JP2017048160A - Fibroin solution, fibroin nano thin film, nano thin film sheet and method for producing the same, and transfer method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fibroin solution having excellent storage stability and coatability.SOLUTION: A fibroin solution comprises fibroin, surface-conditioning agent and water, and has a dissolved oxygen content of 5 mg/L or less.SELECTED DRAWING: Figure 1

Description

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

  In recent years, nano thin films for attaching to organs, skins, etc. have attracted attention in the medical field or cosmetic field. For example, a medical nano thin film to be applied to the skin surface or organ wound surface as a wound dressing material has been proposed (see, for example, Non-Patent Document 1).

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

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

  Fibroin has a long track record of being used as a surgical suture for purposes other than clothing, and is currently used as an additive for food or cosmetics, and there is no problem with safety to the human body. It can be used in the field of thin film applications. However, a fibroin-containing fibroin solution is used as a solution for obtaining a fibroin nanofilm, but the fibroin solution tends to have low storage stability (coating solution stability), and fibroin precipitates over time. May be gelled.

  In addition, when a fibroin nanofilm is obtained by applying a fibroin solution, it is required that the fibroin nanofilm be obtained without formation of streaks or the like.

  The present invention has been made to solve the above-described problems, and an object of the present invention is to provide a fibroin solution having excellent storage stability and coating property. Another object of the present invention is to provide a fibroin nanofilm obtained using the fibroin solution. Furthermore, this invention aims at providing the nano thin film sheet obtained using the said fibroin solution, its manufacturing method, and the transfer method using the said nano thin film sheet.

  The fibroin solution according to the present invention contains fibroin, a surface conditioner and water, and the dissolved oxygen amount is 5 mg / L or less.

  The fibroin solution according to the present invention is excellent in storage stability, and for example, gelation with time is suppressed. In addition, the fibroin solution according to the present invention is excellent in coatability, and for example, a fibroin nanothin film can be obtained without forming streaks or the like. According to the fibroin solution according to the present invention, a fibroin nanofilm having a uniform film thickness can be suitably produced.

  The surface conditioner is preferably at least one selected from the group consisting of a silicone-based surface conditioner, an acrylic-based surface conditioner, a vinyl-based surface conditioner, a fluorine-based surface conditioner, and an acetylene glycol-based surface conditioner. . The content of the surface conditioner in the fibroin solution is preferably 0.1% by mass or more.

  The fibroin nanofilm according to the present invention is formed using the fibroin solution according to the present invention. The film thickness of the fibroin nanofilm according to the present invention is preferably 1 to 300 nm. The fibroin nanothin film according to the present invention may be for skin application or cosmetic.

  The manufacturing method of the nano thin film sheet which concerns on this invention comprises the process of forming a fibroin nano thin film on a base material using the fibroin solution which concerns on this invention. The nano thin film sheet | seat which concerns on this invention is equipped with the 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. In the nano thin film sheet and the manufacturing method thereof according to the present invention, the base material may be a mesh sheet, a nonwoven fabric 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 so that the fibroin nano thin film side faces the transfer target, and the fibroin nano nano sheet is pressed by pressing the substrate side of the nano thin film sheet. A step of transferring the thin film to the transfer target may be provided. The load when pressing the substrate side of the nano thin film sheet is preferably 10 to 1000 g / cm ² .

  ADVANTAGE OF THE INVENTION According to this invention, the fibroin solution excellent in storage stability and coating property, and the fibroin nanothin film obtained using the said fibroin solution can be provided. ADVANTAGE OF THE INVENTION According to this invention, the nano thin film sheet obtained using the said fibroin solution, its manufacturing method, and the transfer method using the said nano thin film sheet can be provided.

It is a schematic cross section showing one embodiment of a nano thin film sheet. It is drawing which shows the evaluation result of coatability.

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

<Fibroin solution, fibroin nanofilm and nanofilm sheet>
The fibroin solution (fibroin nano thin film preparation solution, silk fibroin solution) according to the present embodiment contains fibroin (silk fibroin), a surface conditioner, and water. The fibroin nanothin film (silk fibroin nanothin film) according to the present embodiment can be formed using the fibroin solution according to the present embodiment.

  The fibroin used in the present embodiment is not limited, and examples thereof include natural silkworms such as rabbits, wild silkworms, and tengu, and fibroin produced from transgenic silkworms. Fibroin (silk fibroin) can be expected to be stably supplied because it is easy to obtain raw materials, and furthermore, since the price is also stable, it can be easily used industrially. The fibroin solution according to the present embodiment can be obtained by adding a surface conditioner to an aqueous solution obtained by dissolving fibroin in water (hereinafter referred to as “fibroin solution aqueous solution”). As a method for obtaining an aqueous solution for fibroin solution, any known method may be used. For example, after dissolving fibroin in a high concentration lithium bromide aqueous solution, desalting by dialysis and concentration by air drying are used. Convenient.

