TW201841609A - Method for producing coating film - Google Patents

Abstract

The present invention relates to technological improvement in an electrostatic spraying method for skin, and more specifically, to an increase in the adhesion of a coating film formed on the skin by electrostatic spraying. Provided is a method for producing a coating film on skin, the method being characterized by having, in the following order or reverse order: a liquid agent application step for applying a polymer-containing liquid agent onto the skin by a method other than electrostatic spraying; and a step for electrostatically spraying a composition containing component (a) and component (b) onto the skin directly to form a coating film on the skin. Component (a) is a volatile substance of at least one selected from the group consisting of water, alcohol, and ketone; and component (b) is a polymer having an ability to form a coating film.

Description

 Film manufacturing method  

The present invention relates to a method of producing a film.

Various methods for forming a film by electrostatic spraying are known. For example, Patent Document 1 discloses a skin treatment method comprising electrostatically spraying a composition onto the skin. The composition used in this method contains a liquid insulating material, a conductive material, a particulate powder material, and a tackifier. As such a composition, a cosmetic or skin care composition containing a pigment is typically used. Specifically, a cosmetic foundation is used as a composition. In other words, in the invention described in Patent Document 1, the cosmetic foundation is electrostatically sprayed for the purpose of beauty, and is mainly set to apply makeup to the skin.

Patent Document 2 describes a disposable crucible for use in an electrostatic spray device for cosmetics. This electrostatic spraying device is a hand-held type. This electrostatic coating apparatus is used to spray a cosmetic foundation in the same manner as in Patent Document 1 described above.

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2006-104211

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2003-507165

The present invention provides a method for producing a film on a skin, which comprises the steps of applying a liquid agent containing a polymer to a skin by a method other than electrostatic spraying; And a step of directly electrostatically spraying a composition containing the component (a) and the component (b) onto the skin to form a film on the skin.

(a) one or two or more kinds of volatile substances selected from the group consisting of water, alcohols, and ketones; and (b) a polymer having a film forming ability.

10‧‧‧Electrostatic spraying device

10a‧‧‧One end of electrostatic spraying device

11‧‧‧Low voltage power supply

12‧‧‧High voltage power supply

13‧‧‧Auxiliary circuit

14‧‧‧Micro gear pump

15‧‧‧ Container

16‧‧‧ nozzle

17‧‧‧pipe

18‧‧‧Flexible pipeline

19‧‧‧ Current limiting resistor

20‧‧‧ frame

SW‧‧ switch

Fig. 1 is a schematic view showing the configuration of an electrostatic coating apparatus suitable for use in the present invention.

Fig. 2 is a schematic view showing a state in which an electrostatic spray method is performed using an electrostatic spray device.

When the film is formed on the skin by electrostatic spraying in accordance with the methods described in Patent Documents 1 and 2, the adhesion between the skin and the film formed by electrostatic spraying is insufficient, and the film is damaged or peeled off by external force such as friction. And other issues.

Accordingly, the present invention is an improvement in the technique of electrostatic spraying of the skin, and more specifically, to improve the adhesion of the film formed on the skin by electrostatic spraying.

The inventors of the present invention conducted various reviews and found that the liquid containing the polymer was electrostatically sprayed by electrostatically spraying the composition containing the volatile substance and the polymer having the film forming ability directly or directly to the skin. When the method is applied to the skin, the adhesion of the film formed on the skin is remarkably enhanced, and it is not easily damaged or peeled off by friction of fingers or clothes, and the present invention has been completed.

According to the present invention, the adhesion between the skin and the film formed by electrostatic spraying is improved, and the film formed on the skin is less likely to be damaged or peeled off by friction of fingers or clothes.

The present invention relates to a method for producing a film on a skin, which is characterized by the following sequence or in reverse order: (1) application of a liquid agent containing a polymer to a skin by a method other than electrostatic spraying a step (hereinafter sometimes referred to as a liquid application step); and (2) directly spraying a composition containing the above component (a) and component (b) (hereinafter sometimes referred to as a spray composition) onto the skin. A step of forming a film on the skin (hereinafter also referred to as an electrostatic spraying step).

The liquid agent used in the liquid application step (1) is a liquid preparation containing a polymer.

As the above polymer, any of a water-soluble polymer and a water-insoluble polymer can be used. As the water-soluble polymer, at least one selected from the group consisting of a nonionic polymer, an anionic polymer, a cationic polymer, and an amphoteric polymer can be used. In the present specification, the term "water-soluble polymer" means a polymer which is impregnated in 10 g of ion-exchanged water after weighing 1 g of the polymer in an atmosphere of 1 atm. and 23 ° C, and after 24 hours. 0.5 g or more of the properties dissolved in water. On the other hand, the term "water-insoluble polymer" as used in the present specification means that after weighing 1 g of the polymer in an atmosphere of 1 atm and 23 ° C, it is immersed in 10 g of ion-exchanged water, and after 24 hours, More than 0.5 g of the impregnated polymer does not dissolve in water.

The nonionic polymer is not particularly limited, and any of the nonionic polymers generally used in the cosmetic field can be used. The liquid agent may contain one or two or more kinds of nonionic polymers, and may further contain one or more kinds of anionic, cationic and/or amphoteric polymers in combination with the nonionic polymer.

Examples of the nonionic polymer include (meth)acrylic nonionic polymers, polyvinylpyrrolidone, polyacrylamide, neutral polysaccharides, and derivatives thereof (ethers or esters thereof). . Examples of the neutral saccharides and derivatives thereof include neutral gums (guar gum, hydroxypropyl guar gum, etc.), and cellulose ethers (hydroxyethyl cellulose (HEC), methyl hydroxyethyl bromide). Cellulose (MHEC), ethyl hydroxyethyl cellulose (EHEC), methyl ethyl hydroxyethyl cellulose (MEHEC), hydroxypropyl cellulose (HPC), hydroxypropyl methyl cellulose (HPMC) , hydrophobized derivatives (HM-EHEC, etc.), starch and its derivatives (dextrin, etc.).

Hereinafter, examples of compounds having an ethylenically unsaturated bond which can constitute a nonionic polymer such as the above (meth)acrylic nonionic polymer, polyvinylpyrrolidone or polydecylamine are listed, but the present invention does not. It is limited to the following specific examples.

Examples of the nonionic monomer include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, and (methyl). N-butyl acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-amyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, N-heptyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, decyl (meth)acrylate, decyl (meth)acrylate, (methyl) Dodecyl acrylate, phenyl (meth) acrylate, toluene (meth) acrylate, benzyl (meth) acrylate, isodecyl (meth) acrylate, 2-methoxy B (meth) acrylate Ester, 3-methoxybutyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, stearyl (meth)acrylate, ( Glycidyl methacrylate, 2-aminoethyl (meth) acrylate, γ-((meth) propylene oxypropyl) trimethoxy decane, γ-((meth) propylene oxime Ethyl propyl) dimethoxymethyl decane, epoxy (meth) acrylate Adduct, trifluoromethyl methyl (meth)acrylate, 2-trifluoromethyl ethyl (meth)acrylate, 2-perfluoroethyl ethyl (meth)acrylate, (meth)acrylic acid 2-perfluoroethyl-2-perfluorobutylethyl ester, 2-perfluoroethyl (meth)acrylate, perfluoromethyl (meth)acrylate, diperfluoromethyl methyl (meth)acrylate , (Per)methyl perfluoromethyl-2-perfluoroethyl methyl ester, 2-perfluorohexyl ethyl (meth)acrylate, 2-perfluorodecyl ethyl (meth)acrylate (meth)acrylate such as (meth)acrylic acid-2-perfluorohexadecylethyl ester; aromatic such as styrene, α-methylstyrene, p-methylstyrene or p-methoxystyrene Alkenyl compound; cyanide vinyl compound such as acrylonitrile or methacrylonitrile; conjugated diene compound such as butadiene or isoprene; vinyl chloride, dichloroethylene, perfluoroethylene, perfluoro a halogen-containing unsaturated compound such as propylene or difluoroethylene; a hydrazine-containing unsaturated compound such as vinyl trimethoxy decane or vinyl triethoxy decane; an unsaturated carboxylic anhydride such as maleic anhydride; Dialkyl enedomate, An unsaturated dicarboxylic acid diester such as a dialkyl fumarate; a vinyl ester compound such as vinyl acetate, vinyl propionate, trimethyl vinyl acetate, vinyl benzoate or vinyl cinnamate From maleimide, N-methyl maleimide, N-ethyl maleimide, N-propyl maleimide, N-butyl cis Equinone imine, N-hexyl maleimide, N-octyl maleimide, N-dodecylideneimide, N-stearyl butenylene a maleimide compound such as an imine, N-phenyl maleimide or N-cyclohexylmethyleneimine; polyethylene glycol (meth) acrylate, A Oxypoly (ethylene glycol / propylene glycol) mono (meth) acrylate, polyethylene glycol di (meth) acrylate, N - polyalkyloxy (meth) acrylamide (methyl) a monomer derived from acrylic acid or (meth) acrylamide and an alkylene oxide having 2 to 4 carbon atoms; N-vinylpyrrolidone, N-(methyl)propenylmorpholine, acrylamide, etc. A hydrophilic nonionic monomer or the like.

