WO2018194086A1

WO2018194086A1 - Method for producing ultraviolet protection coating film

Info

Publication number: WO2018194086A1
Application number: PCT/JP2018/015980
Authority: WO
Inventors: 智成岡田
Original assignee: 花王株式会社
Priority date: 2017-04-18
Filing date: 2018-04-18
Publication date: 2018-10-25
Also published as: JP7216484B2; CN110520100A; TW201841607A; JP2018177796A; KR20190137096A

Abstract

Provided is a coating film having a uniform and strong ultraviolet protection effect on the whole skin. Also provided is a method for producing an ultraviolet protection coating film on skin, the method being characterized by electrostatically spraying a composition containing component (a), component (b), and component (c) onto the skin directly. Component (a) is a volatile substance of at least one selected from among water, alcohol, and ketone; component (b) is a polymer having an ability to form a coating film; and component (c) is an ultraviolet protection agent.

Description

Method for producing UV protective coating

The present invention relates to a method for forming an ultraviolet protective film on the skin.

Conventionally, sunscreen cosmetics have been blended with UV protection agents in order to obtain high SPF (Sun protection Factor) values by blocking UV irradiation on the skin.

However, cosmetics containing these UV protection agents have low water resistance and sweat resistance, and are disadvantageous in that they disappear from the skin due to sweat and the like. Moreover, since there are many unevenness | corrugations on skin, a coating film is not uniform, and SPF value becomes low in the location where a coating film is thin. Furthermore, there is a problem that the coating film disappears by contact with skin such as clothes and fingers. In order to solve such problems, a technique is known in which an organic silicone polymer, a water-swellable clay mineral that has been subjected to a specific treatment, a PVP / alkyl copolymer, and the like are blended in cosmetics (Patent Documents 1 to 3). ).

On the other hand, various methods for forming a film by electrostatic spraying are known. For example, Patent Document 4 describes a method for treating skin including electrostatic spraying of a composition onto the skin. The composition used in this method includes a liquid insulating material, a conductive material, a particulate powder material, and a thickener. As this composition, cosmetics and skin care compositions containing pigments are typically used. Specifically, a cosmetic foundation is used as a composition. That is, the invention described in Patent Document 4 mainly assumes that the cosmetic foundation is made by electrostatic spraying for cosmetic purposes.

Patent Document 5 describes a disposable cartridge for use in a cosmetic electrostatic spray device. This electrostatic spray device is a hand-held self-contained device. This electrostatic spray device is used to spray a cosmetic foundation in the same manner as in Patent Document 4 described above.

(Patent Document 1) Japanese Patent Application Laid-Open No. 5-262634 (Patent Document 2) Japanese Patent Application Laid-Open No. 7-258055 (Patent Document 3) Japanese Patent Application Laid-Open No. 8-259430 (Patent Document 4) Japanese Patent Application Laid-Open No. 2006-104211 (Patent Document 3) Reference 5) Japanese Patent Publication No. 2003-507165

The present invention provides a method for producing an ultraviolet protective coating on the skin, characterized in that the composition comprising the component (a), the component (b) and the component (c) is electrostatically sprayed directly onto the skin. is there.
(A) one or more volatile substances selected from water, alcohol and ketone,
(B) a polymer having a film-forming ability,
(C) UV protection agent.

It is the schematic which shows the structure of the electrostatic spray apparatus used suitably by this invention. It is a schematic diagram which shows a mode that an electrostatic spray method is performed using an electrostatic spray apparatus.

Detailed Description of the Invention

However, even with the techniques of Patent Documents 1 to 3, a uniform coating film is not formed because there are many irregularities on the skin, and the distribution of the UV protection agent in the coating film is not uniform. The SPF value was not uniform. In order to obtain a sufficient SPF value, it is necessary to increase the thickness of the coating film, but there is a problem in that the transparency is impaired.
In addition, the film formed by electrostatic spraying described in Patent Documents 4 and 5 has insufficient adhesion to the skin, and foundation color transfer due to contact with clothing or skin occurs.
Accordingly, the present invention provides a new means for forming a UV protective coating that is not only excellent in UV protection but also has a uniform, durable and excellent appearance without forming a thick coating. .

The present inventor has made various studies to form a film having excellent ultraviolet protection ability on the skin, and contains (a) a volatile substance, (b) a polymer having film formation ability, and (c) an ultraviolet protection agent. By directly spraying the composition directly onto the skin, the film formed on the skin is not easily lost by contact with clothing, skin, water, etc., the touch and appearance are good, and the UV protection effect is achieved. The present invention has been completed by finding a dramatic improvement.

According to the present invention, the SPF value is remarkably improved as compared with the case where an ultraviolet protective agent is applied to the skin, and a film having an excellent ultraviolet protective effect is formed on the skin. In addition, the formed film has excellent water resistance and sweat resistance, and has excellent durability that it is not easily lost by contact with skin or clothing, and also has good touch and appearance. In addition, when the UV protection agent is applied to the skin, the application is not uniform due to the unevenness of the skin, and the UV protection effect cannot be obtained uniformly on the skin. Since a film is formed, a uniform UV protection effect can be obtained.

In the present invention, the composition that is electrostatically sprayed directly onto the skin (hereinafter sometimes referred to as a spray composition) is a composition containing the following components (a), (b), and (c). is there.
(A) one or more volatile substances selected from water, alcohol and ketone,
(B) a polymer having a film-forming ability,
(C) UV protection agent.

The volatile substance of component (a) is a substance that is volatile in the liquid state. In the spray composition, the component (a) is discharged from the tip of the nozzle toward the skin after the spray composition placed in an electric field is sufficiently charged, and the component (a) evaporates. The charge density of the spray composition becomes excessive, and the component (a) further evaporates while being further refined by Coulomb repulsion, and is finally blended for the purpose of forming a dry film. For this purpose, 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 at 20 ° C. It is still more preferably 67 kPa or more and 40.00 kPa or less, and further preferably 1.33 kPa or more and 40.00 kPa or less.

Among the volatile substances of component (a), as the alcohol, for example, a monovalent chain aliphatic alcohol, a monovalent cyclic aliphatic alcohol, or a monovalent aromatic alcohol is preferably used. Examples of monovalent chain aliphatic alcohols include C ₁ -C ₆ alcohols, examples of monovalent cyclic alcohols include C ₄ -C ₆ cyclic alcohols, and examples of monovalent aromatic alcohols include benzyl alcohol and phenylethyl alcohol. Each is listed. Specific examples thereof include ethanol, isopropyl alcohol, butyl alcohol, phenylethyl alcohol, n-propanol, n-pentanol and the like. These alcohols can use 1 type, or 2 or more types chosen from these.

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

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. More preferably, it is a volatile substance containing ethanol.

The content of the component (a) in the spray composition is preferably 50% by mass or more, more preferably 55% by mass or more, and further preferably 60% by mass or more. Moreover, it is preferable that it is 98 mass% or less, it is still more preferable that it is 96 mass% or less, and it is still more preferable that it is 94 mass% or less. The content of the component (a) in the spray composition is preferably 50% by mass to 98% by mass, more preferably 55% by mass to 96% by mass, and 60% by mass to 94% by mass. More preferably, it is as follows. By containing the component (a) in the spray composition at this ratio, the spray composition can be sufficiently volatilized when the electrostatic spray method is performed.
Further, ethanol is preferably 50% by mass or more, more preferably 65% by mass or more, and still more preferably 80% by mass or more based on the total amount of the volatile substance of component (a). Moreover, it is preferable that it is 100 mass% or less. 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 more preferably 80% by mass or more and 100% by mass or less with respect to the total amount of the volatile substance of component (a). More preferably, it is at most mass%.

The polymer having film-forming ability as the component (b) is generally a substance that can be dissolved in the volatile material of the component (a). Here, dissolution means that the dispersion is in a dispersed state at 20 ° C., and the dispersed state is a visually uniform state, preferably a visually transparent or translucent state.

As the polymer having a film-forming ability, an appropriate polymer is used according to the nature of the volatile substance of component (a). Specifically, polymers having a film forming ability are roughly classified into water-soluble polymers and water-insoluble polymers. In the present specification, the “water-soluble polymer” means that 1 g of a polymer is weighed in an environment of 1 atm and 23 ° C. and then immersed in 10 g of ion-exchanged water. The thing which has the property which 5g or more melt | dissolves in water. On the other hand, in this specification, “water-insoluble polymer” means that 1 g of a polymer is weighed in an environment of 1 atm and 23 ° C. and then immersed in 10 g of ion-exchanged water. .5g or more has the property of not dissolving.

