power supply 11 to a high voltage. The boosting electric circuit generally includes a transformer, a capacitor, semiconductor elements, etc.

[0048] The electrostatic spray device 10 further includes an auxiliary electric circuit 13. The auxiliary electric circuit 13 is located between the low-voltage power supply 11 and the high-voltage power supply 12, and has the function of adjusting the voltage of the low-voltage power supply 11 to ensure stable operation of the high-voltage power supply 12. The auxiliary electric circuit 13 also has the function of controlling the rotation speed of a motor included in a micro-gear pump 14, which will be described later. By controlling the rotation speed of the motor, the amount of spray composition supplied from a spray composition container 15, which will be described later, to the micro-gear pump 14 is controlled. A switch SW is installed between the auxiliary electric circuit 13 and the low-voltage power supply 11, and the electrostatic spray device 10 can be operated / stopped by turning the switch SW on and off. In addition to the micro-gear pump 14, a piston pump can also be used to control the supply and amount of spray composition.

[0049] The electrostatic spray device 10 further includes a nozzle 16. The nozzle 16 is made of various conductive materials such as metal, or non-conductive materials such as plastic, rubber, or ceramic, and is shaped to allow the spray composition to be discharged from its tip. A minute space through which the spray composition flows is formed within the nozzle 16 along the longitudinal direction of the nozzle 16. The cross-sectional size of this minute space, expressed in diameter, is preferably 100 μm or more and 1000 μm or less. Nozzle 16 is connected to micro gear pump 14 via conduit 17. Conduit 17 may be conductive or non-conductive. Nozzle 16 is also electrically connected to high-voltage power supply 12, which allows a high voltage to be applied to nozzle 16. In this case, nozzle 16 and high-voltage power supply 12 are electrically connected via current-limiting resistor 19 to prevent excessive current from flowing if a human body comes into direct contact with nozzle 16.

[0050] The micro gear pump 14, which is in communication with the nozzle 16 via a conduit 17, functions as a supply device that supplies the spray composition contained in the container 15 to the nozzle 16. The micro gear pump 14 is operated by receiving power from a low-voltage power supply 11. The micro gear pump 14 is also configured to be controlled by an auxiliary electric circuit 13 to supply a predetermined amount of the spray composition to the nozzle 16.

[0051] A container 15 is connected to the micro gear pump 14 via a flexible conduit 18. A spray composition is stored in the container 15. The container 15 is preferably in the form of a replaceable cartridge.

[0052] An electrostatic spray device 10 having the above configuration can be used, for example, as shown in FIG. 2. FIG. 2 shows a handheld electrostatic spray device 10 that is small enough to be held in one hand. In the electrostatic spray device 10 shown in the figure, all of the components shown in the structural diagram of FIG. 1 are housed in a cylindrical housing 20. A nozzle (not shown) is disposed at one longitudinal end 10a of the housing 20. The nozzle is disposed in the housing 20 so that the spray direction of the composition coincides with the vertical direction of the housing 20 and that the nozzle is convex toward the skin. By arranging the nozzle tip so that it is convex toward the skin in the vertical direction of the housing 20, the spray composition is less likely to adhere to the housing, allowing a stable coating to be formed.

[0053] When operating the electrostatic spray device 10, a user, i.e., a person who electrostatically sprays a coating on a target area of ​​the skin, holds the device 10 in their hand and points one end 10a of the device 10, where the nozzle (not shown) is located, toward the application area where electrostatic spraying is to be performed. Figure 2 shows the electrostatic spray device 10 with one end 10a facing the inside of the user's forearm. In this state, the device 10 is switched on to perform electrostatic spraying. When the device 10 is turned on, an electric field is generated between the nozzle and the skin. In the embodiment shown in Figure 2, a positive high voltage is applied to the nozzle, and the skin serves as the negative electrode. When an electric field is generated between the nozzle and the skin, the spray composition at the tip of the nozzle is polarized by electrostatic induction, forming a cone-shaped tip. Charged droplets of the spray composition are ejected from the tip of the cone into the air along the electric field toward the skin. As the solvent component (A) evaporates from the charged spray composition ejected into space, the charge density on the surface of the spray composition becomes excessive, and the droplets are repeatedly atomized by Coulomb repulsion, spreading into space and reaching the skin. In this case, by appropriately adjusting the viscosity of the spray composition, the sprayed composition can be made to reach the application site in the form of droplets. Alternatively, while being discharged into space, the volatile solvent can be evaporated from the droplets, and the solute, a polymer with fiber-forming ability, can be solidified while being stretched and deformed by a potential difference to form fibers, which can then be deposited at the application site. For example, increasing the viscosity of the spray composition makes it easier to deposit the composition in the form of fibers at the application site. This forms a porous coating consisting of a deposit of fibers on the surface of the application site.

[0054] During electrostatic spraying, a high potential difference occurs between the nozzle and the skin. However, because the impedance is very large, the current flowing through the human body is extremely small. The inventors have confirmed that the current flowing through the human body during electrostatic spraying is several orders of magnitude smaller than the current flowing through the human body due to static electricity generated in everyday life.