Among the above nonionic polymers, a (meth)acrylic water-soluble nonionic polymer is preferred.

In addition, the description of "(meth)acrylic" in this specification means "acrylic acid or methacrylic acid."

The anionic polymer is not particularly limited, and any anionic polymer generally used in the field of cosmetics can be used. The liquid agent may contain one or two or more kinds of anionic polymers, and may further contain one or more kinds of nonionic, cationic and/or amphoteric polymers in combination with the anionic polymer.

Examples of the anionic polymer include an anionic polysaccharide and a derivative thereof (alginate, pectin, hyaluronic acid, etc.), an anionic gum (three sensilla, dehydrogenosene, hydroxypropyl sinensis). An anionic cellulose derivative (carboxymethyl cellulose (CMC) or the like), a (meth)acrylic water-soluble anionic polymer, or the like.

The following is an example of a compound having an ethylenically unsaturated bond which can constitute an anionic polymer such as the above (meth)acrylic anionic polymer, but the present invention is not limited to the following specific examples. Examples of the anionic monomer include unsaturated carboxylic acid compounds such as (meth)acrylic acid, maleic acid, maleic anhydride, itaconic acid, fumaric acid, and crotonic acid; Unsaturated polybasic acid anhydride (for example, succinic anhydride, phthalic anhydride, etc.), partial ester compound with hydroxyl group-containing (meth) acrylate (for example, hydroxyethyl (meth) acrylate); styrene sulfonic acid, (methyl) A sulfonic acid group compound such as sulfonic acid ethyl acrylate or the like; a phosphoric acid group compound such as an acid phosphorus oxyethyl (meth) acrylate. These anionic unsaturated monomers may be used as they are, or may be used in partial neutralization or complete neutralization, or may be partially neutralized or completely neutralized by acid directly after copolymerization. As the basic compound used for the neutralization, for example, an alkali metal hydroxide such as potassium hydroxide or sodium hydroxide, an amine compound such as ammonia water, mono-, di-, triethanolamine or trimethylamine.

Among the above anionic polymers, a (meth)acrylic anionic polymer is particularly preferred. As a commercial item, Placize L-53D (Inter-Chemical (Share)), (alkyl acrylate octyl acrylamide) copolymer of (alkyl acrylate / diacetone acrylamide) copolymer is mentioned, for example. Dermacry 179 (Akzo Nobel (share)), acrylate copolymer ammonium YODOSOL GH800F (Akzo Nobel (share)), and (acrylate / C12-22 alkyl methacrylate) copolymer SOLTEX OPT (DOW CHEMICAL (DOW CHEMICAL (DOW CHEMICAL) share)).

Further, an emulsified tackifier containing such a nonionic polymer or an anionic polymer can also be used. For example, polyacrylamide/(C13, C14) isoparaffin/Laureth-7 (Sepigel 305 manufactured by Seppic Co., Ltd.) or the like can be mentioned.

The cationic polymer is not particularly limited, and any of the cationic thickening polymers generally used in the field of cosmetics can be used. The liquid agent may contain one or more cationic polymers, and may further contain one or more nonionic, anionic, and/or amphoteric polymers in combination with the cationic polymer.

The cationic polymer is a polymer having a cationic group such as a quaternary ammonium group or a group such as a primary, secondary or tertiary amine group which can be ionized into a cationic group. The cationic polymer is typically a polymer containing an amine group or an ammonium group in a side chain of a polymer chain or a polymer containing a diallyl quaternary ammonium salt as a constituent unit.

The preferred cationic polymer may, for example, be a cationized cellulose, a cationic starch, a cationic guar gum, a vinyl-based or (meth)acrylic polymer or copolymer having a quaternary ammonium side chain, or four. A polyvinylpyrrolidone, a (meth) acrylate/amino acrylate copolymer, an amine-substituted poly(meth) acrylate crosspolymer, a (meth) acrylic water-soluble cationic polymer, or the like.

Hereinafter, examples of the compound having an ethylenically unsaturated bond which can constitute the cationic polymer such as the above (meth)acrylic cationic polymer are listed, but the present invention is not limited to the following specific examples. Examples of the cationic monomer include N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, and (methyl). N,N-dimethylaminopropyl acrylate, N,N-diethylaminopropyl (meth)acrylate, N,N-dimethylaminoethyl (meth) acrylamide, ( Methyl) acrylamide N,N-diethylaminoethyl ester, (meth) acrylamide N,N-dimethylaminopropyl, (meth) acrylamide N,N-diethyl Aminopropyl propyl ester, p-dimethylaminomethyl styrene, p-dimethylaminoethyl styrene, p-diethylaminomethyl styrene, p-diethylaminoethyl styrene, etc. By a cationizing agent (for example, a halogenated alkyl group such as a methyl chloride group, a methyl bromide group or a methyl iodide group, a dialkyl sulfate such as dimethyl sulfate or the like, N-(3-chloro-2-hydroxyl) An epichlorohydrin adduct of a tertiary amine mineral acid salt such as propyl)-N,N,N-trimethylammonium chloride, an inorganic salt such as hydrochloric acid, hydrogen bromide, sulfuric acid or phosphoric acid, formic acid, A cationic monomer which has been cationized by a carboxylic acid such as acetic acid or propionic acid.

Specific examples of the cationized cellulose include a polymer of a quaternary ammonium salt obtained by adding propylene glycol trimethyl ammonium chloride to hydroxyethyl cellulose (polyquaternium-10) , Polyquaternium-10), hydroxyethyl cellulose/dimethyldiallylammonium chloride copolymer (polyquaternium-4), and epoxy substituted by hydroxyethyl cellulose and trimethylammonium A polymer of a quaternary ammonium salt (polyquaternium-67) obtained by reacting a compound with lauryl dimethylammonium in place of an epoxide.

As an example of the vinyl-based or (meth)acrylic polymer or copolymer having a quaternary ammonium side chain, for example, poly(2-ethyl methacrylate oxyethyltrimethylammonium chloride) (poly season) Ammonium salt - 37).

Specific examples of the quaternized polyvinylpyrrolidone include, for example, a four-stage synthesis of a copolymer of vinylpyrrolidone (VP) and dimethylaminoethyl methacrylate and diethyl sulfate. Ammonium salt (polyquaternium-11).

Examples of the (meth) acrylate/amino acrylate copolymer include (acrylate/amino acrylate/C10-30 alkyl PEG-20 itaconic acid) copolymer.

Examples of the amine-substituted poly(meth)acrylate cross-linking polymer include polyacrylate-1 cross-linked polymer and polyquaternium-52.

Among the above cationic polymers, a (meth)acrylic cationic polymer is particularly preferred. For example, an alkyl acrylamide/acrylate/alkylaminoalkyl acrylamide/polyethylene glycol methacrylate copolymerizable according to the method described in Example 1 of JP-A-2-180911 can be used. Fit.

The amphoteric polymer is a polymer containing both a cationic group and an anionic group. From the viewpoint of structure, it can be derived by further introducing an anionic group or a copolymer to any of the above cationic polymers.

As the amphoteric polymer, an amphoteric polymer generally used in the field of cosmetics can be used. The liquid preparation may contain one or more kinds of amphoteric polymers, and may further contain a nonionic, anionic, and/or cationic polymer in combination with the amphoteric polymer.

Examples of the amphoteric polymer include a carboxyl group-modified or sulfonic acid-modified cationic polysaccharide (carboxymethyl chitosan, etc.), and a phosphorus beet base or a sulfobeta base in a side chain (methyl group). An acrylate-based polymer or a (meth)acrylic-based two-ionic polymer.

The following is an example of a compound having an ethylenically unsaturated bond which can constitute an amphoteric polymer such as the above (meth)acrylic ionic polymer, but the present invention is not limited to the following specific examples. Specific examples of the diionic monomer include a compound obtained by allowing a reforming agent such as sodium or potassium hydride to act as a specific example of the above cationic monomer precursor. Further, specific examples of the polar monomer include N,N-dimethylaminoethyl (meth)acrylate and N,N-diethylaminoethyl (meth)acrylate. N,N-dimethylaminopropyl acrylate, N,N-diethylaminopropyl (meth)acrylate, N,N-dimethylaminoethyl (meth) acrylamide , (meth) acrylamide N, N-diethylaminoethyl ester, (meth) acrylamide N, N-dimethylaminopropyl, (meth) acrylamide N, N- Diethylaminopropyl propyl ester, vinyl N,N-dimethylaminopropionate, p-dimethylaminomethyl styrene, p-dimethylaminoethyl styrene, p-diethylamino An amine oxide such as methyl styrene or p-diethylaminoethyl styrene.