Examples of the water-soluble film-forming polymer include, for example, pullulan, hyaluronic acid, chondroitin sulfate, poly-γ-glutamic acid, modified corn starch, β-glucan, glucooligosaccharide, heparin, keratosulfuric mucopolysaccharide, cellulose, pectin, etc. , Xylan, lignin, glucomannan, galacturonic acid, psyllium seed gum, tamarind seed gum, gum arabic, tragacanth gum, soy water soluble polysaccharide, alginic acid, carrageenan, laminaran, agar (agarose), fucoidan, methylcellulose, hydroxypropylcellulose, hydroxypropyl Natural polymers such as methylcellulose, partially saponified polyvinyl alcohol (when not used in combination with a crosslinking agent), low saponified polyvinyl alcohol, polyvinyl pyrrolidone (PVP), polyethylene Examples thereof include synthetic polymers such as oxide and sodium polyacrylate. These water-soluble polymers can be used alone or in combination of two or more. Among these water-soluble polymers, it is preferable to use pullulan and synthetic polymers such as partially saponified polyvinyl alcohol, low saponified polyvinyl alcohol, polyvinyl pyrrolidone, and polyethylene oxide from the viewpoint of easy production of the coating. When polyethylene oxide is used as the water-soluble polymer, the number average molecular weight is preferably 50,000 or more and 3 million or less, and more preferably 100,000 or more and 2.5 million or less.

On the other hand, examples of the water-insoluble polymer having film-forming ability include, for example, fully saponified polyvinyl alcohol that can be insolubilized after film formation, partially saponified polyvinyl alcohol that can be crosslinked after film formation by using in combination with a crosslinking agent, and poly (N-propylene). Noylethyleneimine) graft-dimethylsiloxane / γ-aminopropylmethylsiloxane copolymer and other oxazoline-modified silicones, polyvinyl acetal diethylaminoacetate, zein (a major component of corn protein), polyester, polylactic acid (PLA), polyacrylonitrile resin, Acrylic resin such as polymethacrylic acid resin, polystyrene resin, polyvinyl butyral resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polyurethane resin, polyamide resin , Polyimide resins, polyamide-imide resins. These water-insoluble polymers can be used alone or in combination of two or more. Among these water-insoluble polymers, fully saponified polyvinyl alcohol that can be insolubilized after film formation, partially saponified polyvinyl alcohol that can be crosslinked after film formation by using in combination with a crosslinking agent, polyvinyl butyral resin, polyurethane resin, poly (N-propanoyl) Ethyleneimine) Graft-dimethylsiloxane / γ-aminopropylmethylsiloxane copolymer and other oxazoline-modified silicones, polyvinyl acetal diethylaminoacetate, zein, etc. are preferably used, one or two selected from polyvinyl butyral resin and polyurethane resin The above is more preferable.

The content of the component (b) in the spray composition is preferably 2% by mass or more, more preferably 4% by mass or more, and further preferably 6% by mass or more. Further, it is preferably 50% by mass or less, more preferably 45% by mass or less, and further preferably 40% by mass or less. The content of the component (b) in the spray composition is preferably 2% by mass or more and 50% by mass or less, more preferably 4% by mass or more and 45% by mass or less, and more preferably 6% by mass or more and 40% by mass. More preferably, it is as follows. By containing the component (b) in the spray composition at this ratio, the intended coating can be efficiently formed.

The ratio ((a) / (b)) of the content of component (a) and component (b) in the spray composition is sufficient to volatilize component (a) when performing electrostatic spraying. It is possible to form a supported film without secondary agglomeration of the powder, and as a result, even after being applied to the skin, it uniformly adheres to the skin dermis, skin grooves and pores, resulting in uneven color. From the viewpoint of preventing white floating and makeup, it is preferably from 0.5 to 40, more preferably from 1 to 30, and even more preferably from 2 to 25.
Moreover, the ratio ((a) / (b)) of the content of ethanol (a) and component (b) in the spray composition sufficiently volatilizes ethanol (a) when performing the electrostatic spray method. It is possible to form a supported film without secondary agglomeration of the powder, and as a result, even after being applied to the skin, it adheres uniformly to the skin dermis, skin grooves and pores, From the viewpoint of preventing uneven color, whitening, and makeup blur, it is preferably from 0.5 to 40, more preferably from 1 to 30, and even more preferably from 2 to 25.

Component (c) is a UV protection agent. As the component (c), an ultraviolet absorber, particularly an organic ultraviolet absorber is preferably used. The organic ultraviolet absorber is preferably an oil-soluble one, such as a benzoic acid-based UV absorber, an anthranilic acid-based UV absorber, a salicylic acid-based UV absorber, a cinnamic acid-based UV absorber, a benzophenone-based UV absorber, or a triazine-based UV absorber. An absorbent etc. are mentioned.

As benzoic acid-based UV absorbers, paraaminobenzoic acid (hereinafter abbreviated as PABA), glyceryl PABA, ethyldihydroxypropyl PABA, N-ethoxylate PABA ethyl ester, N-dimethyl PABA ethyl ester, N-dimethyl PABA butyl ester, N -Dimethyl PABA amyl ester, octyl dimethyl PABA, diethylaminohydroxybenzoyl hexyl benzoate and the like. From the viewpoint of enhancing the ultraviolet absorption effect, paraaminobenzoic acid and diethylaminohydroxybenzoyl hexyl hexyl are preferable, and diethylaminohydroxybenzoyl hexyl hexyl is more preferable.
Examples of the anthranilic acid UV absorber include homomenthyl-N-acetylanthranilate.
Examples of salicylic acid-based ultraviolet absorbers include amyl salicylate, menthyl salicylate, homomenthyl salicylate, octyl salicylate, phenyl salicylate, benzyl salicylate, p-isopropanol phenyl salicylate and the like.
Cinnamic acid UV absorbers include ethyl-4-isopropylcinnamate, ethyl-2,4-diisopropylcinnamate, methyl-2,4-diisopropylcinnamate, propyl-p-methoxycinnamate, isopropyl-p-methoxycinna Mate, isoamyl-p-methoxycinnamate, 2-ethylhexyl-p-methoxycinnamate, 2-ethoxyethyl-p-methoxycinnamate, cyclohexyl-p-methoxycinnamate, ethyl-α-cyano-β-phenylcinnamate 2-ethylhexyl-α-cyano-β-phenylcinnamate, glyceryl mono-2-ethylhexanoyl diparamethoxycinnamate, and the like. Of these, 2-ethylhexyl-p-methoxycinnamate is preferred, and 2-ethylhexyl-p-methoxycinnamate is more preferred from the viewpoint of enhancing the ultraviolet absorption effect. A commercially available product of 2-ethylhexyl-p-methoxycinnamate is ubinal MC80 (manufactured by BASF).
Examples of benzophenone ultraviolet absorbers include 2,4-dihydroxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4,4′-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4′-methylbenzophenone, 2-hydroxy-4-methoxybenzophenone, 4-phenylbenzophenone, 2-ethylhexyl-4′-phenylbenzophenone-2-carboxylate, 2-hydroxy-4-n -Octoxybenzophenone, 4-hydroxy-3-carboxybenzophenone and the like. From the viewpoint of enhancing the ultraviolet absorption effect, it is more preferable to contain 2,4-dihydroxybenzophenone.
Examples of triazine ultraviolet absorbers include 2,4,6-tris [4- (2-ethylhexyloxycarbonyl) anilino] -1,3,5-triazine, 2,4-bis-[{4- (2 One or more selected from -ethylhexyloxy) -2-hydroxy} -phenyl] -6- (4-methoxyphenyl) -1,3,5-triazine is preferred. Including 2,4-bis [{4- (2-ethylhexyloxy) -2-hydroxy} -phenyl] -6- (4-methoxyphenyl) -1,3,5-triazine from the viewpoint of enhancing the ultraviolet absorption effect It is more preferable.
Others include 3- (4′-methylbenzylidene) -dl-camphor, 3-benzylidene-dl-camphor, urocanic acid ethyl ester, 2-phenyl-5-methylbenzoxazole, 2,2′-hydroxy- 5-methylphenylbenzotriazole, 2- (2′-hydroxy-5-t-octylphenyl) benzotriazole, dibenzalazine, dianisoylmethane, 4-methoxy-4′-t-butyldibenzoylmethane, 5- (3 3-dimethyl-2-norbornidene) -3-pentan-2-one, benzene bis-1,3-diketone derivatives described in JP-A-2-212579, benzoylpinacolone derivatives described in JP-A-3-220153, etc. Is mentioned. From the viewpoint of enhancing the ultraviolet absorption effect, 4-methoxy-4′-t-butyldibenzoylmethane is more preferably contained, and a commercially available product is Parasol 1789 (manufactured by DSM Nutrition Japan).

As the component (c), it is preferable to contain an ultraviolet absorber from the viewpoint of enhancing the ultraviolet protective effect, and among them, a benzoic acid ultraviolet absorber, a benzophenone ultraviolet absorber, a cinnamic acid ultraviolet absorber, and a triazine ultraviolet absorber. It is preferable to contain at least one selected from agents, more preferably at least one selected from benzoic acid-based UV absorbers, cinnamic acid-based UV absorbers, and triazine-based UV absorbers. More preferably, it contains at least one selected from an acid UV absorber, a cinnamic acid UV absorber, and a triazine UV absorber. Further, it preferably contains a transdermal acid-based ultraviolet absorber, and more preferably contains 2-ethylhexyl-p-methoxycinnamate.

