JP6544040B2 - Fibroin nano thin film, nano thin film sheet and transfer method - Google Patents

Description

  The present invention relates to a fibroin nano thin film, a nano thin film sheet, and a transfer method.

  BACKGROUND ART In recent years, a nano thin film to be attached to an organ, skin or the like has attracted attention in the medical field or the cosmetic field. For example, a medical nano-thin film to be attached to the skin surface or organ wound surface as a wound covering material has been proposed (see, for example, Non-Patent Document 1).

  In addition, film products that can be produced using bio-derived substances such as saccharides and proteins are cell culture supports and tissues in the medical field, daily necessities field, water purification field, cosmetics / esthetic field, tissue engineering or regenerative medicine engineering. It is used in a wide range of fields in industry, such as recycled supports. As a biological substance, saccharides such as cellulose and chitin, proteins such as collagen, keratin and fibroin (silk fibroin) are known.

T. Fujie et al. , Adv. Funct. Mater. 19, 2009, 2560-2568.

  Since fibroin has a long track record of being used as a surgical suture in addition to clothing applications, it is also used as a food or cosmetic additive and has no problems with human safety. It is sufficiently available for thin film application fields. On the other hand, for the fibroin nano thin film containing fibroin, excellent adhesion to an object, such as an organ or skin, is required.

  The present invention was made in order to solve the above-mentioned subject, and it aims at providing a fibroin nano thin film which has the outstanding pasting nature. Another object of the present invention is to provide a nano thin film sheet using the fibroin nano thin film, and a transfer method using the nano thin film sheet.

  The fibroin nano thin film according to the present invention contains fibroin and has a contact angle to water of 30 ° or more.

  The fibroin nano thin film according to the present invention contains fibroin, and when the contact angle to water is 30 ° or more, it has excellent adhesion to a transferee such as an organ or skin.

  The film thickness of the fibroin nano thin film according to the present invention is preferably 1 to 300 nm. The fibroin nano thin film according to the present invention may be for skin attachment or for cosmetic use.

  The nano thin film sheet which concerns on this invention is equipped with a base material and the fibroin nano thin film which concerns on this invention, and the said fibroin nano thin film is laminated | stacked on the said base material. The substrate may be a mesh sheet, a non-woven sheet or a porous sheet.

In the transfer method according to the present invention, the nano thin film sheet according to the present invention is disposed such that the fibroin nano thin film side faces the transfer target, and the base side of the nano thin film sheet is pressed. You may provide the process of transcribe | transferring a thin film to the said to-be-transferred body. It is preferable that the load at the time of pressing the said base-material side of the said nano thin film sheet is 10-1000 g / cm < ² >.

  ADVANTAGE OF THE INVENTION According to this invention, the fibroin nano thin film which has the outstanding sticking property with respect to to-be-transcribed bodies, such as an organ and skin, can be provided. According to the present invention, it is possible to provide a nano thin film sheet using the fibroin nano thin film, and a transfer method using the nano thin film sheet.

It is a schematic cross section which shows one Embodiment of a nano thin film sheet.

  Hereinafter, embodiments of the present invention will be described. However, the present invention is not limited to the following embodiments.

<Fibroin nano thin film and nano thin film sheet>
The fibroin nano thin film (silk fibroin nano thin film) according to the present embodiment contains fibroin (silk fibroin). The contact angle to water of the fibroin nano thin film according to the present embodiment is 30 ° or more, and for example, the contact angle to water on the surface of the fibroin nano thin film is 30 ° or more.

  The contact angle to water is preferably 40 ° or more, more preferably 60 ° or more, from the viewpoint of obtaining further excellent adhesion. The contact angle is, for example, a contact angle at 23 ° C. The contact angle to water can be measured, for example, by a contact angle meter DM-501 manufactured by Kyowa Interface Science Co., Ltd.

  The fibroin used in the present embodiment is not limited, and includes, for example, fibroin produced from transgenic rabbits, such as smallpox such as rabbits, wild rabbits and pemphigus. Since fibroin (silk fibroin) can be expected to be stably supplied since raw materials can be easily obtained, and its price is also stable, industrial use is easy.

  The fibroin nano thin film according to the present embodiment can be formed using a fibroin aqueous solution containing fibroin. As a method of obtaining fibroin aqueous solution, any known method may be used. For example, after dissolving fibroin in high concentration lithium bromide aqueous solution, a method through desalting by dialysis and concentration by air drying is simple and convenient. is there. Any solvent can be used as a solvent for the fibroin aqueous solution, as long as it can dissolve fibroin, but water (such as pure water) can be used.