As another example, a copolymer of a cationic vinyl or (meth)acrylic monomer and (meth)acrylic acid (dimethyldiallyl ammonium chloride/acrylic acid copolymer (polyquaternary ammonium salt) may, for example, be mentioned. -22) etc.).

Among the above amphoteric polymers, a (meth)acrylic two-ionic polymer is preferred. As a commercially available product, YUKAFORMER (manufactured by Mitsubishi Chemical Corporation) or (octyl acrylamide/acrylic acid hydroxy) of (methacryloxyethyl carboxybetaine/alkyl methacrylate) copolymer may be mentioned. Amphomer 28-4910 (Akzo Nobel), a propyl ester/butylaminoethyl methacrylate copolymer.

The water-insoluble polymer may, for example, be a fully alkalized polyvinyl alcohol which can be insolubilized after the formation of a film, or a partially alkalized polymer which can be crosslinked after being formed into a film by a combination with a crosslinking agent. Vinyl alcohol, poly(N-propionyl extended ethyl imine) graft-dimethyloxane/γ-aminopropylmethyloxane copolymer, etc. Oxazoline modified polyfluorene oxide, polyvinyl acetal diethylaminoacetate, zein (main component of corn protein), polyester, polylactic acid (PLA), polyacrylonitrile resin, polymethyl Acrylic resin such as acrylic resin, polystyrene resin, polyvinyl butyral resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polyurethane resin, polyfluorene An amine resin, a polyimide resin, a polyamidoximine resin, or the like. These water-insoluble polymers may be used alone or in combination of two or more. Among these water-insoluble polymers, it is preferred to use a fully alkalized polyvinyl alcohol which can be insolubilized after formation of a film, and a partial alkalization which can be cross-linked after formation of a film by use together with a crosslinking agent. Polyvinyl alcohol, polyvinyl butyral resin, poly(N-propionylethylidene) graft-dimethyloxane/γ-aminopropylmethyloxane copolymer, etc. The oxazoline is modified by polyoxo, water-insoluble polyester, zein and the like.

The above liquid is a liquid, that is, a fluid composition at normal temperature (0 to 35 ° C). The liquid agent is preferably a viscosity at 30 ° C of 500,000 mPa ‧ s or less from the viewpoint of application to the skin or a film formed by electrostatic spraying, and a film having a good adhesion. Preferably, it is 300,000 mPa‧s or less, and more preferably 100,000 mPa‧s or less. Here, the viscosity of the liquid agent was measured using a BM type viscometer (manufactured by TOKIMEC Co., Ltd., measuring conditions: rotor No. 1, 60 rpm, 1 minute).

The content of the polymer in the liquid preparation is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and still more preferably 1 from the viewpoint of adjusting the viscosity of the liquid agent and improving the adhesion. More than % by mass. Moreover, from the same viewpoint, it is preferably 15% by mass or less, more preferably 7.5% by mass or less, still more preferably 5% by mass or less.

The liquid agent may contain a polyol in addition to water, an alcohol, and a polymer which are solvents. Here, examples of the polyhydric alcohol include alkyl glycols such as ethylene glycol, propylene glycol, 1,3-propanediol, and 1,3-butylene glycol; diethylene glycol, dipropylene glycol, polyethylene glycol, and polypropylene glycol; Polyalkylene glycols such as glycerols such as glycerin, diglycerin and triglycerin. Among these, from the viewpoint of feeling of use such as smoothness at the time of coating, ethylene glycol, propylene glycol, 1,3-butylene glycol, dipropylene glycol, polyethylene glycol, glycerin, diglycerin, and the like are preferable. Preferably, it is propylene glycol, 1,3-butylene glycol, glycerin, and more preferably propylene glycol or 1,3-butanediol.

When the above liquid agent is applied to the skin, various methods other than the electrostatic spray method can be used. The thin layer of the liquid can be formed, for example, by applying a liquid agent to the skin by dripping or squeezing, and spreading the liquid agent to a skin or a film. The step of spreading the liquid agent may be carried out by, for example, using the user's own finger or using an applicator or the like. It is also possible to drip or smear only the liquid agent, but by having a step of spreading the coating, it can be fused to the skin or the film, and the adhesion of the film can be sufficiently enhanced. As another method, the liquid agent is sprayed toward the skin, and a thin layer of the liquid agent may be formed. At this time, it is not particularly necessary to perform the coating expansion separately, but it is also possible to perform the coating expansion after the spraying. Further, when the liquid preparation is applied after the formation of the film, the excess liquid agent can be removed by applying a sufficient liquid agent to the skin by the step of bringing the sheet into contact with the liquid application range.

The amount of the liquid applied to the skin or the film may be sufficient to increase the adhesion between the skin and the film. The amount of the liquid agent applied to the skin or the film is preferably 5 g/m ² or more, more preferably 10 g/m ² or more, from the viewpoint of improving the adhesion between the skin and the film. It is 15 g/m ² or more, and is preferably 50 g/m ² or less, more preferably 45 g/m ² or less.

Next, (2) a step of directly electrostatically spraying a composition containing the component (a) and the component (b) onto the skin to form a film on the skin.

The electrostatic spraying step (2) is a method in which a composition containing a predetermined component is directly applied to the skin to form a film. As a method of forming a film, the present invention employs an electrostatic spray method. The electrostatic spraying method is a method in which a positive or negative high voltage is applied to a composition to charge the composition, and the charged composition is sprayed toward the object. The sprayed composition is repetitively refined by the Coulomb repulsion and spreads into the space. After the process, or after adhering to the object, the solvent belonging to the volatile substance is dried to form a film on the surface of the object. Here, it is preferred to perform the electrostatic spraying step (2) after the liquid agent is applied (1) before the liquid agent is dried.

The above-mentioned composition "spray composition" used in the present invention is a liquid which is liquid in an environment where an electrostatic spray method is applied. This composition contains the following components (a) and (b).

(a) one or two or more kinds of volatile substances selected from the group consisting of water, alcohols, and ketones; and (b) a polymer having a film forming ability.

Each component will be described below.

The volatile substance of the component (a) is a substance which is volatile in the state of a liquid. In the composition for spraying, the component (a) is prepared by appropriately charging the composition for spraying placed in an electric field, and then discharging it from the tip end of the nozzle toward the skin, and when the component (a) evaporates, The charge density of the composition for spraying becomes excessive, which is made finer by the Coulomb repulsion and the component (a) is further evaporated to finally form a dried film. In order to achieve the object, the vapor pressure of the volatile substance 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, and still more preferably 0.67 kPa or more and 40.00 kPa or less at 20 ° C. More preferably, it is 1.33 kPa or more and 40.00 kPa or less.

Among the volatile substances of the component (a), for example, a monohydric chain aliphatic alcohol, a monohydric cyclic aliphatic alcohol, or a monovalent aromatic alcohol is suitably used as the alcohol. The monovalent chain aliphatic alcohol may, for example, be a C ₁ to C ₆ alcohol, and the monocyclic aliphatic alcohol may, for example, be a C ₄ to C ₆ cyclic alcohol, and the monovalent aromatic alcohol may, for example, be benzyl alcohol. Phenylethyl alcohol and the like. Specific examples of such may, for example, be ethanol, isopropanol, butanol, phenylethyl alcohol, propanol or pentanol. One or two or more kinds selected from these may be used.

Among the volatile substances of the component (a), examples of the ketone-based di-C ₁ -C ₄ alkyl ketone include acetone, methyl ethyl ketone, and methyl isobutyl ketone. These ketones may be used alone or in combination of two or more.

The volatile matter of the component (a) is preferably one or more selected from the group consisting of ethanol, isopropanol, butanol and water, more preferably one or more selected from the group consisting of ethanol and butanol, and the best. It contains ethanol.

The composition for spraying contains the polymer having the film forming ability of the component (b) together with the component (a). The polymer having a film forming ability belonging to the component (b) is generally a substance which is soluble in the volatile matter of the component (a). Here, the term "dissolution" means a state of dispersion at 20 ° C, and the state of dispersion is regarded as a uniform state depending on the purpose, and it is preferably a transparent or translucent state.

The polymer having a film forming ability is suitably used in combination with the properties of the volatile substance of the component (a). Specifically, a polymer having a film forming ability is roughly classified into a water-soluble polymer and a water-insoluble polymer.