Component (c) UV protection agent can be used alone or in combination of two or more, and the combination and content thereof are determined according to the UV protection effect. From the viewpoint of further developing the UV protection effect, the content of the component (c) is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and 0.10% by mass or more in the spray composition. More preferably. Further, from the viewpoint of durability and suppression of stickiness of the coating, the content of the component (c) is preferably 15% by mass or less, more preferably 12% by mass or less, and further preferably 10% by mass in the spray composition. It is as follows.

The ratio of the content of the component (c) and the content of the component (b) ((c) / (b)) in the spray composition is preferably 0.02 or more from the viewpoint of UV protection ability. It is more preferably 0.04 or more, more preferably 0.06 or more, and is preferably 0.5 or less from the viewpoint of durability and stickiness of the coating, and is 0.45 or less. More preferably, it is more preferably 0.4 or less.

Furthermore, glycol can be contained in the spray composition. Examples of the glycol include ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, and polypropylene glycol. The component (a) can be sufficiently volatilized when the electrostatic spray method is performed, and from the viewpoint of suppressing secondary aggregation of the powder, 10% by mass or less is preferable in the spray composition, and 3% by mass or less. Is more preferable, 1 mass% or less is preferable, and it is preferable not to contain substantially.

The spray composition may contain only the component (a), component (b) and component (c) described above, or in addition to the component (a), component (b) and component (c). And other components may be included. Other components include, for example, a liquid oil for dissolving the component (c), a plasticizer of a polymer having a film-forming ability of the component (b), a color pigment, an extender pigment, a dye, a surfactant, a fragrance, and a repellent. , Antioxidants, stabilizers, preservatives, various vitamins and the like. When other components are contained in the spray composition, the content of the other components is preferably 0.1% by mass or more and 30% by mass or less, and 0.5% by mass or more and 20% by mass or less. More preferably it is.

In the present invention, the spray composition is directly sprayed onto the skin.

When performing the electrostatic spraying method, a spray composition having a viscosity of preferably 1 mPa · s or more, more preferably 10 mPa · s or more, more preferably 50 mPa · s or more at 25 ° C. is used. In addition, a material having a viscosity at 25 ° C. of preferably 5000 mPa · s or less, more preferably 2000 mPa · s or less, and still more preferably 1500 mPa · s or less is used. The viscosity of the spray composition is preferably 1 mPa · s or more and 5000 mPa · s or less, more preferably 10 mPa · s or more and 2000 mPa · s or less, more preferably 50 mPa · s or more and 1500 mPa · s or less at 25 ° C. It is. By using a spray composition having a viscosity in this range, a porous coating containing an ultraviolet protective agent, particularly a porous coating made of a fiber deposit containing an ultraviolet protective agent, can be successfully formed by electrostatic spraying. Can do. The formation of a porous coating containing an ultraviolet protective agent is advantageous from the viewpoints of enhancing the ultraviolet protective effect, obtaining a uniform ultraviolet protective effect, adhesion of the coating, suppression of coating feeling, prevention of skin stuffiness, etc. . The viscosity of the spray composition is 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. In this case, the rotor No. 43 can be used.

The composition for spraying is sprayed directly on the part of the human skin where UV protection is intended by electrostatic spraying. The electrostatic spray method includes a step of electrostatic spraying the spray composition on the skin using an electrostatic spray device. The electrostatic spray apparatus basically includes a container for storing the composition, a nozzle for discharging the composition, a supply device for supplying the composition stored in the container to the nozzle, A power source for applying a voltage to the nozzle.

FIG. 1 is a schematic diagram showing the configuration of an electrostatic spray apparatus suitably used in the present invention. The electrostatic spray apparatus 10 shown in the figure includes a low voltage power supply 11. The low voltage power supply 11 can generate a voltage of several volts to several tens of volts. In order to increase the portability of the electrostatic spray device 10, the low voltage power supply 11 is preferably composed of one or two or more batteries. Further, by using a battery as the low voltage power supply 11, there is an advantage that replacement can be easily performed as necessary. Instead of the battery, an AC adapter or the like can be used as the low voltage power supply 11.

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 step-up electric circuit is generally composed of a transformer, a capacitor, a semiconductor element, and the like.

The electrostatic spray device 10 further includes an auxiliary electric circuit 13. The auxiliary electric circuit 13 is interposed between the low voltage power supply 11 and the high voltage power supply 12 described above, and has a function of adjusting the voltage of the low voltage power supply 11 and causing the high voltage power supply 12 to operate stably. Further, the auxiliary electric circuit 13 has a function of controlling the rotational speed of a motor provided in the micro gear pump 14 described later. By controlling the number of rotations of the motor, the amount of the spray composition supplied from the spray composition container 15 to be described later to the micro gear pump 14 is controlled. A switch SW is attached between the auxiliary electric circuit 13 and the low voltage power source 11, and the electrostatic spray device 10 can be operated / stopped by turning on / off the switch SW.

The electrostatic spray device 10 further includes a nozzle 16. The nozzle 16 is made of various conductors including metals and non-conductors such as plastic, rubber, and ceramic, and has a shape that allows the spray composition to be discharged from its tip. In the nozzle 16, a minute space through which the spraying composition flows 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.
The nozzle 16 communicates with the micro gear pump 14 through a pipe line 17. The conduit 17 may be a conductor or a non-conductor. The nozzle 16 is electrically connected to the high voltage power supply 12. As a result, a high voltage can be applied to the nozzle 16. In this case, the nozzle 16 and the high voltage power supply 12 are electrically connected via the current limiting resistor 19 in order to prevent an excessive current from flowing when the human body directly touches the nozzle 16.

The micro gear pump 14 that communicates with the nozzle 16 via the pipe line 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 operates by receiving power from the low voltage power source 11. Further, the micro gear pump 14 is configured to supply a predetermined amount of the spray composition to the nozzle 16 under the control of the auxiliary electric circuit 13.

The container 15 is connected to the micro gear pump 14 through a flexible pipe 18. The container 15 contains a spraying composition. The container 15 is preferably in a cartridge-type replaceable form.

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

When the electrostatic spray device 10 is operated, a user, that is, a person who forms a film on a portion of the skin to be protected against ultraviolet rays by electrostatic spray, grasps the device 10 by hand, and a nozzle (not shown). The one end 10a of the apparatus 10 in which is disposed) is directed to the application site where electrostatic spraying is performed. FIG. 2 shows a state where one end 10a of the electrostatic spray device 10 is directed to the inner side of the user's forearm. Under this state, the apparatus 10 is turned on to perform the electrostatic spray method. When the apparatus 10 is turned on, an electric field is generated between the nozzle and the skin. In the embodiment shown in FIG. 2, a positive high voltage is applied to the nozzle and the skin becomes 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, the tip becomes a cone shape, and droplets of the spray composition charged from the tip of the cone are discharged. It is discharged into the air along the electric field toward the skin. As component (a), which is a solvent, evaporates from the spray composition charged and discharged into space, the charge density on the surface of the spray composition becomes excessive and spreads into the space while repeating miniaturization by Coulomb repulsion. Reach the skin. In this case, by appropriately adjusting the viscosity of the spray composition, the sprayed composition can reach the application site in the form of droplets. Alternatively, while being discharged into the space, the volatile substance that is the solvent is volatilized from the droplets, the polymer having the film forming ability that is the solute is solidified, and the fiber is formed while being elongated and deformed by the potential difference. Fibers can also be deposited at the application site. For example, increasing the viscosity of the spray composition tends to deposit the composition at the application site in the form of fibers. As a result, a porous coating made of a fiber deposit is formed on the surface of the application site. A porous film made of a fiber deposit containing an ultraviolet protective agent can also be formed by adjusting the distance between the nozzle and the skin and the voltage applied to the nozzle.

During the electrostatic spray method, 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. For example, the present inventor has confirmed that the current flowing through the human body during the electrostatic spray method is several orders of magnitude smaller than the current flowing through the human body due to static electricity generated in normal life.

When forming a fiber deposit containing an ultraviolet protective agent by an electrostatic spray method, the thickness of the fiber is preferably 10 nm or more, and more preferably 50 nm or more, when expressed in terms of a circle-equivalent diameter. . Moreover, it is preferable that it is 3000 nm or less, and it is still more preferable that it is 1000 nm or less. The thickness of the fiber is observed by, for example, scanning electron microscope (SEM) observation by magnifying the fiber 10,000 times, and removing defects (fiber clumps, fiber intersections, droplets) from the two-dimensional image, It can be measured by selecting 10 fibers arbitrarily, drawing a line perpendicular to the longitudinal direction of the fiber, and directly reading the fiber diameter.