[0055] In the case of skin that contains a lot of sebum, the incorporation of component (C) into the fiber causes the fiber to swell and become more plasticized. As a result, the resulting film is transparent and has good adhesion, but its durability, i.e., its sebum resistance, is thought to be reduced. In contrast, by using a fiber-forming polymer with a specific molecular weight or molecular weight distribution as component (B), the film is flexible, yet its durability in the presence of sebum is improved, and it is thought that it will not tear or lift.

[0056] The contents of components (A), (B), and (C) in the spray composition are measured as follows: Component (A), which is a volatile substance, is not present in the formed coating, or if present, volatilizes. Therefore, components (B) and (C) are measured in the state where they are contained as the main components in the formed coating, and their contents are measured as follows.

[0057] <Method for measuring the contents of component (A), component (B), and component (C) in the spray composition> There are methods for separating and identifying compounds in solution using liquid chromatography (HPLC) or infrared spectroscopy (IR). With liquid chromatography, components with larger molecular weights are eluted first, so it is possible to predict the molecular weight and identify the composition based on the elution position of the components. With IR analysis, it is also possible to assign and identify functional groups from individual absorbers, and generally identification is possible by comparing the IR chart of the component with a standard chart of commercially available additives.

[0058] <Method for measuring the content of component (B) and component (C) in the formed coating> A solvent capable of dissolving the coating is searched for, and after dissolving the coating in the solvent, the coating is separated and identified by high performance liquid chromatography (HPLC) or by infrared spectroscopy (IR).

[0059] In principle, the fibers forming the coating are continuous fibers of infinite length, but preferably have a length at least 100 times the fiber diameter. In this specification, fibers having a length 100 times the fiber diameter are defined as "continuous fibers." The coating produced by the electrostatic spray method is preferably a porous, discontinuous coating composed of a deposit of continuous fibers. This type of coating not only can be handled as a single sheet, but also has the advantage of being very soft, resistant to shear forces, and highly adaptable to body movements. Another advantage is that the coating can be easily removed by peeling. In contrast, continuous coatings without pores are difficult to peel off and have poor sweat dissipation properties, which can cause stuffiness on the skin. Here, "requiring pores" refers to pores between fibers, including cases where, for example, liquid is present between fibers. Furthermore, porous, discontinuous coatings made of aggregates of particles are difficult to completely remove without damaging the skin, as this requires actions such as applying friction to the entire coating in order to completely remove the coating.

[0060] The thickness of the fibers forming the coating, expressed in terms of equivalent circle diameter, is preferably 10 nm or more, more preferably 50 nm or more, and even more preferably 100 nm or more. It is also preferably 3000 nm or less, more preferably 1500 nm or less, and even more preferably 1200 nm or less. The fiber thickness can be measured, for example, by observing the fibers at 10,000x magnification using a scanning electron microscope (SEM), removing defects (fiber clumps, fiber intersections, and droplets) from the two-dimensional image, randomly selecting 10 fibers, drawing a line perpendicular to the longitudinal direction of the fibers, and directly reading the fiber diameter.

[0061] During the electrostatic spraying process using the electrostatic spray device 10, the electrostatically sprayed, fibrous spray composition reaches the skin directly, leaving components (B) and (C) charged, while component (A) evaporates. As previously mentioned, since the skin is also charged, the fibers adhere to the skin in the form of a single film due to electrostatic forces. Because the surface of the skin is formed with fine irregularities such as texture, this, combined with the anchoring effect of these irregularities, is thought to further enhance the adhesion of the fibers to the skin surface in the form of a single film. Once electrostatic spraying is completed, the electrostatic spray device 10 is turned off. This eliminates the electric field between the nozzle and the skin, and the charge is fixed on the skin surface. As a result, the adhesion of the single film coating is enhanced, making it less likely to peel off during wear and improving durability during use. Furthermore, because the fibers constituting the coating contain component (C), the coating can be sufficiently adhered to the skin without the need for a separate liquid application. The reason for this is thought to be that the presence of component (C) in the fiber softens the fiber itself due to a plasticizing effect, improving its ability to conform to finely uneven surfaces, and component (C) bleeds out to the fiber surface, forming a liquid bridge between the fiber and the skin. Furthermore, since the fiber that constitutes the coating has a supported coating in which component (C) is present between the fibers or on the surface of the fibers, the fibers that constitute the coating are less likely to reflect light, making the coating more likely to appear transparent and allowing the skin to be covered in a natural-looking state.

[0062] The distance between the nozzle and the skin depends on the voltage applied to the nozzle, but is preferably 50 mm or more and 150 mm or less to successfully form a coating. The distance between the nozzle and the skin can be measured using a commonly used non-contact sensor or the like.

[0063] Regardless of whether the coating formed by electrostatic spraying is porous or not, the basis weight of the coating shall be 0.1 g / m 2 It is preferable that the content is 1 g / m or more. 2 It is more preferable that the content is 50 g / m or more. 2 Preferably, it is 40 g / m or less. 2For example, the basis weight of the coating is 0.1 g / m or less. 2 More than 50g / m 2 It is preferable that the content is less than 1 g / m 2 More than 40g / m 2 By setting the basis weight of the coating in this way, the adhesion of the coating can be improved.