Examples of the water-soluble polymer having a film forming ability include polytriglucose, hyaluronic acid, chondroitin sulfate, poly-γ-glutamic acid, modified corn starch, β-glucan, grape oligosaccharide, and heparin. Mucopolysaccharide such as keratan sulfate, cellulose, pectin, wood glue, lignin, glucomannan, galacturonic acid, flax-purple seed gum, tamarind seed glue, gum arabic, gum tragacanth, Natural polymer such as soybean water-soluble polysaccharide, alginic acid, carrageenan, laminaria, cold (yellow sugar), fucoidan, methylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, etc. Partially alkalized polyvinyl alcohol (in the case where a crosslinking agent is not used), a synthetic polymer such as a low alkalinized polyvinyl alcohol, polyvinylpyrrolidone (PVP), polyethylene oxide or sodium polyacrylate. These water-soluble polymers may be used alone or in combination of two or more. Among these water-soluble polymers, from the viewpoint of easy production of the film, it is preferred to use polytriglucose, partially alkalized polyvinyl alcohol, low alkalinized polyvinyl alcohol, polyvinylpyrrolidone, and polycyclic ring. A synthetic polymer such as oxyethane. In the case where polyethylene oxide is used as the water-soluble polymer, the number average molecular weight thereof is preferably 50,000 or more and 3,000,000 or less, more preferably 100,000 or more and 2.5 million or less.

On the other hand, as a water-insoluble polymer having a film forming ability, for example, a fully alkalized polyvinyl alcohol which can be insolubilized after formation of a film, and a film formed by using it together with a crosslinking agent can be used. Partially alkalized polyvinyl alcohol, poly(N-propionyl extended ethyl imine) graft-dimethyloxane / γ-aminopropyl methyl sulfoxane copolymer, etc. Oxazoline modified polyfluorene oxide, polyvinyl acetal diethylaminoacetate, zein (main component of corn protein), polyester, polylactic acid (PLA), polyacrylonitrile resin, polymethyl Acrylic resin such as acrylic resin, polystyrene resin, polyvinyl butyral resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polyurethane resin, polyfluorene An amine resin, a polyimide resin, a polyamidoximine resin, or the like. These water-insoluble polymers may be used alone or in combination of two or more. Among these water-insoluble polymers, it is preferred to use a fully alkalized polyvinyl alcohol which can be insolubilized after formation of a film, and a partial alkalization which can be cross-linked after formation of a film by use together with a crosslinking agent. Polyvinyl alcohol, polyvinyl butyral resin, polyurethane resin, poly(N-propionylethylidene) graft-dimethyloxane/γ-aminopropylmethyl Oxane copolymer, etc. The oxazoline-modified polyfluorene oxide, the polyvinyl acetal diethylaminoacetate, the zein, etc., more preferably one or two selected from the group consisting of polyvinyl butyral resin and polyaminomethyl ester resin More than one species.

The content of the component (a) in the composition for spraying is preferably 50% by mass or more, more preferably 55% by mass or more, still more preferably 60% by mass or more. Further, it is preferably 98% by mass or less, more preferably 96% by mass or less, still more preferably 94% by mass or less. The content of the component (a) in the composition for spraying 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, still more preferably 60% by mass or more and 94% by mass. the following. By mixing the component (a) in the composition for spray according to this ratio, the composition for spraying can be sufficiently volatilized when the electrostatic spray method is performed.

Further, the total amount of the volatile matter of the component (a) is preferably 50% by mass or more, more preferably 65% by mass or more, still more preferably 80% by mass or more. Further, it is preferably 100% by mass or less. The total amount of the volatile matter of the component (a) 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 still more preferably 80% by mass or more. And 100% by mass or less.

On the other hand, the content of the component (b) in the composition for spraying is preferably 2% by mass or more, more preferably 4% by mass or more, still more preferably 6% by mass or more. Further, it is preferably 50% by mass or less, more preferably 45% by mass or less, still more preferably 40% by mass or less. The content of the component (b) in the composition for spraying 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, still more preferably 6% by mass or more and 40% by mass. the following. By blending the component (b) in the composition for spray according to this ratio, the target film can be formed well at all times.

The content ratio ((a)/(b)) of the component (a) to the component (b) in the composition for spray is preferably from the viewpoint of sufficiently volatilizing the component (a) when performing the electrostatic spray method. It is 0.5 or more and 40 or less, more preferably 1 or more and 30 or less, still more preferably 2 or more and 25 or less.

Further, the content ratio ((a)/(b)) of the ethanol (a) to the component (b) in the composition for spray is from the viewpoint of sufficiently evaporating the ethanol (a) when performing the electrostatic spray method. It is preferably 0.5 or more and 40 or less, more preferably 1 or more and 30 or less, still more preferably 2 or more and 25 or less.

Further, the composition for spraying may contain a diol. Examples of the diols include ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, and polypropylene glycol. From the viewpoint of sufficiently evaporating the component (a) in the electrostatic spraying method, the composition for spraying is preferably 10% by mass or less, more preferably 3% by mass or less, still more preferably 1% by mass or less. It is not particularly useful.

The spray composition may contain only the above components (a) and (b), and may contain other components in addition to the components (a) and (b). The other component may, for example, be a plasticizer having a film forming ability of the component (b), a coloring pigment, an extender pigment, a dye, a surfactant, a UV defense agent, a fragrance, a repellent, an antioxidant, and a stabilizer. Preservatives, various vitamins, etc. When the spray composition contains other components, the blending ratio of the other components is preferably 0.1% by mass or more and 30% by mass or less, more preferably 0.5% by mass or more and 20% by mass or less.

In the case of the electrostatic spraying method, the viscosity of the composition for spraying is 25 ° C, preferably 1 mPa ‧ or more, more preferably 10 mPa ‧ s or more, still more preferably 50 mPa ‧ s or more. Further, the viscosity is 25 ° C, preferably 5,000 mPa ‧ s or less, more preferably 2,000 mPa ‧ s or less, still more preferably 1500 mPa ‧ s or less. The viscosity of the composition for spraying is 25 ° C, preferably 1 mPa ‧ or more and 5000 mPa ‧ or less, more preferably 10 mPa ‧ or more and 2000 mPa ‧ or less, still more preferably 50 mPa ‧ s or more and 1500 mPa ‧ s the following. By using a composition for a spray having a viscosity in this range, a porous film, in particular, a porous film composed of a deposit of fibers, can be formed uniformly by electrostatic spraying. The formation of the porous film is advantageous from the viewpoint of preventing steaming of the skin and the like. The viscosity of the composition for spraying was measured at 25 ° 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. Rotor No. 43 can be used for the rotor at this time.

The composition for spraying is directly sprayed on the human skin belonging to the object by electrostatic spraying. The electrostatic spray method includes a step of electrostatically spraying the composition of the spray onto the skin using an electrostatic spray device. Fig. 1 is a schematic view showing the configuration of an electrostatic coating apparatus suitable for use in the present invention. The electrostatic spray device 10 shown in Fig. 1 is provided with a low voltage power supply 11. The low voltage power source 11 is a voltage that can generate a voltage of several V to ten volts. For the purpose of improving the portability of the electrostatic coating apparatus 10, the low voltage power source 11 is preferably composed of one or two or more batteries. Further, by using a battery as the low-voltage power source 11, there is an advantage that it can be easily replaced as needed. Instead of a battery, an AC adapter or the like can be used as the low voltage power source 11.

The electrostatic spray device 10 is also provided with a high voltage power supply 12. The high-voltage power source 12 is connected to the low-voltage power source 11 and includes a circuit (not shown) that boosts the voltage generated by the low-voltage power source 11 to a high voltage. The booster circuit is generally composed of a transformer, a capacitor, and a semiconductor element.

The electrostatic spray device 10 further includes an auxiliary circuit 13. The auxiliary circuit 13 is interposed between the low voltage power source 11 and the high voltage power source 12, and has a function of adjusting the voltage of the low voltage power source 11 to stabilize the high voltage power source 12. Further, the auxiliary circuit 13 has a function of controlling the number of rotations of the motor provided in the microgear pump 14 to be described later. By controlling the number of rotations of the motor, the amount of the spray composition supplied to the micro-gear pump 14 by the container 15 of the composition for spray described later is controlled. A switch SW is mounted between the auxiliary circuit 13 and the low voltage power source 11, and the electrostatic spraying device 10 can be operated/stopped by switching of the switch SW.