The film, which is a fiber deposit formed by electrostatic spraying, has an ultraviolet protective agent-supporting film in which component (c) is present on the surface side of the constituent fiber. The surface side of the fiber means the surface or a part of the surface and between the fibers. Although the content of the component (c) in the spray composition depends on the affinity between the polymer and the component (c), if the content is approximately 1% by mass or more, the constituent fibers swell and become softer to the skin. In addition, the component (c) is likely to bleed out from the constituent fibers, and an ultraviolet protective agent-supporting film is easily formed between the constituent fibers, while the components in the spray composition When the content of (c) is less than 1% by mass, it is difficult to form an ultraviolet protective agent-supporting film on the surface of the constituent fibers. When the ultraviolet protective agent-supporting coating is formed on the fibers constituting the coating in this way, the adhesion to the skin is enhanced, the coating tends to become transparent, and the natural appearance is approached. Furthermore, since the persistence of adhesion is increased, it is effective for improving the moisture retention of the skin or improving the skin condition. In addition, the effect of uniformity of these adhesiveness and ultraviolet protection effect is further enhanced by applying a liquid agent described later.

In the case of skin containing sweat, sebum, and the like, the component (c) is combined in the fiber, so that the fiber swells and is easily plasticized. For example, when a thin film is produced by electrostatic spraying the same composition on a metal surface that does not contain moisture or oil and a skin surface that contains moisture or oil, such as the palm for 5 seconds, the change in fiber diameter is observed over time. Then, the fiber electrostatically sprayed on the skin surface becomes larger in diameter due to swelling than the fiber electrostatically sprayed on the metal surface. In this way, the coating film containing fibers formed by electrostatic spraying is plasticized with oil and moisture in the skin and becomes softer, so that the followability of the fibers themselves to the texture of the skin is improved. The component (c) bleeds out and exists between the fiber surface and between the fibers, so that the coating film containing the fibers becomes translucent or transparent, and natural appearance is imparted. When the film formation target is skin containing sweat or sebum, the fiber diameter due to swelling satisfies the following formula (1).
(Fiber diameter after 30 seconds of spinning on the skin)> (fiber diameter after 30 seconds of spinning on the metal plate) (1)

The contents of the component (a), the component (b) and the component (c) which are the spray composition are measured as follows. Since the component (a) which is a volatile substance does not exist in the formed film or volatilizes even if it exists, the formed film contains only the component (b) and the component (c). The content is measured as follows.

<Measurement method of content of component (a), component (b) and component (c) of spray composition>
There are separation identification by liquid chromatograph (HPLC) in solution state and identification by infrared spectrophotometer (IR). In a liquid chromatograph, since it elutes from a component with a large molecular weight, the composition can also be identified by predicting the molecular weight or elution position of the component. In IR analysis, functional groups can be assigned and identified from individual absorbers. Generally, identification can be performed by comparing a standard chart of commercially available additives with an IR chart of components.

<Method of measuring the content of component (b) and component (c) in the formed film>
A solvent capable of dissolving the film is searched, and after the film is dissolved in the solvent, separation and identification by liquid chromatography (HPLC) or infrared spectrophotometer (IR) is performed.

The fiber forming the coating is a continuous fiber having an infinite length on the principle of production, but preferably has a length at least 100 times the thickness of the fiber. In the present specification, a fiber having a length of 100 times or more the thickness of the fiber is defined as “continuous fiber”. And it is preferable that the film manufactured by the electrostatic spray method is a porous discontinuous film made of a continuous fiber deposit. In addition to being able to handle as a single sheet as an aggregate, the coating in such a form has very soft characteristics, and even when shearing force is applied to it, it does not easily break apart, and can follow the movement of the body. There is an advantage of being excellent. There is also an advantage that the complete removal of the coating is easy. On the other hand, the continuous film having no pores is not easily peeled off and has low sweat dissipation, so that there is a risk of stuffiness on the skin. In addition, a porous discontinuous film composed of aggregates of particles is required to be completely removed without damaging the skin, for example, an operation such as rubbing the entire film is required to completely remove the film. Have difficulty.

In the electrostatic spraying process using the electrostatic spraying apparatus 10, the spraying composition that has been electrostatically sprayed into a fibrous form is charged with the component (b) and the component (c) while the component (a) evaporates. Reach the skin directly in the state. As described above, since the skin is also charged, the fibers adhere to the skin in the form of a single film by electrostatic force. Since fine irregularities such as texture are formed on the surface of the skin, the fibers are more closely attached to the surface of the skin in the form of a single film coupled with the anchor effect due to the irregularities. When electrostatic spraying is completed in this way, the electrostatic sprayer 10 is turned off. As a result, the electric field between the nozzle and the skin disappears, and the electric charge is fixed on the surface of the skin. As a result, the adhesion of the film in the form of a single film is further developed, it is difficult for the film to be peeled off during wearing, and durability during use is improved. Moreover, since the fiber which comprises a film contains the component (c), not only the outstanding ultraviolet-ray protective effect is acquired, but it does not apply | coat a liquid separately on the skin, but the film is sufficiently adhered to the skin. be able to. This is because the component (c) is present in the fiber, so that the fiber itself becomes soft due to the plastic effect and the followability to the fine uneven surface is increased, and the component (c) bleeds out to the fiber surface. This is thought to be due to liquid crosslinking between the fiber and the skin. Furthermore, since it has a UV protective agent-supporting coating in which component (c) is present between the fibers of the fibers constituting the coating or on the surface of the fibers, the fibers constituting the coating are difficult to reflect light, and the appearance of the coating is It is easy to be transparent and can cover the skin with a natural appearance. These effects are further enhanced by application of a liquid agent described later.

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 in order to successfully form the coating. The distance between the nozzle and the skin can be measured by a generally used non-contact sensor or the like.

Regardless of whether the film formed by electrostatic spraying is porous or not, the basis weight of the film should be 0.1 g / m ² or more from the viewpoints of UV protection effect and durability. Preferably, it is 1 g / m ² or more, more preferably 3 g / m ² or more. Further, from the viewpoint of coating feeling and appearance, it is preferably 50 g / m ² or less, more preferably 40 g / m ² or less, and further preferably 30 g / m ² or less. For example the basis weight of the coating, 0.1 g / preferably m is ² or more 50 g / m ² or less, more preferably 1 g / m ² or more 40 g / m ² or less, 3 g / m ² or more 20 g / m ² or less is more preferable. By setting the basis weight of the coating in this way, it is possible to improve the ultraviolet protection effect and the adhesion of the coating.
In addition, the amount of the spray composition used is preferably 1 g / m ² or more, more preferably 3 g / m ² or more, and even more preferably 5 g / m ² or more, from the viewpoints of UV protection effect and durability. Further preferably 50 g / m ² or less, more preferably 40 g / m ² or less, 30 g / m ² or less is more preferable. Specifically, it is preferably 1 g / m ² or more and 50 g / m ² or less, more preferably 3 g / m ² or more and 40 g / m ² or less, and still more preferably 5 g / m ² or more and 30 g / m ² or less.

In addition, the electrostatic spray process in which the composition is directly sprayed on the skin to form a film means the process in which the film is formed by electrostatic spraying on the skin. The step of electrostatically spraying the composition to a place other than the skin to produce a sheet made of fibers and applying the sheet to the skin is different from the electrostatic spraying step.

In the present invention, before or after the electrostatic spraying step of forming a film on the skin by the electrostatic spray described above, a step of applying a liquid agent containing liquid oil at 20 ° C. to the skin by a method other than electrostatic spraying May be performed. By performing the liquid agent application step by a method other than electrostatic spraying, the coating formed by the electrostatic spraying step becomes easy to adapt to the application site, and the coating can be highly adhered to the skin and becomes transparent. You can also. For example, it becomes difficult to produce a level | step difference between the edge part of a film, and skin, and, thereby, the adhesiveness of a film and skin improves. As a result, peeling or tearing of the film is less likely to occur. In a more preferred embodiment, when the coating is a porous coating made of a fiber deposit, it has high adhesion to the skin despite a high porosity, and a large capillary force tends to occur. Furthermore, when the fibers are fine, it is easy to increase the specific surface area of the porous coating. Accordingly, the UV protection agent contained in the porous coating is uniformly distributed in the coating, and the UV protection effect is enhanced.

In particular, after forming a porous coating composed of fiber deposits in the electrostatic spraying step, a liquid agent coating step is performed by a method other than electrostatic spraying, so that fibers between the fibers forming the porous coating and / or fibers are formed. An ultraviolet protective agent-supporting film having the liquid on the surface is formed. As a result, the adhesion of the coating is improved, and the transparency of the coating is visually maintained or improved. In particular, when the coating is colorless and transparent or colored and transparent, the coating becomes more difficult to visually recognize, so that it can look like natural skin. In addition, when the coating is colored and transparent, the coating is transparent, so that it can be seen as a part of the skin.