The film thickness of the fibroin nano thin film is not particularly limited, but is preferably in the following range at the time of drying. The thickness of the fibroin nano thin film is preferably 1 nm or more, and more preferably 40 nm or more, from the viewpoint of further excellent properties such as self-adhesion, water absorption, and flexibility in a dry state. The film thickness of the fibroin nano thin film is preferably 300 nm or less, more preferably 250 nm or less, from the viewpoint of further excellent properties such as self-adhesion, water absorption, flexibility in a dry state, and the like. It is further preferred that
The film thickness of the fibroin nano thin film is preferably 1 to 300 nm, more preferably 40 to 300 nm, from the viewpoint of further excellent properties such as self-adhesion, water absorption, and flexibility in a dry state. It is further more preferable that it is -250 nm, and it is especially preferable that it is 40-200 nm.

  The fibroin nano thin film according to the present embodiment can contain a functional substance (for example, a substance that exhibits functionality in a transferee such as an organ or skin). The functional substance may, for example, be a cosmetic, a pigment, a metal ion or a drug. The functional substances can be used alone or in combination of two or more. The content of the functional substance in the fibroin nanothin film is, for example, 1 to 100 parts by mass with respect to 100 parts by mass of fibroin.

  The fibroin nano thin film according to the present embodiment can be suitably used as a fibroin nano thin film for skin application, a fibroin nano thin film for cosmetic use, or a fibroin nano thin film for cosmetic skin application. The fibroin nano thin film can be suitably used as a medical fibroin nano thin film, an organ sticking fibroin nano thin film, and the like.

  The fibroin nano thin film according to the present embodiment can contain a cosmetic such as a moisturizing cream. Thereby, it is possible to hold the cosmetic on the fibroin nano thin film, and when it is attached to the skin etc. (when used), the cosmetic gradually elutes from the fibroin nano thin film and is gradually absorbed to the skin etc Can.

  As the cosmetic, any cosmetic generally used for skin care such as moisturizing cream, skin cream, whitening cream, milky lotion, lotion, cosmetic solution, and cosmetic gel can be used. The cosmetic contains a cosmetic component. The cosmetic component is not particularly limited as long as it is a cosmetically acceptable component effective for the skin and the like. As a cosmetic component, for example, a component used for cosmetics such as a moisturizer, a whitening component, a stain removing component, a mildew component, vitamins, an anti-inflammatory component, a blood flow promoting component, a moist component, an oil component and metal microparticles Can be used. The cosmetic and the cosmetic component can be used singly or in combination of two or more.