The electrostatic spray device 10 further includes a nozzle 16. The nozzle 16 is made of various conductors such as metal, or a non-conductor such as plastic, rubber, or ceramics, and has a shape in which the spray composition for discharge is made possible from the tip end. A minute space through which the composition for spraying is distributed in the nozzle 16 is formed along the longitudinal direction of the nozzle 16. The size of the cross section of the minute space is preferably 100 μm or more and 1000 μm or less in terms of diameter.

Nozzle 16 is in communication with microgear pump 14 via line 17. The conduit 17 can be an electrical conductor or a non-conducting body. Further, the nozzle 16 is electrically connected to the high voltage power source 12. Thereby, a high voltage can be applied to the nozzle 16. At this time, in order to prevent excessive current from flowing when the nozzle 16 is in direct contact with the human body, the nozzle 16 and the high-voltage power source 12 are electrically connected via the current limiting resistor 19.

The micro-gear pump 14 that communicates with the nozzle 16 via the line 17 has a function as a supply device that supplies the composition for spraying contained in the container 15 to the nozzle 16 . The micro gear pump 14 is operated by receiving a power supply from the low voltage power source 11. Further, the micro gear pump 14 is configured to be supplied to the nozzle 16 by a predetermined amount of the spray composition under the control of the auxiliary circuit 13.

The micro gear pump 14 is connected to the container 15 via a flexible line 18. The container 15 contains a composition for spraying. The container 15 is preferably configured to be in an exchangeable configuration.

The electrostatic coating apparatus 10 having the above configuration can be used as shown, for example, in FIG. A hand held electrostatic spray device 10 having a size that can be held in one hand is shown in FIG. In the electrostatic coating apparatus 10 shown in Fig. 2, all of the members of the configuration shown in Fig. 1 are housed in a cylindrical casing 20. A nozzle (not shown) is disposed at one end 10a of the longitudinal direction of the casing 20. The nozzle is arranged such that the blowing direction of the composition coincides with the longitudinal direction of the casing 20, and is disposed in the casing 20 so as to be convex toward the skin side. By arranging the tip end of the nozzle toward the skin in the longitudinal direction of the casing 20, the composition for spraying is less likely to adhere to the frame, and the film can be stably formed.

When the electrostatic spraying device 10 is operated, the user, that is, the person who forms the film by electrostatic spraying on the skin of the user, holds the device 10 by hand, and the one end of the device 10 in which the nozzle (not shown) is disposed. 10a faces the object portion where the electrostatic spraying is performed. Fig. 2 shows a state in which one end 10a of the electrostatic coating apparatus 10 is directed toward the inside of the wrist before the user. In this state, the switch of the apparatus 10 is turned on to perform electrostatic spraying. An electric field is generated between the nozzle and the skin by applying power to the device 10. In the embodiment shown in Fig. 2, a positive high voltage is applied to the nozzle, and the skin becomes a negative electrode. When an electric field is generated between the nozzle and the skin, the composition for spraying at the tip end portion of the nozzle is separated by electrostatic induction, and the tip end portion thereof is tapered, and the droplet of the charged spray composition is discharged from the front end of the cone along the electric field toward the skin. In the air. When the component (a) which is a solvent is ejected from the composition which is discharged into the space and is charged, the charge density on the surface of the composition for the spray is excessive, and the Coulomb repulsive force is repeatedly finely expanded and spread into the space to reach the skin. At this time, by appropriately adjusting the viscosity of the composition for spraying, the sprayed composition can be brought to the skin in a state of droplets. Alternatively, during the period of being discharged into the space, the volatile matter belonging to the solvent is volatilized from the composition, and the polymer having the film forming ability belonging to the solute is solidified while being elongated and deformed by the potential difference to form a fiber. This fiber can also be deposited on the surface of the skin. For example, when the viscosity of the composition for spraying is increased, it is easy to deposit the composition on the surface of the skin in the form of fibers. Thereby, a porous film composed of a deposit of fibers is formed on the surface of the skin. The porous film composed of the deposit of fibers can also be formed by adjusting the distance between the nozzle and the skin or the voltage applied to the nozzle.

During the electrostatic spraying process, a high potential difference is generated between the nozzle and the skin. However, since the impedance is very large, the current flowing through the human body is extremely small. The present inventors have confirmed that the current flowing through the human body during the electrostatic spraying method is reduced by several digits compared to the current flowing through the human body caused by static electricity generated in normal life.

When the fibrous deposit is formed by the electrostatic spraying method, the thickness of the fiber is preferably 10 nm or more, and more preferably 50 nm or more when expressed by a circle equivalent diameter. Further, it is preferably 3,000 nm or less, more preferably 1,000 nm or less. The thickness of the fiber is observed by, for example, scanning electron microscopy (SEM), and the fiber is magnified 10,000 times for observation, and defects (fiber blocks, fiber intersections, droplets) are removed from the two-dimensional image, and 10 fibers are arbitrarily selected. The fibers are drawn perpendicular to the length of the fibers and can be measured by directly reading the fiber diameter.

The above-mentioned fibers are continuous fibers which are infinitely long in the production principle, but are preferably at least 100 times longer than the fiber thickness. In the present specification, a fiber having a length of 100 times or more of the fiber thickness is defined as "continuous fiber". Then, the film produced by the electrostatic spraying method is preferably a porous discontinuous film composed of a deposit of continuous fibers. The film of this form can be handled not only as an aggregate but also as a single sheet, and has a very soft characteristic, and is not easily broken even if a shearing force is applied thereto, and has an advantage of superior followability to the movement of the body. . Moreover, there is also an advantage that the sweat generated by the skin is superior in divergence. Furthermore, there is also an advantage that the peeling of the film is easy. On the other hand, the continuous film which does not have a fine hole is not easy to peel, and the dispersibility of sweat is very low, and the skin is easy to generate steaming.

The composition for the fibrous spray reaches the skin in a charged state. Since the skin is also charged as described above, the fibers are adhered to the skin by electrostatic force. Since fine irregularities such as skin texture are formed on the surface of the skin, the anchoring effect by the unevenness is multiplied and the fibers are more viscous and adhered to the skin surface. After the electrostatic spraying is thus completed, the power of the electrostatic spraying device 10 is turned off. Thereby, the electric field between the nozzle and the skin disappears, and the surface of the skin is fixed in charge. As a result, the adhesion of the film is more apparent.

The above description is directed to a porous film composed of a deposit of fibers as a film. However, the film form is not limited thereto, and a continuous film having no pores may be formed, or a fiber may be formed. The porous film of a form other than the deposit is, for example, a porous film formed by forming a plurality of through holes irregularly or regularly in a continuous film, that is, a discontinuous film. As described above, a film of any shape can be formed by controlling the viscosity of the composition for spraying, the distance between the nozzle and the skin, and the voltage applied to the nozzle.

The distance between the nozzle and the skin also depends on the voltage applied to the nozzle, and is preferably 50 mm or more and 150 mm or less in order to form the film uniformly. The distance between the nozzle and the skin can be measured by a non-contact type sensor or the like which is generally used.

The film formed by the electrostatic spray method is preferably 0.1 g/m ² or more, and more preferably 1 g/m ² or more, regardless of whether it is porous or not. Further, it is preferably 30 g/m ² or less, more preferably 20 g/m ² or less. For example, the basis weight of the film is preferably 0.1 g/m ² or more and 30 g/m ² or less, more preferably 1 g/m ² or more and 20 g/m ² or less. By setting the basis weight of the film in this way, the adhesion of the film can be improved. Further, the electrostatic spraying step of directly spraying the composition onto the skin to form a film means a step of electrostatically spraying the skin or the skin (also referred to simply as skin) to which the liquid agent is applied to form a film. The composition is applied to a sheet made of fibers by electrostatic spraying on a place other than the skin, and the step of applying the sheet to the skin is different from the electrostatic spraying step described above.

In the present invention, the liquid agent is applied to the skin by a method other than electrostatic spraying before or after the electrostatic spraying step of forming the film by the above electrostatic spraying or after the electrostatic spraying step. Application steps. By applying the liquid agent before the electrostatic spraying step, the polymer is more adhesive and easy to adhere. Moreover, since the liquid application step is performed after the electrostatic spraying step, especially after the electrostatic spraying step is completed, the film formed by the electrostatic spraying step is easily fused with the skin by the liquid agent, so that the film is highly dense with the skin. Chemical. The difference between the end of the film and the skin is not easy to occur, so the adhesion between the film and the skin is also improved. As a result, even if a film having a large degree of skin stretch such as a joint or a portion having a large curvature such as a shoulder is formed, peeling, cracking, or the like is less likely to occur. Further, when the coating film is transparent, colored, or translucent, it is difficult to shield the base skin. In the case where the coating film is a porous film composed of a deposit of fibers, it is preferable that the adhesion to the skin is high even if the film has a high void ratio, and a large capillary force is likely to occur. Further, when the fibers are fine, the porous film is likely to have a high specific surface area.