  The content of fibroin in the fibroin solution according to the present embodiment is preferably 0.1% by mass or more based on the total mass of the fibroin solution from the viewpoint of easily producing a nano-order thin film. The content is more preferably 0.5% by mass or more, and further preferably 1% by mass or more. The content of fibroin is preferably 100% by mass or less, more preferably 50% by mass or less, based on the total mass of the fibroin solution, from the viewpoint that it can be easily used as a coating solution. More preferably, it is 10 mass% or less. From these viewpoints, the fibroin content is preferably 0.1 to 100% by mass, more preferably 0.5 to 50% by mass, based on the total mass of the fibroin solution, and 1 to 10%. More preferably, it is mass%.

  The surface conditioner used in the present embodiment is a component used as an additive such as a paint, for example, and functions as an antifoaming agent or a leveling agent by changing the surface tension of a composition such as a paint. It is a component that can be expressed. Examples of the surface conditioner include silicone-based surface conditioners, acrylic-based surface conditioners, vinyl-based surface conditioners, fluorine-based surface conditioners, acetylene glycol-based surface conditioners, and benzoin.

  Examples of the silicone-based surface conditioner include silicone-based polymers such as polyether-modified silicone, polyester-modified silicone, polydimethylsiloxane, and polymethylalkylsiloxane. Examples of the acrylic surface conditioner include acrylic polymers such as polyether-modified acrylic polymer, polyester-modified acrylic polymer, and perfluoroalkyl-modified acrylic polymer. Examples of the vinyl surface conditioner include vinyl polymers such as vinyl ester polymers. Examples of the fluorine-based surface conditioner include fluorine-based polymers such as fluoroalkyl carboxylic acid and perfluoroalkyl carboxylic acid. Examples of the acetylene glycol-based surface conditioner include acetylene glycol-based polymers such as acetylene monool and acetylene diol. A surface conditioning agent can be used individually by 1 type or in combination of 2 or more types.

  Commercially available silicone surface conditioners include Silface SAG Series, Silface SJM Series (trade name, manufactured by Nissin Chemical Industry Co., Ltd.), BYK-300, BYK-302, BYK-306, BYK-307. BYK-310, BYK-315, BYK-320, BYK-322, BYK-323, BYK-325, BYK-330, BYK-331, BYK-333, BYK-337, BYK-344, BYK-370, BYK -375, BYK-377, BYK-UV3500, BYK-UV3510, BYK-UV3570 (above, trade name, manufactured by BYK Japan), 1711, 1751N, 1761, LS-001, LS-050 (above, Enomoto Kasei) Made by DISPARLON series), Granol 00, Granol 115, Granol 200, Granol 400, Granol 410, Granol 440, Granol 435, Granol 450, Granol 482, Granol B-1484, Polyflow ATF-2, Polyflow KL series (above, Kyoeisha Chemical Co., Ltd., trade name) ) And the like.

  Commercially available acrylic surface conditioners include BYK-350, BYK-352, BYK-354, BYK-355, BYK-358N, BYK-361N, BYK-392 (above, manufactured by Big Chemie Japan, Inc., trade name) ), OX-880EF, OX-881, OX-883, OX-883HF, OX-70, OX-77EF, OX-60, OX-710, OX-720, OX-720EF, OX-750HF, LAP-10, LAP-20, LAP-30, 1970, 230, LF-1980, LF-1982, LF-1983, LF-1984, LF-1985, LHP-95, LHP-96 (above, Enomoto Kasei Co., Ltd., DISPARLON series ), Polyflow No. 3, Polyflow No. 7, Polyflow No. 50E, Polyflow No. 50EHF, Polyflow No. 54N, Polyflow No. 55, Polyflow No. 64, polyflow no. 75, Polyflow No. 77, Polyflow No. 85, Polyflow No. 85HF, Polyflow No. S, Polyflow No. 90, polyflow no. 90D-50, Polyflow No. 95, Polyflow No. 300, Polyflow No. 460, polyflow WS, polyflow WS-30, polyflow WS-314 (manufactured by Kyoeisha Chemical Co., Ltd., trade name) and the like.

  Examples of commercially available vinyl surface conditioners include LHP-90, LHP-91, and the like (DISPARLON series, manufactured by Enomoto Kasei Co., Ltd.).