[0064] The electrostatic spraying step of electrostatically spraying a composition directly onto the skin to form a coating means a step of electrostatically spraying the composition onto the skin to form a coating, and is preferably a step of electrospinning. Another method for forming a coating includes electrostatically spinning the composition onto a site other than the skin to produce a fiber deposit that forms an adhesive fiber sheet for transfer onto the skin, and then applying the adhesive fiber sheet to the skin. Such a method using an adhesive fiber sheet is different from the electrostatic spraying process.

[0065] From the viewpoint of ease of application and achieving an inconspicuous appearance, the thickness of the adhesive fiber sheet is preferably set to 100 nm to 500 μm, more preferably 500 nm to 300 μm, even more preferably 1 μm to 100 μm, and even more preferably 10 μm to 50 μm. The color of the adhesive fiber sheet before transfer to the skin is preferably transparent white or translucent white. Its L value is preferably 80 or more, more preferably 90 or more. From the viewpoint of an unobtrusive appearance, the a value and b value are preferably -20 to 30, more preferably -10 to 20, and even more preferably 0 to 10. The L value is a value defined in the CIE 1976 (L*, a*, b*) color space (CIELAB), where 100 is white and 0 is black. The fiber sheet for application is preferably prepared by electrospinning onto a peelable substrate, or formed on another substrate by electrospinning and then laminated onto the peelable substrate. The peelable substrate may be a nonwoven fabric sheet made of a synthetic resin such as a polyolefin resin or a polyester resin, with a fiber diameter larger than that of the fiber sheet, or a sheet having fine irregularities on the surface forming the film fiber sheet, for example, irregularities with a height or width greater than the fiber thickness of the present invention but not exceeding 1 mm, preferably not exceeding 500 μm.

[0066] While the present invention has been described above based on its preferred embodiments, the present invention is not limited to these embodiments. For example, in the above embodiments, a person who wants to form a coating on their skin holds the electrostatic spray device 10 and generates an electric field between the conductive nozzle of the device 10 and their skin. However, as long as an electric field is generated between the two, the person who wants to form a coating on their skin does not need to hold the electrostatic spray device 10.

[0067] In relation to the above-described embodiment, the present invention further discloses the following method for producing a coating. <1> The following components (A), (B) and (C): (A) one or more volatile substances selected from water, alcohols, and ketones; (B) a water-insoluble polymer having fiber-forming properties, and (C) Contains one or more polyols selected from the group consisting of polyols, As component (B), (B1) molecular weight 1 × 10 5 Contains the above polymer, the mass ratio of component (B1) to component (B) ((B1) / (B)) is 0.5 or more, The mass ratio of component (B) to component (C) ((B) / (C)) is 1 or more. A film-forming composition for forming a film consisting of a fibrous deposit directly on the skin by electrostatic spraying. <2> The following components (A), (B) and (C): (A) one or more volatile substances selected from water, alcohols, and ketones; (B) a water-insoluble polymer having fiber-forming properties, and (C) Contains one or more polyols selected from the group consisting of polyols, The number average molecular weight of component (B) is 4.5 x 10 4 That's all, The mass ratio of component (B) to component (C) ((B) / (C)) is 1 or more. A film-forming composition for forming a film consisting of a fibrous deposit directly on the skin by electrostatic spraying. <3> The following components (A), (B) and (C) (A) one or more volatile substances selected from water, alcohols, and ketones; (B) a water-insoluble polymer having fiber-forming properties, and (C) one or more polyols selected from the group consisting of The number average molecular weight of component (B) is 4.5 x 10 4 That's all, The mass ratio (B) / (C) of the component (B) to the component (C) is 1 or more. A film-forming composition for forming a film consisting of a fibrous deposit directly on the skin by electrostatic spraying. <4> The following components (A), (B) and (C) (A) one or more volatile substances selected from water, alcohols, and ketones; (B) a water-insoluble polymer having fiber-forming ability; (C) Contains one or more polyols selected from the group consisting of polyols, The peak of the molecular weight distribution of component (B) is 9.0 × 10 4 It is a polymer exceeding The mass ratio (B) / (C) of the component (B) to the component (C) is 1 or more. A film-forming composition for forming a film consisting of a fibrous deposit directly on the skin by electrostatic spraying.