The liquid application step is performed before, and/or after, the step of forming the porous film composed of the fibrous deposit in the electrostatic spraying step, between the fibers forming the porous film, and/or the fibers The polymer containing the above liquid-containing liquid agent is formed on the surface to contain a liquid agent-carrying film. Thereby, the adhesion of the film is improved. Especially in the case where the film is colorless, transparent or translucent, since the film is less easily recognized, it can be rendered like a natural skin. Further, in the case where the film is colored and opaque, since the film has a transparent feeling, it can be formed as one part of the skin. Moreover, the above-mentioned so-called colored, also includes white.

The film manufacturing method as described above is useful as various cosmetic methods for the purpose of not being subjected to human surgery, treatment or diagnostic methods. For example, the method for producing a film of the present invention can be applied to the skin whitening, the spotting of the skin, the smear of the skin, the blackening of the skin, the shading of the skin wrinkles, the soft coking of the skin, and the protection of the skin from the skin for cosmetic purposes. UV, skin moisturizing. In addition, the film manufacturing method of the present invention can be applied to various behaviors for protecting the skin by individuals in the home, such as abrasion, cut wounds, lacerations, and stab wounds, protection of various wounds, prevention of hemorrhoids, and the like. .

The present invention has been described above based on the preferred embodiments thereof, but the present invention is not limited to the above embodiments. For example, in the above embodiment, the electrostatic spraying device 10 is held by a person who wants to form a film on his or her own skin, and an electric field is generated between the nozzle of the device 10 and the skin of the person, but as long as an electric field is generated between the two. It is not necessary to hold the electrostatic spraying device 10 by a person who wants to form a film on his or her own skin.

In the above embodiment, the present invention further discloses the following method for producing a film.

<1> A method for producing a film on a skin, characterized by having a liquid application step of applying a liquid agent containing a polymer to the skin by a method other than electrostatic spraying, in the following order or in reverse order; a step of directly spraying a composition containing the component (a) and the component (b) onto the skin to form a film on the skin; (a) one or two selected from the group consisting of water, alcohols, and ketones The above volatile substances; (b) a polymer having a film forming ability.

<2> The method for producing a film according to <1>, wherein in the electrostatic spraying step, the composition is electrostatically sprayed onto the skin to form a porous film.

<3> The method for producing a film according to <1> or <2>, wherein a porous film composed of a deposit of fibers is formed in the electrostatic spraying step, and then, in the liquid application step, The above liquid agent is applied to the above porous film.

(4) The method for producing a film according to any one of the above-mentioned, wherein, in the electrostatic spraying step, the composition is electrostatically sprayed onto the skin using an electrostatic spraying device to form a deposit of fibers. a porous coating film comprising: a container for accommodating the composition, a nozzle for discharging the composition, and a supply device for supplying the composition contained in the container to the nozzle; A power source that applies a voltage to the nozzle.

The method for producing a film according to any one of the above-mentioned items, wherein the vapor pressure of the volatile substance (a) is preferably 0.01 kPa or more and 106.66 kPa at 20 ° C. The following is more preferably 0.13 kPa or more and 66.66 kPa or less, still more preferably 0.67 kPa or more and 40.00 kPa or less, and still more preferably 1.33 kPa or more and 40.00 kPa or less.

(6) The method for producing a film according to any one of the above-mentioned items, wherein the volatile substance (a) is an alcohol, and the alcohol is preferably a monohydric chain aliphatic alcohol. a monocyclic aliphatic alcohol or a monohydric aromatic alcohol, which may be used alone or in combination of two or more kinds; as the above alcohol, ethanol, isopropanol, butanol or phenylethyl is particularly suitable. Alcohol, propanol and pentanol.

The method for producing a film according to any one of <1> to <6> wherein the volatile substance (a) is one or two selected from the group consisting of ethanol, isopropanol, butanol, and water. The above is more preferably one or two selected from the group consisting of ethanol and butanol, and more preferably ethanol.

The method for producing a film according to any one of <1> to <7> wherein the polymer having a film forming ability of (b) is a substance soluble in the volatile substance of (a). The present invention includes a water-soluble polymer and a water-insoluble polymer. Here, the term "dissolved" means a dispersed state at 20 ° C, and the dispersed state thereof is regarded as a uniform state, and is preferably in a state of being transparent or translucent.

The method for producing a film according to any one of <1> to <8> wherein the water-soluble polymer having a film forming ability is selected from the group consisting of polytriglucose, hyaluronic acid, chondroitin sulfate, and poly- Mucopolysaccharides such as γ-glutamic acid, modified corn starch, β-glucan, grape oligosaccharide, heparin, keratan sulfate, cellulose, pectin, wood glue, lignin, glucomannan, galactose Aldehydic acid, flax-purple pre-seed gum, tamarind seed gum, gum arabic, tragacanth, soybean water-soluble polysaccharide, alginic acid, carrageenan, laminaria, cold (yellow sugar), fucoidan, methyl A natural polymer such as cellulose, hydroxypropylcellulose or hydroxypropylmethylcellulose, partially alkalized polyvinyl alcohol (in the case where a crosslinking agent is not used), low alkalinized polyvinyl alcohol, polyvinylpyrrolidine One or more water-soluble polymers of ketone (PVP), polyethylene oxide, and sodium polyacrylate; more preferably selected from polytriglucose, partially alkalized polyvinyl alcohol, and low alkalinized polyvinyl alcohol One or more water-soluble polymers of polyvinylpyrrolidone and polyethylene oxide.

The method for producing a film according to any one of <1> to <9> wherein the water-insoluble polymer having a film forming ability is selected from the group consisting of a complete base which can be insolubilized after the film is formed. Partially alkalized polyvinyl alcohol, poly(N-propionyl extended ethyl imine) graft-dimethyl hydrazine which can be cross-linked after formation of a film by a combination with a crosslinking agent Oxylkane/γ-aminopropylmethyloxane copolymer, etc. Oxazoline modified polyfluorene oxide, polyvinyl acetal diethylaminoacetate, zein (main component of corn protein), polyester, polylactic acid (PLA), polyacrylonitrile resin, polymethyl Acrylic resin such as acrylic resin, polystyrene resin, polyvinyl butyral resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polyurethane resin, polyfluorene One or two or more kinds of water-insoluble polymers of an amine resin, a polyimide resin, and a polyamidoximine resin; more preferably, it is selected from fully alkalized polyvinyl alcohol which can be insolubilized after formation of a film. a partially alkalized polyvinyl alcohol, a polyvinyl butyral resin, a polyurethane resin, a poly(N-propionyl group) which can be crosslinked after being formed into a film by a combination with a crosslinking agent. Ethylimine) graft-dimethyloxane/γ-aminopropylmethyloxane copolymer, etc. An oxazoline-modified polyfluorene oxide, a polyvinyl acetal diethylaminoacetate, or one or more water-insoluble polymers of zein; more preferably, a polyvinyl butyral resin and One or two or more kinds of polyurethane resins.

The method for producing a film according to any one of <1> to <10> wherein the component (a) is a volatile substance containing at least ethanol, and the component (b) is selected from the group consisting of polyvinyl butyral. One or two or more kinds of a resin and a urethane resin.

The method for producing a film according to any one of the above aspects, wherein the content of the component (a) in the composition is preferably 50% by mass or more, more preferably 55% by mass. More preferably, it is 60% by mass or more, more preferably 98% by mass or less, still more preferably 96% by mass or less, still more preferably 94% by mass or less; and the content of the component (a) in the above 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, still more preferably 60% by mass or more and 94% by mass or less.

The method of producing a film according to any one of the above aspects, wherein the content of the component (b) in the composition is preferably 2% by mass or more, more preferably 4% by mass. More preferably, it is 6% by mass or more, more preferably 50% by mass or less, more preferably 45% by mass or less, still more preferably 40% by mass or less, and the content of the component (b) in the above 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, still more preferably 6% by mass or more and 40% by mass or less.

The method for producing a film according to any one of the above aspects, wherein the composition contains only the component (a) and the component (b), or the component (a) and the component (b) other components are contained; as the other component, a plasticizer, a coloring pigment, an extender pigment, a dye, a surfactant, a UV defense agent, which is a polymer having a film forming ability of the component (b), is used. Spices, repellents, antioxidants, stabilizers, preservatives, various vitamins.

<15> The method for producing a film according to <14>, wherein when the other component is contained in the composition, the blending ratio of the other component is preferably 0.1% by mass or more and 30% by mass or less, more preferably 0.5% by mass. % or more and 20% by mass or less.