  Examples of the cosmetic component include almond oil, alkyl acrylate copolymer, hemp cellulose, acetaba extract, ascorbic acid, ascorbic acid Na, xanthine, astaxanthin, asparagus extract, aspartic acid, azulene, acerola extract, adenosine triphosphate 2Na , Avocado oil, amacha extract, aminobutyric acid, alanine, allantoin, arginine, sodium alginate, ardylline, altea extract, arunica extract, albumin, aloe vera extract 2-chidathialoe extract, benzoate Na, Ginkgo biloba extract, inositol, turmeric extract, Scutellaria extract, Aget extract, sodium chloride, oyster extract, Scutellaria root extract, Scutellaria root extract, Scutellaria root extract, Ginseng extract, Scutellaria root extract, Dash , Olive oil, oryzanol, sea salt, hydrolyzed keratin, collagen, hydrolyzed collagen, hydrolyzed conchryone, hydrolyzed silk, hydrolyzed eggshell membrane, hydrolyzed egg white, brown algae extract, caffeine, chamomile extract, calamine, cullin extract, Carotene, Carrot extract, Carob extract, Licorice extract, Camphor, Raspberry extract, Kiwi extract, Xylitol, Chitosan, Cucumber extract, Quantanium-73, Gardenia extract, Kumazasa extract, Clara extract, Glycolic acid, Glycine, Glycerin, Glycyrrhizinic acid 2K, Stearyl glycyrrhetinate, glucose, glutathione, glutamate, grapefruit extract, clematis extract, chlorella extract, cape aloe extract, gentiana extract, black tea extract, cohen Im Q10, coffee extract, corn starch, cocoyl hydrolyzed collagen K, cocoyl hydrolyzed collagen Na, cocobetaine, burdock extract, sesame oil, wheat starch, wheat germ extract, rice bran extract, cholesterol, comfrey extract, tocopherol acetate, retinol acetate, sasanka Oil, safflower oil, salicylic acid, salicylic acid Na, zinc oxide, titanium oxide, titanium oxide, hawthorn extract, cyanocobalamin, shiitake extract, diower extract, diglycerin, shikon extract, shiso extract, dihydrocholesterol, diphenyldimethyl mecon, shimoshikiso extract, tartaric acid extract, Shobu root extract, silk, silk extract, hydrogenated lecithin, squalane, stearyl alcohol, glyceryl stearate, stearin Acid Sucrose, Horseradish extract, Horseradish extract, Sage extract, Setanol, Ceramide 3, Serine, Cellulose gum, Souhakuhi extract, Sorbitol, Soy extract, Soy fermented extract, Evening primrose oil, Dokudami extract, Tocopherol, Trehalose, Niacinamide, Nicotinic acid Tocopherol, lactic acid, sodium lactate, urea, bacga extract, honey, papain, hamamelis extract, retinol palmitate, panthenol, sodium hyaluronate, biotin, hydrangea extract, castor oil, sunflower oil, sunflower oil, pyridoxine HCl, loquat leaf extract, rose extract, Butcherbroom Extract, Grape Extract, Grape Seed Oil, Placenta Extract, Pullulan, Betaine, Hematma Extract, Button Extract, Hop Extract, Jojoba Oil, Ufoam oil, Methoxylatex octyl, Melissa extract, Meriloto extract, menthol, peach leaf extract, cornflower extract, coconut oil, eucalyptus extract, eucalyptus oil, eucalyptus oil, yukinoshita extract, lily extract, lily extract, iodized garlic extract, folic acid, yokuinin extract, Mugwort extract, raspberry ketone, lactoferrin, lanolin, lavender extract, lysine, lysine HCl, linoleic acid, sodium sulfate, apple extract, lice extract, lecithin, resorcinol, lettuce extract, lemon extract, lemon oil, leucine, rose water, rosehip oil , Rosemary extract, Roman chamomile extract, royal jelly, cracket extract, AHA (α-hydroxy acid), BG (butylene glycol), DNA (deoxyribonucleic acid), PCA (pyrrolide) Carboxylic acid) -Na, PCA-Na allantoin, PG (propylene glycol), PPG-28 buteth-35 (polyoxyethylene (35) polyoxypropylene (28) butyl ether), RNA (ribonucleic acid)-NA, t-butyl Methoxydibenzoylmethane, α-arbutin, mucopolysaccharide, creatine, diacetylbordine, vitamin A and its derivatives, vitamin C and its derivatives, sodium riboflavin phosphate, hydroquinone, liponic acid and its salts, amino acids and their derivatives, various plants Extracts, extracts from various animals, etc. may be mentioned.

  When using a fibroin nano thin film with respect to skin etc., cosmetics, such as a moisturizing cream, can be apply | coated to skin etc., and a fibroin nano thin film can also be transferred on it. In this case, it is possible to obtain the effect that the cosmetic is retained and it is difficult for the cosmetic to peel off. In addition, after the fibroin nano thin film is transferred to the skin or the like, a cosmetic may be applied thereon. In these cases, it is possible to make the skin inconspicuous such as wrinkles, sags, spots, bruises, freckles, pores, scars, acne marks, burn marks, or discoloration due to skin diseases.

  The fibroin nano thin film according to the present embodiment can also be suitably used as a cosmetic sheet, a moisturizing sheet, a cosmetic auxiliary sticking sheet, and a cosmetic protective sheet, which hold a cosmetic.

  The fibroin nano thin film according to the present embodiment can contain a dye. Thus, the dye can be held on the fibroin nano thin film, and the sticking position when it is stuck on the skin etc. (when used) can be easily confirmed visually or the like.