[0068] <5> The volatile substance of component (A) preferably has a vapor pressure at 20°C of 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. <1> ~ <4> 10. The film-forming composition according to claim 9, wherein the film-forming composition is a film-forming composition according to any one of the preceding items. <6> The volatile substance of component (A) is an alcohol, and the alcohol is preferably one or more selected from monohydric chain aliphatic alcohols, monohydric cyclic aliphatic alcohols, and monohydric aromatic alcohols, and the alcohol is more preferably one or more selected from ethanol, isopropyl alcohol, butyl alcohol, phenylethyl alcohol, propanol, and pentanol, and <1> ~ <5> 10. The film-forming composition according to claim 9, wherein the film-forming composition is a film-forming composition according to any one of the preceding items. <7> The volatile substance of component (A) is one or more selected from ethanol, isopropyl alcohol, butyl alcohol, and water, more preferably one or two selected from ethanol and butyl alcohol, and even more preferably contains ethanol. <1> ~ <6> 10. The film-forming composition according to claim 9, wherein the film-forming composition is a film-forming composition according to any one of the preceding items. <8> The content of component (A) in the composition is preferably 45% by mass or more, more preferably 50% by mass or more, and even more preferably 55% by mass or more, and is preferably 95% by mass or less, more preferably 94% by mass or less, and even more preferably 93% by mass or less. The content of component (A) in the composition is preferably 45% by mass or more and 95% by mass or less, more preferably 50% by mass or more and 94% by mass or less, and even more preferably 55% by mass or more and 93% by mass or less. <1> ~ <7> 10. The film-forming composition according to claim 9, wherein the film-forming composition is a film-forming composition according to any one of the preceding items. <9> The polymer (B) capable of forming a film is preferably one or more selected from the group consisting of partially saponified polyvinyl alcohol, slightly saponified polyvinyl alcohol, fully saponified polyvinyl alcohol, polyvinyl butyral resin, polyurethane resin, polymethacrylic acid resin, oxazoline-modified silicone, polyvinyl acetal diethylaminoacetate, and polylactic acid, more preferably one or more selected from polyvinyl butyral resin, polylactic acid, and polyurethane resin, still more preferably contains polyvinyl butyral resin, and particularly preferably contains polyvinyl butyral resin as the main component. <1> ~ <8> 10. The film-forming composition according to claim 9, wherein the film-forming composition is a film-forming composition according to any one of the preceding items. <10> The mass ratio of the component (B1) to the component (B) ((B1) / (B)) is preferably 0.5 or more, more preferably 0.51 or more, even more preferably 0.53 or more, even more preferably 0.55 or more, and is preferably 1 or less, more preferably 0.95 or less, and even more preferably 0.9 or less. <1> , <5> ~ <9> 10. The film-forming composition according to claim 9, wherein the film-forming composition is a film-forming composition according to any one of the preceding items. <11> The number average molecular weight of component (B) is 4.6 × 10 4 It is preferable that the value is equal to or greater than 4.7×10 4 More preferably, it is 4.8×10 or more. 4 More preferably, it is 3×10 or more. 5 Less than 2 x 10 is preferable. 5 Less than 1.7×10 is preferable. 5 The following is more preferred: <2> , <5> ~ <9> 10. The film-forming composition according to claim 9, wherein the film-forming composition is a film-forming composition according to any one of the preceding items. <12> The number average molecular weight of component (B) is 4.6 × 10 4 It is preferable that the value is equal to or greater than 4.7×10 4 More preferably, it is 4.8×10 or more. 4 More preferably, it is 3×10 or more. 5 Less than 2 x 10 is preferable. 5 Less than 1.7×10 is preferable. 5 The following is more preferred: <3> , <5> ~ <9> 10. The film-forming composition according to claim 9, wherein the film-forming composition is a film-forming composition according to any one of the preceding items. <13> The peak of the molecular weight distribution of component (B) is 9.5 × 10 4 It is preferable that the value is equal to or greater than 1.0×10 5 More preferably, it is 1.1×10 5 More preferably, it is 1.0 × 10 or more. 6 The following is preferable: 7.0 x 10 5 Less than 5.0 x 10 is preferable. 5 Even better: 3.5 x 10 5 The following is even more preferred: <4> ~ <9> 10. The film-forming composition according to claim 9, wherein the film-forming composition is a film-forming composition according to any one of the preceding items. <14> The content of component (B) is preferably 2% by mass or more, more preferably 4% by mass or more, and even more preferably 5% by mass or more, and is preferably 30% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less, and is preferably 2% by mass or more and 30% by mass or less, more preferably 4% by mass or more and 20% by mass or less, and even more preferably 5% by mass or more and 15% by mass or less. <1> ~ <13> 10. The film-forming composition according to claim 9, wherein the film-forming composition is a film-forming composition according to any one of the preceding items. <15> The mass ratio of the component (B) to the component (A) ((B) / (A)) is preferably 0.03 or more and 0.5 or less, more preferably 0.04 or more and 0.4 or less, and even more preferably 0.055 or more and 0.3 or less. <1> ~ <14> 10. The film-forming composition according to claim 9, wherein the film-forming composition is a film-forming composition according to any one of the preceding items. <16> The polyol of component (C) is one or more selected from alkylene glycols, polyalkylene glycols and glycerins. <1> ~ <15> 10. The film-forming composition according to claim 9, wherein the film-forming composition is a film-forming composition according to any one of the preceding items. <17> The content of component (C) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass, and is preferably 30% by mass or less, more preferably 25% by mass or less, and even more preferably 20% by mass or less, and is preferably 0.1% by mass or more and 30% by mass or less, more preferably 0.5% by mass or more and 25% by mass or less, and even more preferably 1% by mass or more and 20% by mass or less. <1> ~ <16> 10. The film-forming composition according to claim 9, wherein the film-forming composition is a film-forming composition according to any one of the preceding items. <18> The mass ratio of the component (B) to the component (C) ((B) / (C)) is more preferably 1.1 or more, even more preferably 1.2 or more, and is preferably 30 or less, more preferably 20 or less, even more preferably 15 or less, preferably 1 or more and 30 or less, more preferably 1.1 or more and 20 or less, even more preferably 1.2 or more and 15 or less. <1> ~ <17> 10. The film-forming composition according to claim 9, wherein the film-forming composition is a film-forming composition according to any one of the preceding items. <19> The above-mentioned compound further containing component (D) oil. <1> ~ <18> 10. The film-forming composition according to claim 9, wherein the film-forming composition is a film-forming composition according to any one of the preceding items. <20> The oil of component (D) is preferably one or more selected from hydrocarbon oils, ester oils, higher alcohols, silicone oils and fatty acids, and more preferably one or more selected from hydrocarbon oils, ester oils and silicone oils. <19> The coating-forming composition described above. <21> The content of component (D) is preferably 0% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass, and is preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less, and is preferably 0% by mass or more and 25% by mass or less, more preferably 0.5% by mass or more and 20% by mass or less, and even more preferably 1% by mass or more and 15% by mass or less. <19> or <20> The film-forming composition according to claim 1. <22> The viscosity at 25°C 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. <1> ~ <21> 10. The film-forming composition according to claim 9, wherein the film-forming composition is a film-forming composition according to any one of the preceding items.