The method for producing a film according to any one of the above aspects, wherein the viscosity of the composition is 25 ° C, preferably 1 mPa ‧ or more, more preferably 10 mPa ‧ s or more More preferably, it is 50 mPa ‧ or more, and preferably 5,000 mPa ‧ or less, more preferably 2000 mPa ‧ s or less, still more preferably 1500 mPa ‧ s or less; the viscosity of the above composition is preferably 1 mPa at 25 ° C ‧ s or more and 5000 mPa ‧ s or less, more preferably 10 mPa ‧ s or more and 2000 mPa ‧ s or less, still more preferably 50 mPa ‧ s or more and 1500 mPa ‧ s or less

The method for producing a film according to any one of <1> to <16> wherein the electrostatic spraying device is used for electrostatic spraying; the electrostatic spraying device is provided with a nozzle; and the nozzle is made of various metals. A conductor, or a non-conductor such as a plastic, a rubber or a ceramic, is formed into a shape in which the composition is discharged from the tip end.

The method for producing a film according to any one of <1> to <17> wherein the electrostatic spraying device is provided with an electrostatic spraying method, and the electrostatic spraying device includes a nozzle and a frame; The nozzle is disposed at one end of the direction, and the nozzle is disposed such that the blowing direction of the composition coincides with the longitudinal direction of the frame and is convex toward the skin side.

The method for producing a film according to any one of <1> to <18> wherein the composition to be sprayed is such that volatile substances belonging to the solvent are volatilized from the droplets, and the coatings belonging to the solute are covered. The film forming ability of the polymer is solidified while being elongated and deformed by a potential difference to form fibers.

The method for producing a film according to any one of the above aspects, wherein the electrostatic spraying device is provided with an electrostatic spraying method; the electrostatic spraying device includes a nozzle; and the distance between the nozzle and the skin is set to be 50mm or more and 150mm or less.

The method for producing a film according to any one of <1> to <20> wherein the basis weight of the film formed by the electrostatic spraying method is preferably 0.1 g/m ² or more, more preferably 1 g. /m ² or more; and preferably 30 g/m ² or less, more preferably 20 g/m ² or less; and the basis weight of the coating film is preferably 0.1 g/m ² or more and 30 g/m ² or less, more preferably 1 g/ m ² or more and 20 g/m ² or less.

The method for producing a film according to any one of <1> to <21> wherein the polymer contained in the liquid agent is selected from the group consisting of a nonionic polymer, an anionic polymer, and a cationic polymer. And at least one water-soluble polymer of the amphoteric polymer, or a water-insoluble polymer.

<23> The method for producing a film according to <22>, wherein the nonionic polymer is selected from the group consisting of (meth)acrylic water-soluble nonionic polymer, polyvinylpyrrolidone, and polypropylene decylamine. One or more kinds of sugars and their derivatives (ether or ester).

<24> The method for producing a film according to <22>, wherein the anionic polymer is selected from the group consisting of an anionic polysaccharide and a derivative thereof (alginate, pectin, hyaluronic acid, etc.), an anionic rubber (Sanxian gum) , dehydrogenase, hydroxypropyl trisin, gum arabic, karaya gum, tragacanth, etc.), anionic cellulose derivatives (carboxymethyl cellulose (CMC), etc.), and (methyl) One or more kinds of acrylic water-soluble anionic polymers.

<25> The method for producing a film according to <22>, wherein the cationic polymer is a cationic group having a quaternary ammonium group or the like, or a primary, secondary or tertiary amine group ionizable to a cationic group. The polymer of the group is preferably a polymer containing an amine group or an ammonium group in a side chain of the polymer chain or a polymer containing a diallyl quaternary ammonium salt as a constituent unit.

<26> The method for producing a film according to <22>, wherein the amphoteric polymer is selected from the group consisting of a carboxyl group-modified or a sulfonic acid-modified cationic polysaccharide (carboxymethyl chitosan, etc.), and a phosphorus beet in a side chain. One or more of a (meth) acrylate polymer having a base or a sulfobeine base and a (meth)acrylic ionic polymer.

The method for producing a film according to any one of the above aspects, wherein the viscosity of the liquid agent at 30 ° C is preferably 5,000 mPa ‧ or less, more preferably 3,000 mPa ‧ s or less, and further More preferably, it is 1000 mPa‧s or less.

The method for producing a film according to any one of the above aspects, wherein the content of the polymer in the liquid agent is preferably 0.5% by mass or more, more preferably 2% by mass or more, and further It is more preferably 4% by mass or more; and is preferably 20% by mass or less, more preferably 15% by mass or less, and still more preferably 7% by mass or less.

The method for producing a film according to any one of <1> to <28> wherein the amount of the liquid agent applied to the skin or the film by a method other than electrostatic spraying is preferably 5 g/m ^{2 .} The above is more preferably 10 g/m ² or more, still more preferably 15 g/m ² or more, and is preferably 50 g/m ² or less, more preferably 45 g/m ² or less.

The method of producing a film according to any one of the above aspects, wherein the content of the component (a) is 30% by mass or more and 98% by mass or less based on the composition, and the component (b) The content of the composition in the spray composition is 2% by mass or more and 50% by mass or less.

The method of producing a film according to any one of the above-mentioned items, wherein the content of the component (a) is 55 mass% or more and 96 mass% or less in the composition, and the component (b) The content of the composition in the spray composition is 4% by mass or more and 45% by mass or less.

The method of producing a film according to any one of the above aspects, wherein the component (a) is contained in the composition in an amount of 60% by mass or more and 94% by mass or less, and the component (b) The content of the composition in the spray composition is 6% by mass or more and 40% by mass or less.

The method for producing a film according to any one of <1> to <32> wherein the component (a) is a volatile substance containing at least ethanol, and the component (b) is selected from the group consisting of polyvinyl butyral. One or two or more kinds of a resin and a urethane resin.

 [Examples]  

Hereinafter, the present invention will be described in more detail by way of examples. However, the scope of the invention is not limited to the embodiments. Unless otherwise specified, "%" means "% by mass".

 [Test 1]    [Example 1]    (1) Modulation of composition A for spraying  

As a component (a) of the composition for the spray, 99.5% ethanol (manufactured by Wako Pure Chemical Industries, Ltd.) was used. As the component (b), polyvinyl butyral (manufactured by Sekisui Chemical Co., Ltd.: trade name: S-LEC B) was used.

In a 1 L glass beaker, the component (a), the component (b), and the additive (ELDEW PS-203 manufactured by Ajinomoto Health Supply Co., Ltd.) were weighed and stirred at room temperature for about 12 hours using a propeller mixer to obtain a uniform transparent solution. This was used as the composition A for spraying.

The component (a), the component (b), and the additive were each 80 parts by mass, 14 parts by mass, and 6.0 parts by mass.

 (2) Preparation of the liquid agent used in the liquid application step  

As a liquid agent, a polymer solution A to K 55 mg was used. Table 2 below shows the composition of the polymer solutions A to K.

 (3) Liquid application steps  

The above polymer solution was dropped onto the inner side of the human forearm and formed into a thin layer by finger coating to expand to a diameter of 4 cm or more and less than 6 cm. The amount of dripping was 55 mg, and the amount by which the area to be expanded was moistened or moistened, or the texture was different, and the degree of the presence of the solution A was understood by visual or tactile sensation was applied. As a result, the amount of the solution A applied to the skin was such that the basis weight of the solution A was 28.0 g/m ² .

 (4) Electrostatic spraying step  

Using the electrostatic coating apparatus 10 having the configuration shown in Fig. 1 and having the appearance shown in Fig. 2, the thin layer formed by the liquid application step of (3) was subjected to electrostatic spraying for 20 seconds. The conditions of the electrostatic spray method are as follows.

‧Applied voltage: 10kV

‧The distance between the nozzle and the skin: 100mm

‧ Discharge of spray composition: 5mL / h

‧Environment: 25 ° C, 30% RH

By this electrostatic spraying, a porous film composed of a deposit of fibers is formed on the surface of the skin. The film is a circle having a diameter of about 4 cm and a mass of about 5.5 mg. The fiber thickness measured by the above method was 0.5 μm.

 [Embodiment 2]  

In Example 1, the liquid application step is reversed from the electrostatic spraying step. Otherwise in the same manner as in Example 1, a porous film composed of a deposit of fibers was obtained.

 [Examples 3 to 14]  

In the same manner as in Example 1, except that the conditions shown in the following Tables 1 to 4 were used, the liquid application step and the electrostatic spray step were sequentially performed to obtain a porous film composed of a fibrous deposit.

 [Comparative Example 1]  

This comparative example is an example in which the liquid application step was not carried out in Example 1. Otherwise in the same manner as in Example 1, a porous film composed of a deposit of fibers was obtained.