  Examples of dyes include azo dyes (naphthol dyes, etc.), mobe, para red, fluorescein, fuxin, phenolphthalein, neutral red, phenazine derivative dyes, methylene blue, dihydrointol, congo red, eosin, indanthrene, aniline black, acridine, Azoic dye, neocyanine, cryptocyanin, indocyanine green, hemoglobin, heme erythrin, pheo porphyrin, pheophorbide, cytochrome, bacteriochlorophyll, chlorophyllide, chlorophyll, melanin, catechin, anthocyan, anthocyan, anthracite, flavanones, flavonoid, lutein, lycopene , Fucoxanthin, zeaxanthin, cryptoxanthin, xanthophylls, carotene, carotenoids, Nistein, chlorocuroline, chlorin, crocetin, curcumin, xanthone matin, carthamin, erythrocuroline, urobiline, indigo, anthraquinone, anthocyan, alizarin, bilirubin, biliberdin, phytochrome, phycoerythrin, phycobiline, phycoglobin, myoglobin, porfin Porphyrin, hemocyanin, hemocyanin, rhodomatin, rhodoxanthin, rhodopsin, leghemoglobin, laminaran, morindine, phorbirin, mangosteen, berberine, betacyanin, purpurin, brazilin, pinnaglobin, hypericin, bixin, tulacin, tannin, stercopilin, commelinin, Gossy pole, cochineal etc. may be mentioned. Among the dyes, ionic dyes are preferable from the viewpoint of excellent solubility in water and alcohol. The dyes may be used alone or in combination of two or more.

  The fibroin nano thin film according to the present embodiment can contain metal ions. Thereby, it is possible to hold metal ions in the fibroin nano thin film, and when it is attached to the skin etc. (when used), the metal ions are gradually eluted from the fibroin nano thin film and gradually absorbed in the skin etc. Can. In addition, fibroin nano thin films having effects such as antibacterial, sterilization, deodorizing and antiperspirant can be obtained by using metal ions.

  As metal ions, alkali metal ions such as lithium, sodium and potassium; alkaline earth metal ions such as magnesium, calcium and barium; transition metal ions such as gold, silver, copper, platinum and palladium; aluminum ion; lead ion; Tin ions and the like can be mentioned. Among metal ions, silver ion is preferable from the viewpoint of having an antibacterial effect and a deodorizing effect. The metal ions can be used singly or in combination of two or more.

  The fibroin nano thin film according to the present embodiment can contain a drug. Thereby, the drug can be held on the fibroin nano thin film, and when applied to the skin (when used), the drug can be gradually eluted from the fibroin nano thin film and can be gradually absorbed on the skin etc. . In addition, fibroin nano thin film having an effect such as wound healing can be obtained.

  Examples of the drug include anti-inflammatory agents, hemostatic agents, vasodilators, thrombolytic agents, anti-atherosclerotic agents and the like. The drugs can be used alone or in combination of two or more.

  When the cosmetic or the drug is hydrophobic, a method of binding the cosmetic or the drug by hydrophobic interaction to the hydrophobic region of the fibroin nanofilm may be used. When the cosmetic or the drug is hydrogen bondable, a method of bonding the cosmetic or the drug to the hydrogen bondable region of the fibroin nano thin film by hydrogen bond may be used. When the cosmetic or the drug has a charge, a method of binding the cosmetic or the drug by electrostatic interaction to the oppositely charged region of the fibroin nanofilm may be used.

  As a crosslinking agent, alkyldiimidates, acyldiazides, diisocyanates, bismaleimides, triazinyls, diazo compounds, glutaraldehyde, N-succinimidyl-3- (2-pyridyldithio) alkyonate, bromocyan, etc. The components described above may be crosslinked with predetermined functional groups in the fibroin nanothin film. A crosslinking agent can be used individually by 1 type or in combination of 2 or more types.

  FIG. 1 is a schematic cross-sectional view showing an embodiment of a nano thin film sheet. As shown in FIG. 1, the nano thin film sheet 1 according to the present embodiment includes a support base (base) 2 and a fibroin nano thin film 3 laminated on the support base 2. The nano thin film sheet 1 is, for example, a nano thin film transfer sheet. The nano thin film sheet 1 may further include a cover film laminated on the fibroin nano thin film 3. As the support base 2, a base on which the fibroin nano thin film 3 of the nano thin film sheet 1 can be transferred to a transfer target is used. For example, as the support substrate 2, a support substrate having a smaller adhesion to the fibroin nano thin film 3 than that of the transfer target is used.

  The support substrate is not particularly limited as long as it has a smooth surface, and may be in the form of a film (sheet) or a roll. The support substrate may be a permeable substrate capable of penetrating or permeating the solvent. The permeable substrate has, for example, pores through which a solvent can permeate or permeate. The permeable substrate is a mesh sheet, a non-woven sheet, or a porous structure, from the viewpoint that the fibroin nano thin film can be easily suppressed from remaining on the substrate side when peeling the substrate from the nano thin film sheet. It may be a sex sheet. The mesh sheet is, for example, a sheet in which a thread-like material having a diameter of 100 μm or less is knitted in a lattice shape. When a permeable substrate is used, a fibroin nano thin film is formed on the permeable substrate through a soluble support layer dissolved in a solvent or the like, and then the soluble support layer is formed by the solvent which penetrates or permeates the permeable substrate. By dissolving, a structure in which the permeable substrate and the fibroin nano thin film are laminated may be obtained.