[0069] <23> The following components (A), (B) and (C): (A) one or more volatile substances selected from water, alcohols, and ketones; (B) a water-insoluble polymer having fiber-forming properties, and (C) Contains one or more polyols selected from the group consisting of polyols, As component (B), (B1) molecular weight 1 × 10 5 Contains the above polymer, the mass ratio of component (B1) to component (B) ((B1) / (B)) is 0.5 or more, A method for producing a coating, which uses a composition in which the mass ratio of component (B) to component (C) ((B) / (C)) is 1 or more, to form a coating consisting of a deposit containing fibers on the surface of an object to be coated. <24> The following components (A), (B) and (C): (A) one or more volatile substances selected from water, alcohols, and ketones; (B) a water-insoluble polymer having fiber-forming properties, and (C) Contains one or more polyols selected from the group consisting of polyols, The number average molecular weight of component (B) is 4.5 x 10 4 That's all, A method for producing a coating, which uses a composition in which the mass ratio of component (B) to component (C) ((B) / (C)) is 1 or more, to form a coating consisting of a deposit containing fibers on the surface of an object to be coated. <25> The following components (A), (B) and (C): (A) one or more volatile substances selected from water, alcohols, and ketones; (B) a water-insoluble polymer having fiber-forming properties, and (C) one or more polyols selected from the group consisting of The number average molecular weight of component (B) is 4.5 x 10 4 The method for producing a coating includes forming a coating made of a deposit containing fibers on the surface of an object to be coated using a composition having the above-mentioned components and a mass ratio (B) / (C) of component (B) to component (C) of 1 or more. <26> The following components (A), (B) and (C) (A) one or more volatile substances selected from water, alcohols, and ketones; (B) a water-insoluble polymer having fiber-forming ability; (C) Contains one or more polyols selected from the group consisting of polyols, The peak of the molecular weight distribution of component (B) is 9.0 × 10 4and a composition in which the content by mass of component (B) to component (C), (B) / (C), is 1 or more, is used to form a coating consisting of a deposit containing fibers on the surface of an object to be coated. <27> The above-mentioned coating film forming object is skin. <23> ~ <26> 10. A method for producing the coating according to any one of the preceding claims. <28> The following components (A), (B) and (C): (A) one or more volatile substances selected from water, alcohols, and ketones; (B) a water-insoluble polymer having fiber-forming properties, and (C) Contains one or more polyols selected from the group consisting of polyols, As component (B), (B1) molecular weight 1 × 10 5 Contains the above polymer, the mass ratio of component (B1) to component (B) ((B1) / (B)) is 0.5 or more, A method for applying a composition having a mass ratio of component (B) to component (C) ((B) / (C)) of 1 or more to an area of ​​human skin that contains a large amount of sebum. <29> The following components (A), (B) and (C): (A) one or more volatile substances selected from water, alcohols, and ketones; (B) a water-insoluble polymer having fiber-forming properties, and (C) Contains one or more polyols selected from the group consisting of polyols, The number average molecular weight of component (B) is 4.5 x 10 4 That's all, A method for applying a composition having a mass ratio of component (B) to component (C) ((B) / (C)) of 1 or more to an area of ​​human skin that contains a large amount of sebum. <30> The following components (A), (B) and (C): (A) one or more volatile substances selected from water, alcohols, and ketones; (B) a water-insoluble polymer having fiber-forming properties, and (C) one or more polyols selected from the group consisting of The number average molecular weight of component (B) is 4.5 x 10 4 The method comprises applying a composition having a mass ratio (B) / (C) of component (B) to component (C) of 1 or more to an area including a region of human skin where sebum is secreted in large amounts. <31> The following components (A), (B) and (C) (A) one or more volatile substances selected from water, alcohols, and ketones; (B) a water-insoluble polymer having fiber-forming ability; (C) Contains one or more polyols selected from the group consisting of polyols, The peak of the molecular weight distribution of component (B) is 9.0 × 10 4 and the mass ratio (B) / (C) of component (B) to component (C) is 1 or more, to an area including a region where human sebum is secreted in large amounts. <32> The following components (A), (B) and (C): (A) one or more volatile substances selected