 [Comparative Example 2]    (1) Modulation of the composition for spraying  

The composition for spray A was prepared in the same manner as in Example 1.

 (2) Sheet production by electrostatic spraying step  

An electrostatic spray method 10 having the appearance shown in Fig. 1 and having the appearance shown in Fig. 2 was used, and an electrostatic spray method was applied to a stainless steel plate for 20 seconds. The conditions of the electrostatic spray method are as follows.

‧Applied voltage: 10kV

‧The distance between the nozzle and the skin: 100mm

‧ Discharge of spray composition: 5mL / h

‧Environment: 25 ° C, 30% RH

By this electrostatic spraying, a porous film composed of a deposit of fibers is formed on the surface of the stainless steel sheet. The film is a circle having a diameter of about 4 cm and a mass of about 5.5 mg. The fiber thickness measured by the above method was 0.5 μm.

 (3) Liquid application steps  

The above polymer solution A was dropped onto the inner side of the human forearm and formed into a thin layer by finger coating to expand to an area of 4 cm or more and less than 6 cm in diameter. The amount of dripping was 55 mg, and the amount by which the area to be expanded was moistened or moistened, or the texture was different, and the degree of the presence of the solution A was understood by visual or tactile sensation was applied. As a result, the amount of the solution A applied to the skin was such that the basis weight of the solution A was 28.0 g/m ² .

 (4) Sheeting step  

The sheet obtained by the electrostatic spraying step of (2) is stably lightly pressed onto the thin layer formed by the liquid application step obtained in the step (4).

 [Comparative Example 3]  

In Comparative Example 2, the liquid application step was reversed to the order of the sheet application step. In the same manner as in Comparative Example 2, a porous film composed of a deposit of fibers was obtained.

 [Evaluation]  

The film formed in the examples and the comparative examples was evaluated for adhesion to the skin. The evaluation was performed by touching the film with a finger in a direction perpendicular to the skin and applying a fine vibration load for 5 seconds, and applying a shearing force to the film 5 times in a direction parallel to the skin to visually observe the subsequent film. The filming state is carried out. The results are shown in Table 1. The evaluation criteria are as follows.

1: When a fine vibration load is applied with a finger in the vertical direction, the film is almost completely peeled off.

2: When a fine vibration load is applied in a vertical direction with a finger, the fiber portion forming the film is partially peeled off.

3: No peeling in the vertical direction, but the coating film was almost completely peeled off when a shearing force was applied in the parallel direction.

4: No peeling in the vertical direction, but the film or the fiber portion was peeled off when a finger was applied with a shearing force in the parallel direction.

5: No peeling in the vertical direction, and the film or the fiber was not peeled off even when a shearing force was applied in the parallel direction.

(alkyl acrylate octyl acrylamide) copolymer: Dermacryl 79 (Akzo) obel (share))

Acrylate copolymer ammonium: YODOSOL GH800F (Akzo Nobel)

(alkyl acrylate / diacetone acrylamide) copolymer AMPD: Plascize L-53D (mutual chemistry (share))

(octyl acrylamide/hydroxypropyl acrylate/butylaminoethyl methacrylate) copolymer: Amphomer 28-4910 (Akzo Nobel)

2-Amino-2-methyl-1-propanol: AMP Ultra PC 1000 (ANGUS Chemical Company)

(Acrylamide/acrylic acid DMAPA/methoxy methacrylate PEG) copolymer: It was synthesized according to the method described in Example 1 of JP-A-2-180911.

Polyoxyl-9: It is synthesized according to the method described in Example 1 of JP-A-2-276824.

(Acrylate/C12-22 alkyl methacrylate) copolymer: SOLTEX OPT (DOW CHEMICAL)

(Methethyloxyethylcarboxycarboxybetaine/alkyl methacrylate) copolymer: YUKAFORMER R205 (Mitsubishi Chemical Co., Ltd.)

Ethanol: 99.5% ethanol Test drug grade (Wako Pure Chemical Industries Co., Ltd.)

*1: ELDEW PS-203 (Ajinomoto (share))

*1: Dermacryl 79 (Akzo Nobel)

*1: ELDEW PS-203 (Ajinomoto (share))

*2: AEA (Mitsubishi Chemical Foods Co., Ltd.)

Ethanol: Ethanol (99.5) Test drug premium (Wako Pure Chemical Industries Co., Ltd.)

1-butanol: 1-butanol test drug grade (Wako Pure Chemical Industries Co., Ltd.)

II (Phytosterol/octyldodedo) Laurel-based glutamate: ELDEW PS-203 (Ajinomoto (share))

Polyacrylic acid: Dermacryl 79 (Akzo Nobel)

Polyvinyl butyral: S-LCE B BM-1 (Shuishui Chemical Co., Ltd.)

Polyvinyl acetal diethylaminoacetate: AEA (Mitsubishi Chemical Foods Co., Ltd.)

*Comparative Examples 2 and 3 are examples in which a film is formed in advance of the skin by electrostatic spraying, and then applied to the skin.

As is apparent from the results shown in Table 1, the film formed by the method of each of the examples had a high adhesion to the skin as compared with the film formed by the method of the comparative example. Further, although not shown in the table, the film formed by the method of the comparative example was visually observed to have a fiber color (white), and the film formed by the method of the example was confirmed to have transparency.

Claims (17)

 A method for producing a film on a skin, characterized in that, in the following order or in reverse order, there is a liquid application step of applying a liquid agent containing a polymer to the skin by a method other than electrostatic spraying; The component (a) and the component (b) are directly electrostatically sprayed onto the skin to form a film on the skin; (a) one or more selected from the group consisting of water, alcohols, and ketones. a volatile substance; (b) a polymer having a film forming ability.    The method for producing a film according to claim 1, wherein in the electrostatic spraying step, the composition is electrostatically sprayed onto the skin to form a porous film.    The method for producing a film according to claim 1, wherein a porous film composed of a deposit of fibers is formed in the electrostatic spraying step, and then, in the liquid application step, the liquid agent is applied to the above On the porous film, a liquid carrier film in which the liquid agent is present is formed between the fibers constituting the porous film and/or the surface of the fiber.    The method for producing a film according to claim 1, wherein in the electrostatic spraying step, the composition is electrostatically sprayed onto the skin using an electrostatic spraying device to form a porous film composed of a deposit of fibers; The apparatus includes a container for accommodating the composition, a nozzle for discharging the composition, a supply device for supplying the composition accommodated in the container to the nozzle, and a power source for applying a voltage to the nozzle.    The method for producing a film according to claim 1, wherein the component (a) is at least one selected from the group consisting of ethanol, isopropyl alcohol, butanol, and water.    The method for producing a film according to claim 1, wherein the component (a) is a volatile substance containing at least ethanol.    The method for producing a film according to claim 1, wherein the component (a) is a volatile substance containing at least ethanol, and the content of the alcohol in the volatile substance is 50% by mass or more and 100% by mass or less.    The method for producing a film according to claim 1, wherein the content of the component (a) is 30% by mass or more and 98% by mass or less based on the composition.   The method for producing a film according to claim 1, wherein the component (b) is selected from the group consisting of fully alkalized or partially alkalized polyvinyl alcohol, polyvinyl butyral resin, polyurethane resin, One or more of oxazoline-modified polyfluorene oxide, water-soluble polyester, and zein.  The method of producing a film according to claim 1, wherein the component (b) is one or more selected from the group consisting of a polyvinyl butyral resin and a polyurethane resin.    The method of producing a film according to claim 1, wherein the content of the component (b) is 2% by mass or more and 50% by mass or less based on the composition for spraying.    The method for producing a film according to claim 1, wherein the content ratio ((a)/(b)) of the component (a) to the component (b) is 0.5 or more and 40 or less.    The method for producing a film according to claim 7, wherein the content ratio ((a)/(b)) of the ethanol (a) to the component (b) is 0.5 or more and 40 or less.    The method for producing a film according to claim 1, wherein the content of the component (a) is 30% by mass or more and 98% by mass or less based on the composition, and the content of the component (b) is in the composition for spraying. 2% by mass or more and 50% by mass or less.    The method for producing a film according to claim 1, wherein the content of the component (a) is 55 mass% or more and 96 mass% or less in the composition, and the content of the component (b) is in the spray composition. 4% by mass or more and 45% by mass or less.    The method for producing a film according to claim 1, wherein the content of the component (a) is 60% by mass or more and 94% by mass or less based on the composition, and the content of the component (b) is in the composition for spraying. 6 mass% or more and 40 mass% or less.    The method for producing a film according to claim 1, wherein the component (a) is a volatile substance containing at least ethanol, and the component (b) is selected from the group consisting of a polyvinyl butyral resin and a polyurethane resin. Kind or more than two.