  Examples of the mesh sheet include polyester mesh sheet, nylon mesh sheet, carbon mesh sheet, fluorine resin mesh sheet, polypropylene mesh sheet, silk mesh sheet and the like. Among these, polyester mesh sheets, nylon mesh sheets and polypropylene mesh sheets are preferable, and polyester mesh sheets are more preferable. As a polyester mesh sheet, a polyethylene terephthalate mesh sheet is preferable. These mesh sheets may be used in combination with non-woven sheets.

  As a support base material, base films, such as a resin film, can also be used. As a constituent material of a support base material, any of a thermoplastic resin and a thermosetting resin may be sufficient, for example, polyethylene (high density, medium density or low density), polypropylene (isotactic type or syndiotactic type), Polybutene, polyolefin such as ethylene-prepylene copolymer, ethylene-vinyl acetate copolymer (EVA), ethylene-propylene-butene copolymer, cyclic polyolefin, modified polyolefin, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, Polyimide, polyamide imide, polycarbonate, poly- (4-methyl-1-pentene), ionomer, acrylic resin, polymethyl methacrylate, polybutyl (meth) acrylate, methyl (meth) acrylate-butyl (meth) acrylate copolymer, Methi (Meth) acrylate-styrene copolymer, acryl-styrene copolymer (AS resin), butadiene-styrene copolymer, polio copolymer (EVOH), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), ethylene -Polyesters such as terephthalate-isophthalate copolymer, polyethylene naphthalate, and precyclohexane terephthalate (PCT), polyether, polyether ketone (PEK), polyether ether ketone (PEEK), polyether imide, polyacetal (POM), Polyphenylene oxide, modified polyphenylene oxide, polyarylate, aromatic polyester (liquid crystal polymer), polytetrafluoroethylene, polyvinylidene fluoride, other fluorine resin, styrene resin Various thermoplastic elastomers such as polyolefins, polyvinyl chlorides, polyurethanes, fluororubbers, chlorinated polyethylenes, epoxy resins, epoxy resins, phenol resins, urea resins, melamine resins, unsaturated polyesters, silicone resins, polyurethanes, nylons, nitros Examples thereof include cellulose resins such as cellulose, cellulose acetate and cellulose acetate propionate, or copolymers, blends and polymer alloys containing these as main components. One or more of these may be used in combination (for example, as a laminate of two or more layers).

  Among these resin films, plastic films of polyethylene terephthalate, polyethylene, polypropylene, polyvinyl chloride and the like are preferable, and a polyethylene terephthalate film is more preferable from the viewpoint of being further excellent in the adhesiveness in the laminated film containing fibroin nano thin film.

  The surface of the supporting substrate may be subjected to corona discharge treatment, glow discharge treatment, plasma treatment, ultraviolet irradiation treatment, ozone treatment, chemical etching treatment with alkali, acid or the like.

  A resin film, an inorganic film, or a film (organic-inorganic film) containing an organic material and an inorganic material may be laminated on a supporting substrate. The laminated structure which consists of these resin films, an inorganic film, or an organic-inorganic film should just cover a part of base material surface. Further, in the laminated structure, the film which is not located on the outermost surface layer does not have to have a polar group.

  The thickness of the supporting substrate is preferably 1 to 500 μm, more preferably 3 to 300 μm, and still more preferably 5 to 200 μm.

  The thickness of the cover film is preferably 1 to 500 μm, more preferably 3 to 300 μm, and still more preferably 5 to 200 μm.

<Method of manufacturing fibroin nano thin film, and method of manufacturing nano thin film sheet>
The method for producing a fibroin nano thin film according to the present embodiment includes, for example, a step of obtaining a fibroin nano thin film using a fibroin aqueous solution as a fibroin nano thin film forming step. The fibroin nano thin film according to the present embodiment can be obtained, for example, by applying a fibroin aqueous solution on a supporting substrate. Examples of the method of applying the fibroin aqueous solution onto the supporting substrate include a casting method, a spin coating method, a spray coating method, a die coating method and the like, but are not limited thereto.