from water, alcohols, and ketones; (B) a water-insoluble polymer having fiber-forming properties, and (C) Contains one or more polyols selected from the group consisting of polyols, As component (B), (B1) molecular weight 1 × 10 5 Contains the above polymer, the mass ratio of component (B1) to component (B) ((B1) / (B)) is 0.5 or more, A method for producing a sebum-resistant coating, which comprises forming a coating consisting of a deposit containing fibers on the surface of an object to be coated using a composition in which the mass ratio of component (B) to component (C) ((B) / (C)) is 1 or more. <33> The following components (A), (B) and (C): (A) one or more volatile substances selected from water, alcohols, and ketones; (B) a water-insoluble polymer having fiber-forming properties, and (C) Contains one or more polyols selected from the group consisting of polyols, The number average molecular weight of component (B) is 4.5 x 10 4 That's all, A method for producing a sebum-resistant coating, which comprises forming a coating consisting of a deposit containing fibers on the surface of an object to be coated using a composition in which the mass ratio of component (B) to component (C) ((B) / (C)) is 1 or more. <34> The following components (A), (B) and (C): (A) one or more volatile substances selected from water, alcohols, and ketones; (B) a water-insoluble polymer having fiber-forming properties, and (C) one or more polyols selected from the group consisting of The number average molecular weight of component (B) is 4.5 x 10 4 The method for producing a sebum-resistant coating comprises forming a coating made of deposits containing fibers on the surface of an object to be coated using a composition having the above-mentioned components and a content mass ratio (B) / (C) of component (B) to component (C) of 1 or more. <35> The following components (A), (B) and (C) (A) one or more volatile substances selected from water, alcohols, and ketones; (B) a water-insoluble polymer having fiber-forming ability; (C) Contains one or more polyols selected from the group consisting of polyols, The peak of the molecular weight distribution of component (B) is 9.0 × 10 4 and a composition in which the content by mass of component (B) to component (C), (B) / (C), is 1 or more, is used to form a coating consisting of a deposit containing fibers on the surface of an object to be coated. <36> The following components (A), (B) and (C): (A) one or more volatile substances selected from water, alcohols, and ketones; (B) a water-insoluble polymer having fiber-forming properties, and (C) Contains one or more polyols selected from the group consisting of polyols, As component (B), (B1) molecular weight 1 × 10 5 Contains the above polymer, the mass ratio of component (B1) to component (B) ((B1) / (B)) is 0.5 or more, A method for applying a sebum-resistant sheet, comprising forming a coating consisting of a deposit containing fibers on the surface of an object to be coated using a composition in which the mass ratio of component (B) to component (C) ((B) / (C)) is 1 or more. <37> The following components (A), (B) and (C): (A) one or more volatile substances selected from water, alcohols, and ketones; (B) a water-insoluble polymer having fiber-forming properties, and (C) Contains one or more polyols selected from the group consisting of polyols, The number average molecular weight of component (B) is 4.5 x 10 4 That's all, A method for applying a sebum-resistant sheet, comprising forming a coating consisting of a deposit containing fibers on the surface of an object to be coated using a composition in which the mass ratio of component (B) to component (C) ((B) / (C)) is 1 or more. <38> The following components (A), (B) and (C): (A) one or more volatile substances selected from water, alcohols, and ketones; (B) a water-insoluble polymer having fiber-forming properties, and (C) one or more polyols selected from the group consisting of The number average molecular weight of component (B) is 4.5 x 10 4 A method for applying a sebum-resistant sheet, comprising forming a coating consisting of deposits containing fibers on the surface of an object to be coated using a composition having a mass ratio (B) / (C) of component (B) to component (C) of 1 or more. <39> The following components (A), (B) and (C) (A) one or more volatile substances selected from water, alcohols, and ketones; (B) a water-insoluble polymer having fiber-forming ability; (C) Contains one or more polyols selected from the group consisting of polyols, The peak of the molecular weight distribution of component (B) is 9.0 × 10 4and a composition in which the content by mass of component (B) to component (C), (B) / (C), is 1 or more, is used to form a coating consisting of a deposit containing fibers on the surface of an object to be coated.