  Examples of commercially available fluorine-based surface conditioners include Florard (trade name, manufactured by 3M), Unidyne (trade name, manufactured by Daikin Industries, Ltd.), and Surflon (trade name, manufactured by Asahi Glass Co., Ltd.).

  Examples of commercially available acetylene glycol surface conditioners include Olphine EXP series (manufactured by Nissin Chemical Industry Co., Ltd., trade name).

  The surface conditioner is selected from the group consisting of a silicone-based surface conditioner, an acrylic-based surface conditioner, a vinyl-based surface conditioner, a fluorine-based surface conditioner, and an acetylene glycol-based surface conditioner from the viewpoint of further excellent storage stability. At least one selected from the above is preferred. By the way, the fibroin nano thin film is required to be insoluble in water depending on applications. As the surface conditioner, a silicone-based surface conditioner is preferable from the viewpoint of easily obtaining an insolubilized fibroin nanofilm.

  The dissolved oxygen content of the fibroin solution according to the present embodiment is 5 mg / L or less from the viewpoint of obtaining excellent coating properties. The amount of dissolved oxygen is preferably 4.75 mg / L or less, and more preferably 4.5 mg / L or less, from the viewpoint of obtaining further excellent coatability. The amount of dissolved oxygen is, for example, the amount of dissolved oxygen at 25 ° C. The amount of dissolved oxygen can be measured by, for example, DO meter B-506 manufactured by Iijima Electronics Co., Ltd.

  The content of the surface conditioner contained in the fibroin solution is preferably 0.1% by mass or more and 0.5% by mass or more based on the total mass of the fibroin solution from the viewpoint of further excellent storage stability. More preferably, it is more preferably 1% by mass or more. The content of the surface conditioning agent is preferably 90% by mass or less, more preferably 50% by mass or less, and more preferably 10% by mass based on the total mass of the fibroin solution from the viewpoint of further excellent storage stability. More preferably, it is more preferably 5% by mass or less.

  As a solvent for the fibroin solution, any solvent can be used as long as it can dissolve fibroin, but water (pure water or the like) can be used. The fibroin solution may contain an inorganic salt. Inorganic salts include calcium chloride, lithium bromide, sodium chloride and the like. An inorganic salt can be used individually by 1 type or in combination of 2 or more types.

  The film thickness of the fibroin nanothin film is not particularly limited, but is preferably in the following range during drying. The thickness of the fibroin nanothin film is preferably 1 nm or more, and more preferably 40 nm or more, from the viewpoint of further improving characteristics 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, and more preferably 200 nm or less from the viewpoint of further excellent properties such as self-adhesion, water absorption, and flexibility in a dry state. More preferably it is. 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. More preferably, it is -250 nm, and it is especially preferable that it is 40-200 nm.

  The fibroin solution and the fibroin nanothin film according to the present embodiment can contain a functional substance (for example, a substance that exhibits functionality in a transferred body such as an organ or skin). Examples of the functional substance include cosmetics, pigments, metal ions, drugs and the like. A functional substance can be used individually by 1 type or in combination of 2 or more types.

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

  The fibroin solution and the fibroin nanofilm according to the present embodiment can contain cosmetics such as a moisturizing cream. As a result, cosmetics can be retained on the fibroin nano thin film, and when applied to the skin, etc. (during use), the cosmetic gradually elutes from the fibroin nano thin film and is gradually absorbed by the skin, etc. Can do.

  As cosmetics, general cosmetics used for skin care such as moisturizing cream, skin cream, whitening cream, milky lotion, skin lotion, cosmetic liquid, and cosmetic gel can be used. Cosmetics contain cosmetic ingredients. The cosmetic ingredient is not particularly limited as long as it is cosmetically acceptable and effective for the skin. Cosmetic ingredients include, for example, moisturizers, whitening ingredients, stain-removing ingredients, antifungal ingredients, vitamins, anti-inflammatory ingredients, blood flow promoting ingredients, moistening ingredients, oils, metal particulates, and other ingredients used in cosmetics. Can be used. Cosmetics and cosmetic ingredients can be used alone or in combination of two or more.