  The manufacturing method of the nano thin film sheet (for example, nano thin film transfer sheet) which concerns on this embodiment comprises the process of forming a fibroin nano thin film on a support base material (base material) using fibroin aqueous solution, for example. The nano thin film sheet according to the present embodiment may be obtained, for example, by forming a fibroin nano thin film by applying a fibroin aqueous solution on a support base, and supporting the fibroin nano thin film formed using the fibroin aqueous solution. You may be obtained by affixing to a base material.

<Transfer method>
The transfer method according to the present embodiment is a transfer method (sticking method) of fibroin nano thin film, and includes a step of transferring the fibroin nano thin film of the nano thin film sheet to a transfer target.

  The transfer method according to the present embodiment arranges the nano thin film sheet so that the fibroin nano thin film side faces the transfer target body, and presses the base side of the nano thin film sheet to transfer the fibroin nano thin film to the transfer target body. The process may be provided. In such a transfer method, since the fibroin nano thin film is transferred to the transfer target body by pressing the base side of the nano thin film sheet in a state where the base material covers the fibroin nano thin film, a transferred body and a nano thin film layer The followability with and the adhesion are improved. Therefore, such a transfer method is, for example, compared to a method in which the fibroin nano thin film is transferred to the transfer target after the base material is peeled in advance, or a fibroin nano thin film is transferred to the transfer target without pressing. Thus, the fibroin nano thin film can be suitably transferred to a transfer target.

  When pressing the substrate side of the nano thin film sheet, it is preferable to apply pressure substantially uniformly to the entire surface of the substrate. The pressing can be performed more simply and suitably by using a jig such as a roller.

The load at the time of pressing the substrate side of the nano thin film sheet is 10 g / cm ² or more from the viewpoint that the fibroin nano thin film can be easily suppressed to remain on the substrate side when peeling the substrate from the nano thin film sheet. Is more preferably 30 g / cm ² or more, and still more preferably 50 g / cm ² or more. The load is preferably 1000 g / cm ² or less, more preferably 900 g / cm ² or less, and more preferably 800 g / cm ² or less, from the viewpoint of easily suppressing damage to a material to be transferred such as skin. It is further preferred that From these viewpoints, the load is preferably 10 to 1000 g / cm ^2, more preferably 30~900g / cm ^2, further preferably 50 to 800 g / cm ^2.

  Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to the examples.

<Preparation of nano thin film>
Example 1
First, 150 g of high-pressure scoured chopsticks (silk fibroin, manufactured by Nagasa Co., Ltd.) was added to 1000 mL of a 9 M aqueous solution of lithium bromide, and dissolved by stirring at room temperature (25 ° C.) for 6 hours. Next, after centrifugation (rotational speed: 12000 rpm, 5 minutes) to remove the precipitate by decantation, the dialysis tube (Spectra / Por (registered trademark) 1 Dialysis Membrane, MWCO 6000-8000, Spectrum Laboratories, Inc.) 12 hours of dialysis against 5 liters of ultrapure water collected from the ultrapure water production system (PRO-0500 and FPC-0500 (model number), Organo Co., Ltd.) The

  2 mL of the obtained solution was aliquoted into an aluminum container and weighed. Thereafter, the dried product was dried in a drier at 100 ° C. for 2 hours, air-cooled, and weighed. The silk fibroin concentration (unit: g / L) in the solution was quantified from the mass loss.

  Glycerin and ultrapure water were added to the solution whose concentration was measured to prepare a silk fibroin aqueous solution having a silk fibroin concentration of 1% by mass and a glycerin concentration of 1% by mass.

  A silk fibroin aqueous solution was coated on a polyethylene terephthalate film (PET film, manufactured by Toyobo Co., Ltd., trade name “A4100”, 150 mm × 100 mm × 100 μm thickness), which is a supporting substrate, using an applicator. Thereafter, drying was performed at 100 ° C. for 1 hour to form a silk fibroin nano thin film. As a result of measuring the film thickness of the silk fibroin nano thin film according to Model No. F20 manufactured by Filmetrics, Inc., the film thickness of the silk fibroin nano thin film was 100 nm.

  Subsequently, a 10% by mass aqueous solution of polyvinyl alcohol 500 (Kanto Chemical Co., Ltd., average degree of polymerization: 500) dissolved in ultrapure water is applied by bar coater on the nano thin film so that the film thickness after drying becomes 5 μm. It apply | coated and formed the soluble support layer.