[0070] <40> A patch fiber sheet composed of a deposit of fibers and used by transferring it to the skin, the patch fiber sheet comprising (B) polyvinyl butyral resin as the main fiber component and containing one or more polyols selected from component (C), the number-average molecular weight of component (B) being 4.5 × 10 4 The above-mentioned adhesive fiber sheet has a mass ratio of component (B) to component (C) ((B) / (C)) of 1 or more. <41> The thickness of the fibers constituting the fiber sheet for application is 10 nm or more and 3000 nm or less, preferably 50 nm or more and 1500 nm or less, more preferably 100 nm or more and 1200 nm or less, in terms of circle equivalent diameter. <40> 1. The adhesive fiber sheet according to claim 1. <42> The thickness of the adhesive fiber sheet is 100 nm to 500 μm, preferably 500 nm to 300 μm, more preferably 1 μm to 100 μm, and even more preferably 10 μm to 50 μm. <40> or <41> The adhesive fiber sheet described above. [Example]

[0071] The present invention will be described in more detail below with reference to examples. However, the scope of the present invention is not limited to such examples. Unless otherwise specified, "%" means "% by mass."

[0072] [Examples 1 to 11 and Comparative Examples 1 to 3] (1) Preparation of spray composition Compositions for spraying were prepared according to the formulations shown in Tables 1 to 3. The amounts of ethanol shown in Tables 1 to 3 are effective amounts and do not include water. (2) Electrostatic spray process Electrostatic spraying was performed for 20 seconds by directly spraying onto the skin using an electrostatic spraying device 10 having the configuration shown in Figure 1 and the appearance shown in Figure 2. The conditions for the electrostatic spraying were as follows: Applied voltage: 10kV Distance between nozzle and skin: 100mm Discharge rate of spray composition: 5mL / h ·Environment: 25℃, 30%RH The electrostatic spray produced a film of fiber deposits on the skin surface. The film was circular, approximately 4 cm in diameter, and weighed approximately 3.8 mg. The fiber diameter, measured using the method described above, was 660 nm.

[0073] 〔evaluation〕 The coatings formed in the examples and comparative examples were evaluated for sebum resistance, feel, and resistance to octyl paramethoxycinnamate by the following methods. The results are shown in Tables 1 to 3.

[0074] <Sebum resistance> Oleic acid was used as the sebum. A 7 cm x 7 cm coating was formed on a 5 cm x 5 cm aluminum foil using the same electrostatic spraying process as described above. Immediately after coating formation, 1 μL of oleic acid was dropped onto the coating, and the time until a hole was formed in the coating was evaluated. Evaluation criteria: 4: No holes for 6 hours 3: No holes for more than 3 hours 2: No holes for over an hour 1: Holes appear immediately after oleic acid is added

[0075] <Sensation (film-like sensation, tightness, discomfort)> In Examples 1 to 11 and Comparative Examples 1 to 3, the coating film formed by electrostatic spraying of fibers on the skin after application of skin care cosmetics (RISE Lotion, Milk II) was evaluated for film feel, tightness, and discomfort. The film-forming composition was applied to the skin by electrostatic spraying immediately after application of the skin care cosmetics, forming a film made of fibers. The film was then lightly pressed from above with the hand to completely blend, and after 10 minutes, the film feel, tightness, and discomfort were evaluated by sensory evaluation. The evaluation site was the cheek of a human face. Complete blending of the skin care cosmetics and the film meant that the film was colorless and transparent to the naked eye. The evaluation results are shown in Table 1. The evaluation criteria were as follows: 5: Even when the film is on the skin under normal circumstances, there is no particular feeling of filminess, tightness, or discomfort, and even when changing facial expressions, there is no feeling of filminess, tightness, or discomfort, and the sensation is no different from when the film is not on the skin. 4: Even when the film is on the skin under normal circumstances, there is no particular feeling of filminess, tightness, or discomfort, but when changing facial expressions, a slight feeling of filminess, tightness, or discomfort is felt, but the person can go about their day without feeling particularly uncomfortable. 3: Even when the film is on the skin under normal circumstances, there is no particular feeling of filminess, tightness, or discomfort, but when changing facial expression, a strong feeling of filminess, tightness, or discomfort is felt, causing discomfort. 2: When the film is on the skin under normal circumstances, it causes a slight filmy, tight, and strange feeling, and is particularly strong when changing facial expressions, causing discomfort. 1: When the film is on the skin under normal circumstances, it gives a strong filmy feeling, a tight feeling, and a strange sensation, causing discomfort.

[0076] <Octyl para-methoxycinnamate resistance> A 7 cm x 7 cm coating was formed on a 5 cm x 5 cm piece of aluminum foil using the same electrostatic spraying process as described above. 1 μL of a 2 / 8 mixed solution of octyl paramethoxycinnamate and neopentyl glycol dicaprate was dropped onto the coating, and the time it took for a hole to form in the coating was evaluated. Evaluation criteria: 4: No holes 3: No holes for more than 3 hours 2: No holes for over an hour 1: A hole appears immediately after dripping

[0077] <Measurement of molecular weight and distribution of component (B)> The molecular weight was determined by preparing a calibration curve using gel permeation chromatography (GPC) with standard polystyrene. Apparatus: HLC-8320 GPC (Tosoh Corporation, integrated detector) Column: α-M + α-M (anion) Eluent: 60mmol / L phosphoric acid + 50mmol / L lithium bromide in dimethylformamide ·Flow rate: 1.0mL / min Column temperature: 40℃ Detector: RI detector Standard material: Polystyrene

[0078] [Table 1]

[0079] [Table 2]

[0080] [Table 3]

[0081] <Evaluation of peelability of sebum-containing coating> Artificial leather suppler 5 x 5 cm 2 4 μL of oleic acid was applied to the skin, and then 50 mg of emulsion (RISE MILK II) was applied thereon. The composition was electrostatically sprayed in the same manner as above to form a coating consisting of a fiber deposit with a uniform basis weight. After leaving the coating to stand for 15 minutes, the edge of the coating was grasped and peeled off, and the releasability of the coating containing sebum (oleic acid) was evaluated. The releasability evaluation criteria were as follows. The results are shown in Table 4.