  Cosmetic ingredients include, for example, almond oil, alkyl acrylate copolymer, hemp cellulose, ashitaba extract, ascorbic acid, sodium ascorbate, xanthine, astaxanthin, asparagus extract, aspartic acid, azulene, acerola extract, adenosine triphosphate 2Na , Avocado oil, achacha extract, aminobutyric acid, alanine, allantoin, arginine, sodium alginate, argylline, altea extract, arnica extract, albumin, aloe vera extract-2-kidachi aloe extract, benzoate Na, ginkgo extract, inositol, turmeric extract, Ouurushi extract, Ages extract, Sodium chloride, Oyster extract, Ogon extract, Oat extract, Panax ginseng extract, Odori extract, Dutch carashier , Olive oil, oryzanol, sea salt, hydrolyzed keratin, collagen, hydrolyzed collagen, hydrolyzed conkylion, hydrolyzed silk, hydrolyzed eggshell membrane, hydrolyzed egg white, brown algae extract, caffeine, chamomile extract, calamine, karin extract, Carotene, carrot extract, arabesque extract, licorice extract, camphor, raspberry extract, kiwi extract, xylitol, chitosan, cucumber extract, quaternium-73, gardenia extract, kumazasa extract, clara extract, glycolic acid, glycine, glycerin, glycyrrhizic acid 2K, Stearyl glycyrrhetinate, glucose, glutathione, glutamic acid, grapefruit extract, clematis extract, chlorella extract, cape aloe extract, gentian extract, tea extract, coen Im Q10, coffee extract, cornstarch, 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, sasanqua Oil, safflower oil, salicylic acid, sodium salicylate, zinc oxide, titanium oxide, hawthorn extract, cyanocobalamin, shiitake extract, diau extract, diglycerin, shikon extract, shiso extract, dihydrocholesterol, diphenyldimethylmekone, shimotake extract, tartaric acid, ginger extract, Ginger root extract, silk, silk extract, hydrogenated lecithin, squalane, stearyl alcohol, glyceryl stearate, stearin Acid sucrose, citrus extract, mint extract, sage extract, cetanol, ceramide 3, serine, cellulose gum, Sakuha extract, sorbitol, soybean extract, soybean fermented extract, evening primrose oil, dodami extract, tocopherol, trehalose, niacinamide, nicotinic acid Tocopherol, Lactic acid, Na lactate, Urea, Bakuga extract, Honey, Papain, Hamelis extract, Retinol palmitate, Panthenol, Hyaluronic acid Na, Biotin, Hachikoshi extract, Castor oil, Sunflower oil, Pyridoxine HCl, Biwa leaf extract, Buddle extract, Butcher bloom extract, grape extract, grape seed oil, placenta extract, pullulan, betaine, loofah extract, button extract, hop extract, jojoba oil, mesa Ufoam oil, methoxy cinnamon octyl, melissa extract, merirot extract, menthol, peach leaf extract, cornflower extract, coconut oil, eucalyptus extract, eucalyptus oil, yukinoshita extract, yuzu extract, lily extract, iodized garlic extract, folic acid, yokuinin extract, Artemisia extract, raspberry ketone, lactoferrin, lanolin, lavender extract, lysine, ricin HCl, linoleic acid, sodium sulfate, apple extract, litchi extract, lecithin, resorcin, lettuce extract, lemon extract, lemon oil, leucine, rose water, rosehip oil , Rosemary extract, Roman chamomile extract, royal jelly, bitumen extract, AHA (α-hydroxy acid), BG (butylene glycol), DNA (deoxyribonucleic acid), PCA (pyrrolide) Carboxylic acid) -Na, PCA-Na allantoin, PG (propylene glycol), PPG-28 butes-35 (polyoxyethylene (35) polyoxypropylene (28) butyl ether), RNA (ribonucleic acid) -NA, t-butyl Methoxydibenzoylmethane, α-arbutin, mucopolysaccharide, creatine, diacetylbordin, vitamin A and derivatives thereof, vitamin C and derivatives thereof, riboflavin sodium phosphate, riboflavin, hydroquinone, liponucleic acid and salts thereof, amino acids and derivatives thereof, Examples include various plant extracts and various animal-derived extracts.

  When the fibroin nano thin film is used on the skin or the like, a cosmetic such as a moisturizing cream can be applied to the skin or the like, and the fibroin nano thin film can be transferred thereon. In this case, the effect that it is difficult to peel off while the cosmetic is held is obtained. Further, after the fibroin nano thin film is transferred to the skin or the like, a cosmetic can be applied thereon. In these cases, skin with wrinkles, sagging, spots, bruises, freckles, pores, scars, acne scars, thermal scars, or discoloration due to skin diseases can be made inconspicuous.

  The fibroin nano thin film according to the present embodiment can also be suitably used as a cosmetic sheet, a moisturizing sheet, a makeup-assisting patch sheet, and a cosmetic protective sheet in which a cosmetic is held.

  The fibroin solution and the fibroin nanofilm according to the present embodiment can contain a dye. Thereby, it is possible to hold | maintain a pigment | dye to a fibroin nanothin film, and when applying on a skin etc. (at the time of use), the application position can be confirmed easily visually.