Examples of liquid oil at 20 ° C. include linear or branched hydrocarbon oils such as liquid paraffin, light isoparaffin, liquid isoparaffin, squalane and squalene; vegetable oil such as jojoba oil and olive oil; animal oil such as liquid lanolin; monoalcohol fatty acid Examples include ester oils such as esters and polyhydric alcohol fatty acid esters; silicone oils such as dimethylpolysiloxane, dimethylcyclopolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, and higher alcohol-modified organopolysiloxane. Among these, from the viewpoint of feeling of use such as smoothness at the time of application, polar oils such as vegetable oils and silicone oils containing hydrocarbon oils, ester oils, triglycerides, etc. are preferred, and hydrocarbon oils, ester oils and silicone oils are preferred. More preferred. Moreover, the liquid oil chosen from these can be used 1 type or in combination of 2 or more types.

Examples of the hydrocarbon oil include liquid paraffin, squalane, squalene, n-octane, n-heptane, cyclohexane, light isoparaffin, liquid isoparaffin, and liquid paraffin and squalane are preferable from the viewpoint of feeling of use. Further, from the viewpoint of bringing the electrostatically sprayed film into close contact with the skin, the viscosity of the hydrocarbon oil at 30 ° C. is preferably 10 mPa · s or more, and more preferably 30 mPa · s or more. From such a viewpoint, the total content in the liquid agent of isododecane, isohexadecane, and hydrogenated polyisobutene having a viscosity of less than 10 mPa · s at 30 ° C. is preferably 10% by mass or less, more preferably 5% by mass or less. More preferably, it is 1 mass% or less, More preferably, it is 0.5 mass% or less, and does not need to contain.
Similarly, from the viewpoint of bringing the electrostatically sprayed film into close contact with the skin, the viscosity of the ester oil and the silicone oil at 30 ° C. is preferably 10 mPa · s or more, more preferably 30 mPa · s or more.
The viscosity here is measured at 30 ° C. with a BM viscometer (manufactured by Tokimec, measurement conditions: rotor No. 1, 60 rpm, 1 minute).
From the same point of view, the total content in a liquid agent of ether oil such as cetyl-1,3-dimethylbutyl ether, dicapryl ether, dilauryl ether, diisostearyl ether is preferably 10% by mass or less, More preferably, it is 5 mass% or less, More preferably, it is 1 mass% or less.

Examples of the ester oil include esters composed of linear or branched fatty acids and linear or branched alcohols or polyhydric alcohols. Specifically, isopropyl myristate, cetyl octanoate, octyldodecyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, myristyl myristate, decyl oleate, hexyl decyl dimethyloctanoate, cetyl lactate, myristyl lactate, Lanolin acetate, isocetyl stearate, isocetyl isostearate, cholesteryl 12-hydroxystearylate, ethylene glycol di-2-ethylhexanoate, dipentaerythritol fatty acid ester, monoisostearic acid N-alkyl glycol, dicaprate neopentyl glycol, dimalate Isostearyl, glycerin di-2-heptylundecanoate, trimethylolpropane tri-2-ethylhexanoate, trimethylotriisostearate Rupropane, tetra-2-ethylhexanoate pentaerythritol, glyceryl tri-2-ethylhexanoate, trimethylolpropane triisostearate, cetyl 2-ethylhexanoate, 2-ethylhexyl palmitate, diethylhexyl naphthalenedicarboxylate, benzoic acid ( 12 to 15 carbon atoms) alkyl, cetearyl isononanoate, tri (caprylic acid / capric acid) glycerin, (dicaprylic acid / capric acid) butylene glycol, glyceryl trilaurate, glyceryl trimyristate, glyceryl tripalmitate, triisostearin Glyceryl acid, glyceryl tri-2-heptylundecanoate, glyceryl tribehenate, triglyceride fatty acid glyceryl, castor oil fatty acid methyl ester, oleyl oleate, palmitic 2-heptylundecyl, diisobutyl adipate, N-lauroyl-L-glutamic acid-2-octyldodecyl ester, 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, tripropylene glycol dipivalate, and the like.

Of these, octyldodecyl myristate, myristyl myristate, isocetyl stearate, isocetyl isostearate, and cetearyl isononylate are preferred because of the excellent adhesion to the skin and the sensation when applied to the skin. Nanoate, diisobutyl adipate, di-2-ethylhexyl sebacate, isopropyl myristate, isopropyl palmitate, diisostearyl malate, neopentyl glycol dicaprate, alkyl benzoate (carbon number 12 to 15), tri (caprylic acid, Capric acid) At least one selected from glycerin is preferable, isopropyl myristate, isopropyl palmitate, diisostearyl malate, neopentyl glycol dicaprate, benzoic acid (C12-15) al And at least one selected from tri (caprylic acid / capric acid) glycerin, more preferably selected from neopentyl glycol dicaprate, benzoic acid (12 to 15 carbon atoms) alkyl, tri (caprylic acid / capric acid) glycerin At least one is more preferred.

The triglyceride is preferably a fatty acid triglyceride, for example, olive oil, jojoba oil, macadamia nut oil, medfoam oil, castor oil, safflower oil, sunflower oil, avocado oil, canola oil, kyonin oil, rice germ oil, rice bran oil, etc. .

Examples of the silicone oil include methylpolysiloxane, dimethylcyclopolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, and higher alcohol-modified organopolysiloxane.
The kinematic viscosity of the silicone oil, the electrostatic sprayed coating from the viewpoint of adhesion to the skin, preferably 3 mm ² / s, more preferably 4 mm ² / s, more preferably not less than 5 mm ² / s at 25 ° C., 30 mm ² / S or less is preferable, 20 mm ² / s or less is more preferable, and 10 mm ² / s or less is more preferable.
Among these, it is preferable to contain methylpolysiloxane from the viewpoint of bringing the electrostatically sprayed film into close contact with the skin.

The content of liquid oil in the liquid is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and further preferably 5% by mass or more. Moreover, Preferably it is 100 mass% or less. The content of the liquid oil in the liquid is preferably 0.1% by mass or more and 100% by mass or less, and more preferably 0.5% by mass or more and 100% by mass or less.

In addition, the liquid may further contain a polyol. When a polyol is included, examples of the polyol include alkylene glycols such as ethylene glycol, propylene glycol, 1,3-propanediol, and 1,3-butanediol; diethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, and the like. Polyalkylene glycols; glycerins such as glycerin, diglycerin, triglycerin and the like. Of these, one or more selected from ethylene glycol, propylene glycol, 1,3-butanediol, dipropylene glycol, polyethylene glycol, glycerin and diglycerin from the viewpoint of feeling of use such as smoothness during coating. More preferred is one or more selected from propylene glycol, 1,3-butanediol and glycerin, and more preferred is one or more selected from propylene glycol and 1,3-butanediol.

The liquid agent preferably has a viscosity of about 5000 mPa · s or less at 25 ° C. from the viewpoint of improving the adhesion between the coating formed by the electrostatic spray method and the application site. The method for measuring the viscosity of the liquid is as described above.

Various methods other than electrostatic spraying can be used to apply a liquid agent containing liquid oil to the skin. For example, by applying a solution to the skin by a method such as dripping or sprinkling, and applying a step of spreading the solution, it is possible to adjust to the skin or film, and a thin layer of the solution can be formed. For the step of spreading the liquid agent, for example, a method such as rubbing using a user's finger or a tool such as an applicator can be employed. Although the liquid agent may be simply dropped or sprinkled, it can be applied to the skin or the coating by providing a spreading step, and the adhesion of the coating can be sufficiently improved. Alternatively, the solution can be sprayed onto the skin to form a thin layer of the solution. In this case, separate spreading is not particularly necessary, but it is not hindered to perform the spreading operation after spraying. In addition, when applying a liquid agent after formation of a film, a sufficient liquid agent is applied to skin, and the excess liquid agent can be removed by the process which makes a sheet material contact the range which applied the liquid agent.

The amount of the liquid applied to the skin may be an amount necessary and sufficient for improving the adhesion between the skin and the film. When the liquid oil is contained in the liquid agent, the basis weight of the liquid oil is preferably 0.1 g / m ² from the viewpoint of ensuring adhesion between the skin and the film. More preferably, the amount is 0.2 g / m ² or more, preferably 40 g / m ² or less, more preferably 35 g / m ² or less. For example, the amount of liquid applied to the skin is such that the basis weight of the liquid oil is preferably from 0.1 g / m ^{2 to} 40 g / m ² , more preferably from 0.2 g / m ^{2 to} 35 g / m ^2. Amount.
Further, the amount of the solution applied to the skin or the film is preferably 5 g / m ² or more, more preferably 10 g / m ² from the viewpoint of improving the adhesion between the skin and the film and the transparency. Or more, more preferably 15 g / m ² or more, preferably 50 g / m ² or less, more preferably 45 g / m ² or less.