[0082] Evaluation Criteria 1 "How the film mixed with sebum peels off (the film peels off as a whole)" 4: Can be peeled off as a clean single film 3: There are small holes, but the film can be peeled off in one piece 2: Large holes and tears 1: The film has become tattered and cannot be peeled off Evaluation Criteria 2 "Easy to remove the film mixed with sebum" 4: Light and easy to remove 3: Some parts are difficult to peel off, but can be peeled off with some force. 2: Many areas are difficult to peel off, and only partial peeling is possible 1: Most of the surface is barely removable

[0083] [Table 4] [Explanation of symbols]

[0084] 10 Electrostatic spray device 11 Low voltage power supply 12 High voltage power supply 13 Auxiliary Electrical Circuits 14 Micro Gear Pump 15 Container 16 nozzles 17 Conduit 18 Flexible Pipe 19 Current limiting resistor 20 Case

Claims

1. The following components (A), component (B) and component (C): (A) One or more volatile substances selected from water, alcohol and ketone, (B) A water-insoluble polymer having fiber-forming ability, and (C) One or more selected from polyols, and contains As component (B), it contains (B1) the polymer having a molecular weight of 1×105 or more, The content mass ratio of component (B1) to component (B) ((B1) / (B)) is 0.5 or more, The content mass ratio of component (B) to component (C) ((B) / (C)) is 1 or more, A film-forming composition for forming a film composed of a deposit containing fibers directly on the skin by electrostatic spraying.

2. The following components (A), component (B) and component (C): (A) One or more volatile substances selected from water, alcohol and ketone, (B) A water-insoluble polymer having fiber-forming ability, and (C) One or more selected from polyols, and contains The number average molecular weight of component (B) is 4.5×104 or more, The content mass ratio of component (B) to component (C) ((B) / (C)) is 1 or more, A film-forming composition for forming a film composed of a deposit containing fibers directly on the skin by electrostatic spraying.

3. The film-forming composition according to claim 1 or 2, wherein the content of component (A) is 45% by mass or more and 95% by mass or less, and the content of component (B) is 3% by mass or more and 30% by mass or less.

4. The film-forming composition according to claim 1 or 2, wherein the content of component (C) is 0.1% by mass or more and 30% by mass or less.

5. (B) The polymer having film-forming ability is at least one selected from the group consisting of partially saponified polyvinyl alcohol, low-saponification polyvinyl alcohol, completely saponified polyvinyl alcohol, polyvinyl butyral resin, polyurethane resin, polymethacrylic acid resin, oxazoline-modified silicone, polyvinyl acetal diethylamino acetate, and polylactic acid. The film-forming composition according to claim 1 or 2.

6. The film-forming composition according to claim 1 or 2, wherein the content mass ratio of component (B) to component (C) ((B) / (C)) is 1.1 or more and 30 or less.

7. The film-forming composition according to claim 1 or 2, wherein the content mass ratio of component (B) to component (A) ((B) / (A)) is 0.03 or more and 0.5 or less.

8. Further, the film-forming composition according to claim 1 or 2, which contains component (D) oil.

9. The following component (A), component (B) and component (C) (A) One or more volatile substances selected from water, alcohol and ketone, (B) A water-insoluble polymer having fiber-forming ability, and (C) One or more selected from polyols are added to obtain, The number average molecular weight of component (B) is 4.5×104 or more, The content mass ratio (B) / (C) of component (B) to component (C) is 1 or more, A film-forming composition for forming a film composed of a deposit containing fibers directly on the skin by electrostatic spraying.

10. The following component (A), component (B) and component (C) (A) One or more volatile substances selected from water, alcohol and ketone, (B) A water-insoluble polymer having fiber-forming ability, (C) One or more selected from polyols are contained, The peak of the molecular weight distribution of component (B) is a polymer exceeding 9.0×104, The content mass ratio (B) / (C) of component (B) to component (C) is 1 or more, A film-forming composition for forming a film composed of a deposit containing fibers directly on the skin by electrostatic spraying.

11. The following component (A), component (B) and component (C): (A) One or more volatile substances selected from water, alcohol and ketone, (B) A water-insoluble polymer having fiber-forming ability, and (C) One or more selected from polyols are contained, As component (B), it contains (B1) the polymer having a molecular weight of 1×105 or more, The content mass ratio ((B1) / (B)) of component (B1) to component (B) is 0.5 or more, Using a composition in which the content mass ratio ((B) / (C)) of component (B) to component (C) is 1 or more, a film composed of a deposit containing fibers is formed on the surface of the object to be film-formed. Manufacturing method of film Method.

12. The following component (A), component (B) and component (C): (A) One or more volatile substances selected from water, alcohol and ketone, (B) A water-insoluble polymer having fiber-forming ability, and (C) One or more selected from polyols are contained, The number average molecular weight of component (B) is 4.5×104 or more, Using a composition in which the content mass ratio ((B) / (C)) of component (B) to component (C) is 1 or more, a film composed of a deposit containing fibers is formed on the surface of the object to be film-formed. Manufacturing method of film

13. The method for manufacturing a film according to claim 11 or 12, wherein the object to be film-formed is the skin.

14. A fiber sheet for sticking, which is composed of fiber deposits and is used by being transferred to the skin, wherein the fiber sheet for sticking has (B) polyvinyl butyral resin as the main component of the fiber, contains one or more selected from component (C) polyols, the number average molecular weight of component (B) is 4.5×104 or more, and the content mass ratio ((B) / (C)) of component (B) to component (C) is 1 or more.

15. The fiber sheet for sticking according to claim 14, wherein the thickness of the fiber constituting the fiber sheet for sticking is 10 nm or more and 3000 nm or less in terms of the equivalent circle diameter.

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