  As pigments, azo dyes (naphthol dyes, etc.), mauve, para red, fluorescein, fuchsin, phenolphthalein, neutral red, phenazine derivative pigments, methylene blue, dihydrointol, congo red, eosin, indanthrene, aniline black, acridine, Azoic dyes, neocyanine, cryptocyanine, indocyanine green, hemoglobin, heme erythrin, pheoporphyrin, pheophorbide, cytochrome, bacteriochlorophyll, chlorophyllide, chlorophyll, melanin, catechin, anthocyan, anthrochlor, flavanone, flavones, flavonoids, lutein, lycopene , Fucoxanthin, zeaxanthin, cryptoxanthin, xanthophylls, carotene, carotenoids, Nistain, chlorocruoline, chlorin, crocetin, curcumin, xanthone matine, carthamin, erythrocruoline, urobilin, indigo, anthraquinone, anthocyanin, alizarin, bilirubin, biliverdin, phytochrome, phycoerythrin, phycobilin, phycocyanin, myoglobin, porphine, Porphyrin, hemocyanin, hemovanadine, rhodomatine, rhodoxanthine, rhodopsin, litmus, leghemoglobin, laminaran, moringin, horbilin, mangosteen, berberine, betacyanin, purpurin, bradylin, pinnaglobin, hypericin, bixin, thulosine, tannin, sturpin, ninnin Gossy Paul, Cochineal and so on. Among the dyes, an ionic dye is preferable from the viewpoint of excellent solubility in water. A pigment | dye can be used individually by 1 type or in combination of 2 or more types.

  The fibroin solution and the fibroin nanofilm according to the present embodiment can contain metal ions. This allows metal ions to be retained on the fibroin nanofilm, and when they are applied to the skin, etc. (during use), the metal ions are gradually eluted from the fibroin nanofilm and gradually absorbed into the skin. Can do. Moreover, the fibroin nano thin film which has effects, such as antibacterial, disinfection, deodorizing, and antiperspirant, can be obtained using a metal ion.

  Examples of metal ions include 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 ions; lead ions; Examples include tin ions. Among metal ions, silver ions are preferable from the viewpoint of having an antibacterial effect and a deodorizing effect. A metal ion can be used individually by 1 type or in combination of 2 or more types.

  The fibroin solution and the fibroin nanofilm according to the present embodiment can contain a drug. As a result, the drug can be held on the fibroin nano thin film, and when it is applied to the skin or the like (during use), the drug gradually elutes from the fibroin nano thin film and can be gradually absorbed by the skin or the like. . Moreover, a fibroin nanofilm having an effect such as wound healing can be obtained.

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

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

  As a crosslinking agent, using alkyldiimidates, acyldiazides, diisocyanates, bismaleimides, triazinyls, diazo compounds, glutaraldehyde, N-succinimidyl-3- (2-pyridyldithio) alkionate, bromocyan, etc. You may bridge | crosslink said component and the predetermined functional group in a fibroin nano thin 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, a nano thin film sheet 1 according to this embodiment includes a support base material (base material) 2 and a fibroin nano thin film 3 laminated on the support base material 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 material 2, a base material on which the fibroin nanothin film 3 of the nanothin film sheet 1 can be transferred to a transfer target is used. For example, as the support base material 2, a support base material having an adhesive force to the fibroin nanothin film 3 smaller than that of the transfer target is used.

  As a support base material, if it has a smooth surface, it will not specifically limit, A film form (sheet form) or a roll form may be sufficient. The support substrate may be a permeable substrate capable of penetrating or permeating the solvent. The permeable substrate has, for example, pores through which the solvent penetrates or permeates. From the viewpoint of easily preventing the fibroin nano thin film from remaining on the substrate side when the substrate is peeled from the nano thin film sheet, the permeable substrate is a porous sheet having a mesh sheet, a nonwoven fabric sheet, or a porous structure. May be an adhesive 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, after forming a fibroin nano thin film on the permeable substrate via a soluble support layer that dissolves in a solvent or the like, the soluble support layer is formed by a solvent that permeates 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 a polyester mesh sheet, a nylon mesh sheet, a carbon mesh sheet, a fluororesin mesh sheet, a polypropylene mesh sheet, and a silk mesh sheet. Among these, a polyester mesh sheet, a nylon mesh sheet, and a polypropylene mesh sheet are preferable, and a polyester mesh sheet is more preferable. As the polyester mesh sheet, a polyethylene terephthalate mesh sheet is preferable. These mesh sheets may be used in combination with a nonwoven fabric sheet.