The method for producing an ultraviolet protective coating of the present invention as described above is useful as a cosmetic method for the purpose of protecting ultraviolet rays that is not intended for surgery, treatment or diagnosis of the human body.

As mentioned above, although this invention was demonstrated based on the preferable embodiment, this invention is not restrict | limited to the said embodiment. For example, in the above-described embodiment, a person who wants to form a film on his skin grips the electrostatic spray device 10 and generates an electric field between the conductive nozzle of the device 10 and his skin. As long as an electric field is generated between the two, it is not necessary for a person who wants to form a film on his skin to hold the electrostatic spray device 10.

In relation to the above-described embodiment, the present invention further discloses the following method for producing a coating film.
<1> A method for producing an ultraviolet protective coating on the skin, wherein the composition comprising the component (a), the component (b) and the component (c) is electrostatically sprayed directly onto the skin.
(A) one or more volatile substances selected from water, alcohol and ketone,
(B) a polymer having a film-forming ability,
(C) UV protection agent.

<2> The method for producing an ultraviolet protective coating according to <1>, further comprising a step of applying a liquid containing liquid oil at 20 ° C. to the skin by means other than electrostatic spraying before or after the electrostatic spraying step. .
<3> The method for producing a film according to <1> or <2>, wherein the ultraviolet protective agent is an ultraviolet absorber, preferably an organic ultraviolet absorber.
<4> The electrostatic spray container that contains the composition, the nozzle that discharges the composition, the supply device that supplies the composition contained in the container to the nozzle, and the nozzle <1>-<3> The method for producing a coating film according to any one of <1> to <3>, which is performed using an electrostatic spraying device having a power source for applying a voltage to the surface.
<5> The volatile substance of component (a) preferably has a vapor pressure of 0.01 kPa to 106.66 kPa at 20 ° C., more preferably 0.13 kPa to 66.66 kPa, The method for producing a coating film according to any one of <1> to <4>, further preferably 0.67 kPa or more and 40.00 kPa or less, and further preferably 1.33 kPa or more and 40.00 kPa or less. .
<6> The volatile substance of component (a) is an alcohol, and the alcohol is a monovalent chain aliphatic alcohol, a monovalent cyclic aliphatic alcohol, or a monovalent aromatic alcohol, or Two or more are preferable, and the alcohol is preferably one or two or more selected from ethanol, isopropyl alcohol, butyl alcohol, phenylethyl alcohol, propanol, and pentanol, and any of the above <1> to <5> A method for producing the film according to claim 1.
<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 The method for producing a coating film according to any one of the above <1> to <6>, which is a seed, and more preferably contains ethanol.
<8> The polymer having the ability to form a film of component (b) is a substance that can be dissolved in the volatile substance of component (a), and includes a water-soluble polymer and a water-insoluble polymer. Then, the coating film according to any one of <1> to <7>, wherein the coating film is in a dispersed state at 20 ° C., and the dispersed state is a visually uniform state, preferably a visually transparent or translucent state. Method.

<9> A water-soluble polymer having a film-forming ability includes pullulan, hyaluronic acid, chondroitin sulfate, poly-γ-glutamic acid, modified corn starch, β-glucan, glucooligosaccharide, heparin, keratosulfuric acid, etc. Pectin, xylan, lignin, glucomannan, galacturonic acid, psyllium seed gum, tamarind seed gum, gum arabic, tragacanth gum, soybean water-soluble polysaccharide, alginic acid, carrageenan, laminaran, agar (agarose), fucoidan, methylcellulose, hydroxypropylcellulose, hydroxy Natural polymers such as propylmethylcellulose, partially saponified polyvinyl alcohol (when not used in combination with a crosslinking agent), low saponified polyvinyl alcohol, polyvinyl pyrrolidone (PVP), polyethylene oxide , One or more water-soluble polymers selected from sodium polyacrylate, more preferably pullulan and one or more selected from partially saponified polyvinyl alcohol, low saponified polyvinyl alcohol, polyvinyl pyrrolidone and polyethylene oxide The method for producing a coating according to <8>, wherein the coating is a water-soluble polymer of two or more types.
<10> Fully saponified polyvinyl alcohol, which is a water-insoluble polymer having a film-forming ability, can be insolubilized after the film is formed, and partially saponified polyvinyl alcohol, poly (N-propanoyl) which can be crosslinked after the film is formed by using in combination with a crosslinking agent Ethyleneimine) graft-dimethylsiloxane / γ-aminopropylmethylsiloxane copolymer oxazoline-modified silicone, polyvinyl acetal diethylaminoacetate, zein (a major component of corn protein), polyester, polylactic acid (PLA), polyacrylonitrile resin, poly Acrylic resin such as methacrylic acid resin, polystyrene resin, polyvinyl butyral resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polyurethane resin, polyamide resin, polyimide resin 1 or 2 or more types of water-insoluble polymers selected from fats and polyamide-imide resins, and more preferably, a part that can be cross-linked after forming a film by using in combination with a completely saponified polyvinyl alcohol that can be insolubilized after forming the film, or a cross-linking agent 1 selected from saponified polyvinyl alcohol, polyvinyl butyral resin, polyurethane resin, oxazoline-modified silicone such as poly (N-propanoylethyleneimine) graft-dimethylsiloxane / γ-aminopropylmethylsiloxane copolymer, polyvinyl acetal diethylaminoacetate, and twein The method for producing a coating according to the above <8>, which is a seed or two or more water-insoluble polymers, and more preferably one or two or more water-insoluble polymers selected from polyvinyl butyral resins and polyurethane resins. .
<11> The content of the component (a) in the composition is preferably 50% by mass or more, more preferably 55% by mass or more, still more preferably 60% by mass or more, and 98 It is preferably at most mass%, more preferably at most 96 mass%, further preferably at most 94 mass%, and the content of component (a) in the composition is 50 mass% or more and 98 mass% or less. % Or less, more preferably 55% by mass or more and 96% by mass or less, and still more preferably 60% by mass or more and 94% by mass or less, in any one of the above items <1> to <10>. The manufacturing method of the film of this.
<12> The content of the component (b) in the composition is preferably 2% by mass or more, more preferably 4% by mass or more, still more preferably 6% by mass or more, and 50 It is preferably at most mass%, more preferably at most 45 mass%, even more preferably at most 40 mass%, and the content of component (b) in the composition is 2 mass% or more and 50 mass% or less. % Or less, more preferably 4% by mass or more and 45% by mass or less, and further preferably 6% by mass or more and 40% by mass or less. Any one of the above items <1> to <11> The manufacturing method of the coating film of description.
<13> Component (c) is selected from benzoic acid-based UV absorbers, anthranilic acid-based UV absorbers, salicylic acid-based UV absorbers, cinnamic acid-based UV absorbers, benzophenone-based UV absorbers, and triazine-based UV absorbers The method for producing a coating film according to any one of <1> to <14>, wherein the coating film is one kind or two or more kinds.
<14> The benzoic acid-based ultraviolet absorber of component (c) is paraaminobenzoic acid (hereinafter abbreviated as PABA), glyceryl PABA, ethyldihydroxypropyl PABA, N-ethoxylate PABA ethyl ester, N-dimethyl PABA ethyl ester, A compound selected from N-dimethyl PABA butyl ester, N-dimethyl PABA amyl ester, octyl dimethyl PABA, and hexyl diethylaminohydroxybenzoyl benzoate; the anthranilic acid-based UV absorber is homomenthyl-N-acetylanthranylate A salicylic acid ultraviolet absorber is amyl salicylate, menthyl salicylate, homomenthyl salicylate, octyl salicylate, phenyl salicylate, benzyl salicylate, and p-isopropano A compound selected from phenyl salicylates; cinnamic acid-based UV absorbers are ethyl-4-isopropylcinnamate, ethyl-2,4-diisopropylcinnamate, methyl-2,4-diisopropylcinnamate, propyl-p -Methoxycinnamate, isopropyl-p-methoxycinnamate, isoamyl-p-methoxycinnamate, 2-ethylhexyl-p-methoxycinnamate, 2-ethoxyethyl-p-methoxycinnamate, cyclohexyl-p-methoxycinnamate, A compound selected from ethyl-α-cyano-β-phenylcinnamate, 2-ethylhexyl-α-cyano-β-phenylcinnamate, and glyceryl mono-2-ethylhexanoyldiparamethoxycinnamate; benzophenone ultraviolet light absorption 2,4-dihydroxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4,4′-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4 -Methoxy-4'-methylbenzophenone, 2-hydroxy-4-methoxybenzophenone, 4-phenylbenzophenone, 2-ethylhexyl-4'-phenylbenzophenone-2-carboxylate, 2-hydroxy-4-n-octoxybenzophenone, A compound selected from 4-hydroxy-3-carboxybenzophenone; a triazine-based ultraviolet absorber is 2,4,6-tris [4- (2-ethylhexyloxycarbonyl) anilino] -1,3,5- Triazine, 2,4-bis-[{4- (2- Tilhexyloxy) -2-hydroxy} -phenyl] -6- (4-methoxyphenyl) -1,3,5-triazine; and 3- (4′-methylbenzylidene) -dl- Camphor, 3-benzylidene-dl-camphor, urocanic acid ethyl ester, 2-phenyl-5-methylbenzoxazole, 2,2'-hydroxy-5-methylphenylbenzotriazole, 2- (2'-hydroxy-5- t-octylphenyl) benzotriazole, dibenzalazine, dianisoylmethane, 4-methoxy-4′-t-butyldibenzoylmethane, 5- (3,3-dimethyl-2-norbornylidene) -3-pentan-2-one, One or two selected from benzene bis-1,3-diketone derivatives and benzoyl pinacolone derivatives Method for producing a film according to a top <13>.
<15> The content of the component (c) in the composition is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, further preferably 0.10% by mass or more, and 15% by mass. The method for producing a coating film according to any one of <1> to <14>, preferably 12% by mass or less, more preferably 10% by mass or less.
<16> The composition has a viscosity at 25 ° C. of preferably 1 mPa · s or more, more preferably 10 mPa · s or more, more preferably 50 mPa · s or more, preferably 5000 mPa · s or less, more preferably Is 2000 mPa · s or less, more preferably 1500 mPa · s or less, and the viscosity of the 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. The method for producing a film according to any one of <1> to <15>, which is more preferably 50 mPa · s or more and 1500 mPa · s or less.
<17> Linear oil or branched hydrocarbon oil such as liquid paraffin, light isoparaffin, liquid isoparaffin, squalane and squalene at 20 ° C .; vegetable oil such as jojoba oil and olive oil; animal oil such as liquid lanolin; monoalcohol Ester oils such as fatty acid esters and polyhydric alcohol fatty acid esters; selected from silicone oils such as dimethylpolysiloxane, dimethylcyclopolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, higher alcohol-modified organopolysiloxane, Of these, a hydrocarbon oil, vegetable oil containing ester oil, triglyceride and the like, polar oil such as silicone oil, more preferably one or more selected from hydrocarbon oil, ester oil and silicone oil Ah Method for producing a film according to any one of <2> - <16>.
<18> The hydrocarbon oil is one or more selected from liquid paraffin, squalane, squalene, n-octane, n-heptane, cyclohexane, light isoparaffin, and liquid isoparaffin, more preferably liquid paraffin and squalane. The method for producing a coating according to <17>, wherein the coating is one or more selected from the group consisting of:
<19> An ester oil is an ester composed of a linear or branched fatty acid and a linear or branched alcohol or a polyhydric alcohol. Specifically, isopropyl myristate, cetyl octanoate, octyl myristate Dodecyl, isopropyl palmitate, butyl stearate, hexyl laurate, myristyl myristate, decyl oleate, hexyl decyl dimethyl octoate, cetyl lactate, myristyl lactate, lanolin acetate, isocetyl stearate, isocetyl isostearate, 12-hydroxystearyl acid Cholesteryl, ethylene glycol di-2-ethylhexanoate, dipentaerythritol fatty acid ester, N-alkyl glycol monoisostearate, 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, diethyl hexyl naphthalene dicarboxylate, alkyl benzoate (C12-15), cetearyl isononanoate, tri (caprylic acid / capric acid) glycerin, (dicaprylic acid) / Capric acid) butylene glycol, glyceryl trilaurate, glyceryl trimyristate, glyceryl tripalmitate, glyceryl triisostearate, glyceryl tri-2-heptylundecanoate Glyceryl tribehenate, triglyceride fatty acid glyceryl, castor oil fatty acid methyl ester, oleic acid oleyl, 2-heptylundecyl palmitate, diisobutyl adipate, N-lauroyl-L-glutamic acid-2-octyldodecyl ester, adipic acid diester 2-heptylundecyl, ethyl laurate, di-2-ethylhexyl sebacate, 2-hexyldecyl myristate, 2-hexyldecyl palmitate, 2-hexyldecyl adipate, diisopropyl sebacate, di-2-ethylhexyl succinate, citrate <17> The method for producing a coating according to <17>, wherein the coating material is one or more selected from triethyl acid, 2-ethylhexyl paramethoxycinnamate, and tripropylene glycol dipivalate.