Thereafter, as a permeable base material, polyethylene terephthalate mesh sheet (PET mesh, manufactured by Daiki Shoji Co., Ltd., trade name "OKILON HYBRID", air permeability 3600 cc / cm ² · sec according to the flanged method described in JIS L1096, thickness : 90 μm) was laminated on the soluble support layer, and the water was evaporated at room temperature (25 ° C.). As a result, a laminate A1 was obtained in which a silk fibroin nano thin film, a soluble support layer (polyvinyl alcohol) and a permeable substrate (polyethylene terephthalate mesh sheet) were laminated in this order on a supporting substrate (polyethylene terephthalate film) .

Polyethylene terephthalate mesh sheet (PET mesh, manufactured by Daiki Shoji Co., Ltd., trade name "OKILON-SHA 2516", air permeability 5850 cc / cm ² · sec according to the flanged method described in JIS L1096, the thickness: A laminate A2 was obtained in the same manner as the laminate A1, except that the thickness was changed to 80 μm.

  The supporting substrate is peeled from each of the laminate A1 and the laminate A2, the nano thin films of the laminates A1 and A2 are bonded to each other, and the soluble support layer is immersed in water with the end fixed for 24 hours. It was dissolved. Thereafter, the water was evaporated at room temperature (25 ° C.).

  As a result, a nano thin film transfer sheet was obtained in which a silk fibroin nano thin film and a permeable base ("OKILON-SHA 2516") were laminated in this order on a permeable base ("OKILON HYBRID"). Although these permeable substrates are both polyethylene terephthalate mesh sheets, they have different adhesion strengths with the nano thin film. Moreover, since these differ in the state (mesh) of a mesh, the contact area with a nano thin film mutually differs.

Example 2
Glycerin and ultrapure water were added to the solution whose concentration was measured in the same manner as in Example 1 to prepare a silk fibroin aqueous solution having a silk fibroin concentration of 1% by mass and a glycerin concentration of 1% by mass. Furthermore, a nano thin film transfer sheet was obtained in the same manner as in Example 1 except that 0.1% by mass of Sulface SAG 503A as a surface conditioner was added to the silk fibroin aqueous solution.

Comparative Examples 1 and 2
An aqueous solution containing 0.3% by mass of chitosan (manufactured by Kimica Co., Ltd., viscosity average molecular weight: 90,000) was prepared as a solution A containing a polycation. Sodium alginate aqueous solution (manufactured by Kimica Co., Ltd., viscosity average molecular weight: 100,000, viscosity: 6.7 mPa · s, concentration: 0.1 mass%) 100 parts by mass as a solution B containing polyanion, malic acid (Wako Pure Chemical Industries, Ltd. A solution obtained by mixing with 1 part by mass of Co., Ltd.) was prepared.

  A polyethylene terephthalate film (PET film, manufactured by Toyobo Co., Ltd., trade name “A4100”, 150 mm × 100 mm × 100 μm thickness) as a supporting substrate was prepared. (A) immersing the supporting substrate in the solution A containing polycation for 1 minute, and then immersing in a rinse ultrapure water (specific resistance: 18 MΩ · cm) for 1 minute; (b) solution B containing polyanion After immersing the supporting substrate for 1 minute, this cycle was repeated 18 times, with the procedure of alternately repeating the steps of 1 minute immersion in ultrapure water for rinsing (specific resistance: 18 MΩ · cm). Thereby, on the polyethylene terephthalate film (support base material), the nano thin film which consists of a layer derived from chitosan and a layer derived from sodium alginate was formed. As a result of measuring the film thickness of the formed nano thin film according to Model No. F20 manufactured by Filmetrics, Inc., the film thickness of the nano thin film was 100 nm.

  Subsequently, a 10% by mass aqueous solution of polyvinyl alcohol 500 (Kanto Chemical Co., Ltd., average degree of polymerization: 500) dissolved in ultrapure water is applied by bar coater on the nano thin film so that the film thickness after drying becomes 5 μm. It apply | coated and formed the soluble support layer.

Thereafter, as a permeable base material, polyethylene terephthalate mesh sheet (PET mesh, manufactured by Daiki Shoji Co., Ltd., trade name "OKILON HYBRID", air permeability 3600 cc / cm ² · sec according to the flanged method described in JIS L1096, thickness : 90 μm) was laminated on the soluble support layer, and the water was evaporated at room temperature (25 ° C.). As a result, on a supporting substrate (polyethylene terephthalate film), nano thin films (laminated laminated films of a layer derived from chitosan and a layer derived from sodium alginate), a soluble supporting layer (polyvinyl alcohol) and a permeable substrate (polyethylene terephthalate) A mesh sheet B) was obtained in this order to obtain a laminate B1.