  As the support substrate, a substrate film such as a resin film can also be used. The constituent material of the supporting substrate may be either a thermoplastic resin or a thermosetting resin, for example, polyethylene (high density, medium density or low density), polypropylene (isotactic or syndiotactic type), Polyolefins such as polybutene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer (EVA), ethylene-propylene-butene copolymer, cyclic polyolefin, modified polyolefin, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, Polyimide, polyamideimide, polycarbonate, poly- (4-methyl-1-pentene), ionomer, acrylic resin, polymethyl methacrylate, polybutyl (meth) acrylate, methyl (meth) acrylate-butyl (meth) acrylate copolymer, Mechi (Meth) acrylate-styrene copolymer, acrylic-styrene copolymer (AS resin), butadiene-styrene copolymer, polio copolymer (EVOH), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), ethylene -Terephthalate-isophthalate copolymer, polyethylene naphthalate, polyester such as precyclohexane terephthalate (PCT), polyether, polyetherketone (PEK), polyetheretherketone (PEEK), polyetherimide, polyacetal (POM), Polyphenylene oxide, modified polyphenylene oxide, polyarylate, aromatic polyester (liquid crystal polymer), polytetrafluoroethylene, polyvinylidene fluoride, other fluororesins, styrene Various thermoplastic elastomers such as polyolefin, polyvinyl chloride, polyurethane, fluororubber, chlorinated polyethylene, ethoxy resin, phenol resin, urea resin, melamine resin, unsaturated polyester, silicone resin, polyurethane, nylon, nitro Examples thereof include cellulose resins such as cellulose, cellulose acetate, and cellulose acetate propionate, and copolymers, blends, and polymer alloys mainly containing these resins. One or two or more of these can be used in combination (for example, as a laminate of two or more layers).

  Among these resin films, plastic films such as polyethylene terephthalate, polyethylene, polypropylene, and polyvinyl chloride are preferable, and a polyethylene terephthalate film is more preferable from the viewpoint of further excellent adhesion in a laminated film including a 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 containing an organic material and an inorganic material (organic-inorganic film) may be laminated on the supporting substrate. The laminated structure consisting of these resin film, inorganic film, or organic-inorganic film only needs to cover a part of the substrate surface. Moreover, the film | membrane which is not located in an outermost surface layer in a laminated structure does not need to have a polar group.

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

  The film 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 for producing fibroin nano thin film and method for producing nano thin film sheet>
The manufacturing method of the fibroin nano thin film which concerns on this embodiment comprises the process of obtaining a fibroin nano thin film using the fibroin solution which concerns on this embodiment as a fibroin nano thin film formation process. The fibroin nanofilm according to the present embodiment can be obtained, for example, by applying a fibroin solution on a support substrate. Examples of the method for applying the fibroin 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 is equipped with the process of forming a fibroin nano thin film on a support base material (base material) using a fibroin 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 solution on a support substrate, and supports the fibroin nano thin film formed using the fibroin solution. You may obtain by affixing on a base material.

<Preservation of fibroin nanofilm>
The fibroin nano thin film product according to the present embodiment includes a fibroin nano thin film and a packaging material for packing the fibroin nano thin film, and may further include a desiccant. The fibroin nano thin film of the fibroin nano thin film product according to the present embodiment may be a fibroin nano thin film of a nano thin film sheet. Since it is preferable to store the fibroin nano thin film in an environment with little water vapor, it is preferable to store the fibroin nano thin film using a packaging material having a water vapor barrier property and a desiccant. Even if the packaging material has a water vapor barrier property, it does not pass water vapor at all, and a slight water permeation is inevitable, so it is more effective to keep the humidity inside the packaging material constant by adding a desiccant. It is.

(Packing material)
The performance of the packaging material having a water vapor barrier property is represented by a water vapor transmission rate. The smaller this value, the better the water vapor barrier property, which is suitable for packaging fibroin nano thin films. On the other hand, a packaging material having a low water vapor transmission rate is expensive. Taking these into consideration, the packaging material having a water vapor barrier property is packed with a packaging material composed of a packaging material having a water vapor transmission rate of 1.5 g / m ² · day (temperature 40 ° C., humidity 90% RH) or less. be able to. If the water vapor transmission rate is greater than 1.5 g / m ² · day, moisture penetration into the packing material increases, the burden on the desiccant increases, and economic efficiency decreases.

As a packing material satisfying such a water vapor transmission rate, an aluminum vapor deposition film (water vapor transmission rate of about 0.7 to 1.0 g / m ² · day (temperature 40 ° C., humidity 90% RH)), SiO vapor deposition film ( Water vapor transmission rate 0.1 to 0.7 g / m ² · day (temperature 40 ° C., humidity 90% RH)), alumina vapor deposition film (water vapor transmission rate 1.5 g / m ² · day (temperature 40 ° C., humidity 90) % RH)) and the like.