<20> Triglyceride is preferably fatty acid triglyceride, selected from olive oil, jojoba oil, macadamia nut oil, medofoam oil, castor oil, safflower oil, sunflower oil, avocado oil, canola oil, kyonin oil, rice germ oil, rice bran oil The manufacturing method of the film as described in said <17> which is 1 type or 2 types or more.
<21> The <21>, wherein the silicone oil is one or more selected from methylpolysiloxane, dimethylcyclopolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, and higher alcohol-modified organopolysiloxane. The manufacturing method of the film of this.
<22> The content of the liquid oil in the liquid is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and further preferably 5% by mass or more. Moreover, Preferably it is 100 mass% or less. The content of the liquid oil in the liquid agent is preferably 0.1% by mass or more and 100% by mass or less, more preferably 0.5% by mass or more and 100% by mass or less, and any one of the above items <2> to <21> The method for producing a coating film according to claim 1.
<23> An electrostatic spray method is performed using an electrostatic spray device,
The electrostatic spray device includes a nozzle,
The nozzle is made of various conductors including metal, or non-conductor such as plastic, rubber, ceramic, etc., and has a shape capable of discharging the composition from the tip thereof <1> to <22> The manufacturing method of the film in any one of.
<24> Perform electrostatic spraying using electrostatic spraying equipment,
The electrostatic spray device includes a nozzle and a housing,
The nozzle is arranged at one end in the longitudinal direction of the housing,
The nozzles are arranged in the casing so that the blowing direction of the composition coincides with the longitudinal direction of the casing and is convex toward the skin side. The manufacturing method of the film in any one.
<25> The above-mentioned sprayed composition forms a fiber while volatilizing a volatile substance as a solvent from droplets and solidifying a polymer having a film-forming ability as a solute while stretching and deforming by a potential difference < [1] The method for producing a coating film according to any one of [1] to <24>.

<26> Perform electrostatic spraying using an electrostatic spraying device,
The electrostatic spray device includes a nozzle,
The method for producing a coating film according to any one of <1> to <25>, wherein the distance between the nozzle and the skin is 50 mm or more and 150 mm or less.
<27> The basis weight of the coating formed by the electrostatic spray method is preferably 0.1 g / m ² or more, more preferably 1 g / m ² or more, and 3 g / m ² or more. Is more preferably 50 g / m ² or less, more preferably 40 g / m ² or less, still more preferably 20 g / m ² or less, and the basis weight of the coating is 0.1 g / m ² or more and 50 g. preferably / m ² or less, any more preferably 1 g / m ² or more 40 g / m ² or less, 3 g / m ² or more 20 g / m ² or less is more preferable that the <1> to the <26> A method for producing the film according to claim 1.
<28> The method for producing a coating film according to any one of <1> to <27>, wherein the composition further contains 10% by mass or less of glycol.
<29> The component (a) is a volatile substance containing at least ethanol, and the component (b) is one or more selected from polyvinyl butyral resin and polyurethane resin. The manufacturing method of the film in any one.
<30> The method for producing a coating film according to any one of <1> to <29>, wherein the component (a) is a volatile substance containing at least ethanol and further contains 10% by mass or less of glycol.
<31> The component (a) is a volatile substance containing at least ethanol, and the ethanol content in the volatile substance is 50% by mass or more and 100% by mass, and contains 10% by mass or less of glycol <1> The method for producing a coating film according to any one of to <30>.
<32> The content of component (a) is 30% by mass to 98% by mass in the composition, and the content of component (b) is 2% by mass to 50% by mass in the spray composition. The method for producing a coating film according to any one of <1> to <31>, wherein the content of (c) is 0.001% by mass to 50% by mass in the spray composition.
<33> The content of component (a) is 55% by mass or more and 96% by mass or less in the composition, and the content of component (b) is 4% by mass or more and 45% by mass or less in the composition for spraying. The method for producing a coating film according to any one of <1> to <31>, wherein the content of (c) is 0.01% by mass or more and 30% by mass or less in the spray composition.
<34> The content of component (a) is 60% by mass or more and 94% by mass or less in the composition, and the content of component (b) is 6% by mass or more and 40% by mass or less in the composition for spraying. The method for producing a coating film according to any one of <1> to <31>, wherein the content of (c) is 0.1% by mass or more and 15% by mass or less in the spray composition.
<35> The component (a) is a volatile substance containing at least ethanol, and the component (b) is one or more selected from polyvinyl butyral resins and polyurethane resins. The manufacturing method of the film in any one.
<36> The method for producing a coating film according to any one of <1> to <35>, wherein the component (a) is a volatile substance containing at least ethanol and further contains 10% by mass or less of glycol.
<37> The component (a) is a volatile substance containing at least ethanol, and the ethanol content in the volatile substance is 50% by mass or more and 100% by mass, and contains 10% by mass or less of glycol <1> The method for producing a coating film according to any one of to <36>.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the scope of the present invention is not limited to such examples. Unless otherwise specified, “%” means “mass%”.