Polyethylene terephthalate mesh sheet (PET mesh, manufactured by Daiki Shoji Co., Ltd., trade name "OKILON-SHA 2516", air permeability 5850 cc / cm ² · sec according to the flange type method described in JISL 1096, a thickness of the permeable substrate: A laminate B2 was obtained in the same manner as the laminate B1, except that the thickness was changed to 80 μm.

  The supporting substrate is peeled from each of the laminate B1 and the laminate B2, the nano thin films of the laminates B1 and B2 are adhered to each other, and the soluble support layer is immersed in water with the end fixed for 24 hours. It was dissolved. Thereafter, the water was evaporated at room temperature (25 ° C.).

  As a result, on a permeable substrate ("OKILON HYBRID"), a nano thin film (a laminated film of a layer derived from a chitosan and a layer derived from sodium alginate), a permeable substrate ("OKILON-SHA 2516") A nano thin film transfer sheet laminated in order was obtained.

  In addition, when performing the said process (a) and process (b), in the comparative example 1, it exposes when the surface (The permeable base material of a nano thin film transfer sheet is exfoliated formed on a polyethylene terephthalate film. It adjusted so that the layer derived from chitosan was exposed to the surface. Moreover, in the comparative example 2, it adjusts so that the layer derived from sodium alginate may be exposed to the surface (The surface exposed when the permeable base material of a nano thin film transfer sheet is exfoliated) formed on a polyethylene terephthalate film. did.

<Measurement of contact angle>
In the measurement of the contact angle to water, ultrapure water (electrical resistivity: 18 MΩ · cm or more) collected from an ultrapure water production apparatus (PRO-0500 (model number), manufactured by Organo Corporation) was used as water.

  The contact angle was measured using a contact angle meter DM-501 manufactured by Kyowa Interface Science Co., Ltd. Specifically, the permeable substrate (“OKILON-SHA 2516”) of a sample piece of about 50 mm × 50 mm obtained by cutting out a nano thin film transfer sheet under an environment of temperature 23 ° C. and humidity 50% RH is peeled off. After that, the nano thin film surface was attached to the silicon wafer. The contact angle was measured 5 times each using ultrapure water, and the average value was obtained as the contact angle. In the case of the measurement of the contact angle with respect to water, the dripping amount of water was set to 1.0 μl, and the contact angle after standing for 10 seconds was read. The contact angle of Example 1 is 60.2 °, the contact angle of Example 2 is 30.2 °, and the contact angle of Comparative Example 1 (target to be measured: a layer derived from chitosan) is 8.0 °. The contact angle of Comparative Example 2 (target to be measured: layer derived from sodium alginate) was 6.3 °.

<Evaluation of pasteability>
On the surface of the skin moistened with water and a lotion, the nano thin film which peeled the pervious substrate ("OKILON-SHA 2516") of the nano thin film transfer sheet was exposed, and it exposed. The permeable substrate ("OKILON HYBRID") was then peeled off to transfer the nanofilm to the skin. In Examples 1 and 2, upon sticking, it was possible to stick without pressing. On the other hand, in Comparative Examples 1 and 2, sticking was difficult without pressing.

1 ... nano thin film sheet, 2 ... support base material (base material), 3 ... fibroin nano thin film.

Claims (7)

Contains fibroin,
The fibroin nano thin film for cosmetics whose contact angle with respect to water is 30 degrees or more.   The fibroin nano thin film according to claim 1, which has a thickness of 1 to 300 nm.   The fibroin nano thin film according to claim 1 or 2, which is for application to the skin. A substrate, and the fibroin nano thin film according to any one of claims 1 to 3 ;
The nano thin film sheet by which the said fibroin nano thin film is laminated | stacked on the said base material. The nano thin film sheet according to claim 4 , wherein the substrate is a mesh sheet, a non-woven sheet or a porous sheet. A nano thin film sheet according to claim 4 or 5 is disposed such that the fibroin nano thin film side faces the transfer target, and the base of the nano thin film sheet is pressed to thereby receive the fibroin nano thin film A transfer method comprising the step of transferring to a transfer body. The load at the time of pressing the substrate side of the nano-thin film sheet is 10 to 1000 g / cm ^2, the transfer method according to claim 6.

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