As a packaging material having a water vapor barrier property, a base film (for example, a polyethylene film (water vapor permeability of 10 to 20 g / m ² · day (temperature 40 ° C., humidity 90% RH))), a barrier layer and a heat seal layer are laminated. A laminated film configured as described above can be used. As a constituent material of the barrier layer, aluminum, nickel, titanium, magnesium, or the like can be used.

  It is preferable to pack the fibroin nano thin film with a plurality of layers of packing materials composed of a plurality of packing materials, and to use a packing material having a water vapor barrier property for at least one layer other than the innermost layer.

(desiccant)
In the fibroin nano thin film product according to the present embodiment, it is preferable to put a desiccant inside the packaging material having water vapor barrier properties. Moreover, it is preferable to maintain the humidity in the packaging material in an atmosphere of 70% RH or less.

  Examples of the desiccant (for example, desiccant placed inside the packing material) include calcium chloride, quicklime, silica gel, aluminosilicate, etc. Silica gel that does not cause deliquescence (liquefaction due to moisture absorption) from the viewpoint of guaranteeing product quality. Or aluminosilicate is preferable.

  The amount of the desiccant used is determined according to the ability of the desiccant so as to absorb the water penetration amount predicted from the hydrogen barrier properties of the packaging material to be combined and the storage days.

  The operation of packing the fibroin nano thin film into the packing material (packing, etc.) is preferably performed in a low temperature and low humidity atmosphere, and the initial atmosphere in the packing material is preferably adjusted to a low temperature and low humidity. As the atmosphere, specifically, a temperature of 18 to 22 ° C. and a humidity of 30 to 50% RH are preferable. This is especially important when no desiccant is used.

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

  In the transfer method according to the present embodiment, the nano thin film sheet is disposed so that the fibroin nano thin film side faces the transferred object, and the substrate side of the nano thin film sheet is pressed to transfer the fibroin nano thin film to the transferred object. The process to perform may be provided. In such a transfer method, the fibroin nano thin film is transferred to the transfer target by pressing the base side of the nano thin film sheet while the base material covers the fibroin nano thin film. Followability and adhesion are improved. Therefore, in such a transfer method, for example, compared with a method of transferring the fibroin nano thin film to the transfer target after peeling the substrate in advance, or a method of transferring the fibroin nano thin film to the transfer target without pressing. Thus, the fibroin nano thin film can be suitably transferred to the transfer target.

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

The load when pressing the substrate side of the nano thin film sheet is 10 g / cm ² or more from the viewpoint of easily suppressing the fibroin nano thin film from remaining on the substrate side when the substrate is peeled from the nano thin film sheet. It is preferably 30 g / cm ² or more, 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 the transferred body such as skin. More preferably. 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.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to an Example.

(Preparation of aqueous solution for silk fibroin solution)
First, 150 g of high-pressure squeezed chopped wood (silk fibroin, manufactured by Nagasuna Coffee Co., Ltd.) was added to 1000 mL of a 9M lithium bromide aqueous solution, and dissolved by stirring for 6 hours at room temperature (25 ° C.). Subsequently, after centrifugation (rotation speed: 12000 rpm, 5 minutes) and removal of the precipitate by decantation, a dialysis tube (Spectra / Por (registered trademark) 1 Dialyzation Membrane, MWCO 6000-8000, manufactured by Spectrum Laboratories, Inc.). ), And dialysis for 12 hours was repeated 5 times against 5 L of ultrapure water collected from ultrapure water production equipment (PRO-0500 and FPC-0500 (model number), manufactured by Organo Corp.) to obtain a silk fibroin solution. An aqueous solution was obtained.

  2 mL of the obtained aqueous solution for silk fibroin solution was dispensed into an aluminum container and weighed. Then, it freezes for 12 hours in the freezer of the non-fluorocarbon refrigerated freezer ("R-Y370 (model number)", manufactured by Hitachi, Ltd.) whose internal temperature is adjusted to about -20 ° C in advance, and freeze-dried ("FDU-1200 (model number)", manufactured by Tokyo Rika Kikai Co., Ltd.) was lyophilized for 7 hours. The obtained dried product was taken out from the freeze dryer and weighed within 30 seconds, and the silk fibroin concentration in the aqueous solution for silk fibroin solution was determined from the mass reduction.

(Preparation of silk fibroin nanofilm production solution)
A silk fibroin solution (solution for producing fibroin nano thin film. Silk fibroin concentration: 1% by mass) was prepared by the following procedure. In addition, the reference | standard of silk fibroin density | concentration and content of a surface conditioning agent is the total mass reference | standard of a silk fibroin solution.