[Test Example 1]
Examples 1 and 2
(1) Preparation of spraying composition 99.5% ethanol (manufactured by Wako Pure Chemical Industries, Ltd.) was used as component (a) of the spraying composition. As the component (b), polyvinyl butyral (manufactured by Sekisui Chemical Co., Ltd .: trade name ESREC B) was used. As component (c), an ultraviolet absorbent mixed oil having the composition shown in Table 1 was used. The component (c) used what became the uniform state by stirring about 3 hours, heating each component at 80 degreeC.

The components (a), (b) and (c) were measured in a 1 L glass beaker and stirred for about 12 hours at room temperature using a propeller mixer to obtain a uniform transparent solution. This was made into the composition for spraying.
Component (a), component (b), and component (c) were 85.6 parts by mass and 12.0 parts by mass, respectively, and 2.4 parts by mass.

(2) Electrostatic spraying process Using the electrostatic spraying apparatus 10 having the configuration shown in FIG. 1 and the appearance shown in FIG. 2, the electrostatic spraying method was performed for 30 seconds toward the cosmetic application site. The conditions of the electrostatic spray method were as shown below.
・ Applied voltage: 10 kV
・ Distance between conductive nozzle and skin: 100 mm
・ Discharge rate of spray composition: 5 mL / h
-Environment: 25 ° C, 40% RH
By this electrostatic spraying, a porous film made of a fiber deposit was formed over the entire region where the cosmetic was applied. The coating was a circle with a diameter of about 4 cm and the mass was about 7 mg.

(3) Liquid agent application process The liquid agent was applied before or after the electrostatic spraying process. As a solution, JERGENS Ultra Healing (manufactured by Kao USA) was used.

Example 3
A film was formed in the same manner as in Example 1 except for the step of applying the oil agent before or after the electrostatic spraying step. As an oil agent, Estesmol N-01 manufactured by Nisshin Oilio Co., Ltd. was used.

Example 4
A film was formed in the same manner as in Example 1 except for the step of applying water before or after the electrostatic spraying step.

Example 5
A film was formed in the same manner as in Example 1 except that the step of applying the liquid agent was omitted before or after the electrostatic spraying step.

[Comparative Example 1]
The spray composition of Example 1 was applied directly without spraying. The coating amount was the same as in Example 1.

[Comparative Example 2]
The spray composition of Example 1 in which component (b) was completely replaced with component (a) was applied directly without spraying. The coating amount was the same as in Example 1.

[Comparative Example 3]
The spray composition of Comparative Example 2 was sprayed in the same manner as in Example 1 to obtain a coating.

[Comparative Example 4]
The spray composition of Example 1 in which component (c) was completely replaced with component (a) was sprayed in the same manner as in Example 1 to obtain a coating.

(3) Evaluation [SPF]
An SPF test was performed for comparison of the ultraviolet protection performance of the obtained coating. Five coatings sprayed onto the substrate (Labsphere HD-6) were measured, and the average value was defined as SPF. An SPF analyzer (UV-2000S manufactured by Labsphere) was used for the measurement. The SPF display value was 50 or more, a was 25 or more and less than 50, b was 10 or more and less than 20, and c was less than 10 or d.
〔durability〕
SPF before and after rubbing the film 10 times with a finger was measured and used as an index of film durability. What SPF was maintained at 80% or more after 10 times of grinding compared to the first SPF was a, what was maintained 60% or more and less than 80% b, and what was maintained less than 60% Was c.
[Film feeling]
The sense of incongruity when the film was formed on the back of the hand was determined by sensory evaluation. The one that did not feel uncomfortable was a, the one that was a little worrisome was b, and the one that was very worrisome was c.
〔appearance〕
The appearance when the film was formed on the back of the hand was determined by sensory evaluation. The one with a sense of unity with the back of the hand was designated as a, the one with a little sense of unity was designated as b, and the one with a slight sense of unity was designated as c.

The results are shown in Table 3.

[Example 6-16]
Using the compositions shown in Table 4 (component (a), component (b), component (c)), SPF, durability, film feeling and appearance were evaluated in the same manner as in Example 1. The results are shown in Table 5.

From Tables 3 and 5, according to the method of the present invention, the SPF was dramatically improved and the durability of the SPF value was also good. Furthermore, there was no sense of incongruity in the coating and the appearance was good. The effect of improving the SPF value of the method of the present invention is considered to be based not only on the presence of the UV absorber on the skin but also on the film and evenly distributed on the skin. It is done.

DESCRIPTION OF SYMBOLS 10 Electrostatic spray apparatus 11 Low voltage power supply 12 High voltage power supply 13 Auxiliary electric circuit 14 Microgear pump 15 Container 16 Nozzle 17 Pipe line 18 Flexible pipe line 19 Current limiting resistor 20 Case

Claims

A method for producing an ultraviolet protective coating on a skin, comprising electrostatically spraying a composition containing the component (a), the component (b) and the component (c) directly onto the skin.
(A) one or more volatile substances selected from water, alcohol and ketone,
(B) a polymer having a film-forming ability,
(C) UV protection agent.
Furthermore, the manufacturing method of the ultraviolet protective film of Claim 1 which has the process of apply | coating a liquid agent to skin by methods other than electrostatic spraying before or after an electrostatic spraying process.
The method for producing an ultraviolet protective coating according to claim 1 or 2, wherein the liquid agent contains oil which is liquid at 20 ° C.
The method for producing a coating film according to any one of claims 1 to 3, wherein the ultraviolet protective agent is an organic ultraviolet absorber.
The electrostatic spray includes a container that contains the composition, a nozzle that discharges the composition, a supply device that supplies the composition contained in the container to the nozzle, and a voltage applied to the nozzle. The method for producing a coating film according to any one of claims 1 to 4, which is carried out using an electrostatic spray apparatus having a power source to be applied.
The method for producing a coating film according to any one of claims 1 to 5, wherein the component (a) is at least one selected from ethanol, isopropyl alcohol, butyl alcohol and water.
The method for producing a coating film according to any one of claims 1 to 6, wherein the component (a) is a volatile substance containing at least ethanol.
The method for producing a coating film according to any one of claims 1 to 7, wherein the component (a) is a volatile substance containing at least ethanol, and the content of ethanol in the volatile substance is 50% by mass or more and 100% by mass. .
The method for producing a coating film according to any one of claims 1 to 8, wherein the content of the component (a) is 30% by mass or more and 98% by mass or less in the composition.
The component (b) is one or more selected from fully saponified or partially saponified polyvinyl alcohol, polyvinyl butyral resin, polyurethane resin, oxazoline-modified silicone, water-soluble polyester, and twein. The manufacturing method of the film of description.
The method for producing a coating film according to any one of claims 1 to 10, wherein the component (b) is one or more selected from polyvinyl butyral resins and polyurethane resins.
The method for producing a coating film according to any one of claims 1 to 11, wherein the content of the component (b) is 2% by mass or more and 50% by mass or less in the spray composition.
The method for producing a coating film according to any one of claims 1 to 12, wherein a 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 coating film according to any one of claims 7 to 13, wherein the content ratio ((a) / (b)) of ethanol (a) to component (b) is 0.5 or more and 40 or less.
The method for producing a coating film according to any one of claims 1 to 14, wherein the composition has a glycol content of 10% by mass or less.
The content of the component (a) is 30% by mass or more and 98% by mass or less in the composition, the content of the component (b) is 2% by mass or more and 50% by mass or less in the spray composition, and the component (c). The method for producing a coating film according to any one of claims 1 to 15, wherein the content of is from 0.001% by mass to 50% by mass in the spray composition.
The content of component (a) is 55 to 96% by mass in the composition, the content of component (b) is 4 to 45% by mass in the spray composition, and component (c) The method for producing a coating film according to any one of claims 1 to 15, wherein the content of is from 0.01% by mass to 30% by mass in the spray composition.
The content of the component (a) is 60% by mass or more and 94% by mass or less in the composition, the content of the component (b) is 6% by mass or more and 40% by mass or less in the composition for spraying, and the component (c). The method for producing a coating film according to any one of claims 1 to 15, wherein the content of is from 0.1% by mass to 15% by mass in the spray composition.
The component (a) is a volatile substance containing at least ethanol, and the component (b) is one or more selected from a polyvinyl butyral resin and a polyurethane resin. The manufacturing method of the film of this.
The method for producing a coating film according to any one of claims 1 to 19, wherein the component (a) is a volatile substance containing at least ethanol and further contains 10% by mass or less of glycol.
The component (a) is a volatile substance containing at least ethanol, and the ethanol content in the volatile substance is 50% by mass or more and 100% by mass, and contains 10% by mass or less of glycol. The manufacturing method of the film of any one of Claims 1.