[Example 1]
A silk fibroin solution is prepared by adding 0.1% by mass of a silicone-based surface conditioner (Silface SAG503A, manufactured by Nissin Chemical Industry Co., Ltd.) and ultrapure water to an aqueous solution for silk fibroin solution and then subjecting it to ultrasonic treatment under reduced pressure. did. The vacuum ultrasonic treatment was performed under the conditions of 10 kPa and 30 min using an explosion-proof ultrasonic deaerator (GSC1000DG-BS) manufactured by Sonic Technology Co., Ltd. It was confirmed that a silk fibroin solution was obtained without gelation.

[Comparative Example 1]
A silk fibroin solution was prepared by adding 0.1% by mass of a silicone-based surface conditioner (Silface SAG503A, manufactured by Nissin Chemical Industry Co., Ltd.) and ultrapure water to an aqueous solution for silk fibroin solution. It was confirmed that a silk fibroin solution was obtained without gelation.

[Comparative Example 2]
A silk fibroin solution was prepared by adding ultrapure water to the silk fibroin solution. It was confirmed that a silk fibroin solution was obtained without gelation.

[Comparative Example 3]
After adding ultrapure water to the silk fibroin solution for aqueous solution, vacuum ultrasonic treatment was performed in the same manner as in Example 1, and it was confirmed that the solution was gelled.

(Measurement of dissolved oxygen)
Except for Comparative Example 3 which gelled, the dissolved oxygen content of the silk fibroin solution was measured by the following procedure. The dissolved oxygen amount was measured at room temperature (25 ° C.) using a DO meter (B-506, manufactured by Iijima Electronics Co., Ltd.).

(Evaluation of coatability)
Silk of Example 1 and Comparative Examples 1 and 2 using PET film (polyethylene terephthalate film, manufactured by Toyobo Co., Ltd., trade name “A4100”, 150 mm × 100 mm × 100 μm thickness) as a supporting substrate using an applicator A fibroin solution was applied. Then, it dried at 100 degreeC for 1 hour, and formed the silk fibroin nano thin film.

  In Example 1, streaks were not observed in the silk fibroin nano thin film, and it was confirmed that the coating property was excellent. In Comparative Examples 1 and 2, streaks were observed in the silk fibroin nanofilm, and it was confirmed that the coating property was inferior. FIG. 2 shows the results of measuring the film thickness of the silk fibroin nanofilms of Example 1 and Comparative Example 1 in the width direction. In Comparative Example 1, it is confirmed that streaks occur near the center and the film thickness uniformity in the width direction is low.

  Table 1 shows the measurement results of the dissolved oxygen amount, the presence or absence of gelation, and the evaluation results of coating properties.

DESCRIPTION OF SYMBOLS 1 ... Nano thin film sheet, 2 ... Support base material (base material), 3 ... Fibroin nano thin film.

Claims (13)

Contains fibroin, surface conditioner and water,
A fibroin solution having a dissolved oxygen amount of 5 mg / L or less.   The surface conditioner is at least one selected from the group consisting of a silicone-based surface conditioner, an acrylic-based surface conditioner, a vinyl-based surface conditioner, a fluorine-based surface conditioner, and an acetylene glycol-based surface conditioner. 2. The fibroin solution according to 1.   The fibroin solution according to claim 1 or 2, wherein the content of the surface conditioner is 0.1% by mass or more.   The manufacturing method of a nano thin film sheet provided with the process of forming a fibroin nano thin film on a base material using the fibroin solution as described in any one of Claims 1-3.   The manufacturing method of the nano thin film sheet of Claim 4 whose said base material is a mesh sheet, a nonwoven fabric sheet, or a porous sheet.   The fibroin nano thin film formed using the fibroin solution as described in any one of Claims 1-3.   The fibroin nano thin film according to claim 6, wherein the film thickness is 1 to 300 nm.   The fibroin nanothin film according to claim 6 or 7, which is for skin application.   The fibroin nanofilm according to any one of claims 6 to 8, which is for cosmetic use. A base material and the fibroin nano thin film according to any one of claims 6 to 9,
A nano thin film sheet in which the fibroin nano thin film is laminated on the substrate.   The nano thin film sheet according to claim 10, wherein the substrate is a mesh sheet, a nonwoven fabric sheet, or a porous sheet.   The nano thin film sheet according to claim 10 or 11 is disposed so that the fibroin nano thin film side faces a transfer target, and the substrate side of the nano thin film sheet is pressed, so that the fibroin nano thin film is applied to the target film. A transfer method comprising a step of transferring to a transfer body. The transfer method according to claim 12, wherein a load when pressing the substrate side of the nano thin film sheet is 10 to 1000 g / cm ² .

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