JP2015221086A - Fibroin nanothin film transfer sheet and method for producing the fibroin nanothin film transfer sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fibroin nanothin film transfer sheet capable of easily producing a fibroin nanothin film layer and also capable of easily transferring the same to the body to be adhered.SOLUTION: Provided is a fibroin nanothin transfer sheet in which a first permeable base material, a fibroin nanothin film layer and a second permeable base material are laminated in this order, and in which the first permeable base material and the second permeable base material can permeate or penetrate a solvent.

Description

  The present invention relates to a fibroin nano thin film transfer sheet and a method for producing the nano thin film transfer sheet.

  In recent years, a nano thin film transfer sheet for attaching a nano thin film layer to an organ, skin or the like has attracted attention. For example, a medical nano-thin film transfer sheet to be applied to a skin surface or an organ wound as a wound dressing has been proposed (for example, see Non-Patent Document 1).

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

In the conventional nano thin film transfer sheet, when the nano thin film layer is stuck to an adherend such as skin, the nano thin film layer contracts, causing wrinkles, breakage, or dropping, and it may be difficult to apply evenly. Therefore, the nano thin film layer is sandwiched between the permeable base material, the soluble support layer and the cover film, and only the cover film is peeled off at the time of application to laminate the permeable base material, the soluble support layer and the nano thin film layer. Nano-thin film transfer sheets that adhere to the adherend have been studied. However, in the nanothin film transfer sheet provided with the soluble support layer, the final removal of the soluble support layer has been a problem in use.
Furthermore, higher biocompatibility is required in consideration of application to organs, skin, and the like.

  The present invention has been made to solve the above-mentioned problems, and can be used to easily produce a fibroin nano thin film layer and easily transfer it to an adherend, and a method for producing a fibroin nano thin film transfer sheet. The purpose is to provide.

  The fibroin nano thin film transfer sheet according to the present invention comprises a first permeable base material, a fibroin nano thin film transfer sheet, and a second permeable base material, which are laminated in this order. The second permeable substrate is a substrate capable of penetrating or permeating a solvent.

  Moreover, it is preferable that a solvent dissolves the soluble support layer which supports the fibroin nano thin film transfer sheet mentioned later on the 1st permeable base material or the 2nd permeable base material. That is, in this fibroin nano thin film transfer sheet, it is preferable that the permeable base material is a base material that can permeate or permeate a solvent that dissolves the soluble support layer. By allowing the solvent to permeate or permeate the permeable substrate, the soluble support layer that supports the fibroin nanofilm layer on the permeable substrate can be removed in advance. Therefore, the fibroin nano thin film layer can be easily transferred to the adherend without the need to remove the final soluble support layer in use.

  Moreover, it is preferable that the first permeable base material and the second permeable base material have different adhesion strengths with the fibroin nano thin film layer. In this case, when transferring the fibroin nano thin film layer, one of the permeable substrates can be easily peeled without damaging the fibroin nano thin film layer. Furthermore, the adhesion strength between one of the first permeable substrate and the second permeable substrate and the fibroin nano thin film layer is the fibroin nano thin film layer when the fibroin nano thin film layer is bonded to the adherend. It is preferable that it is weaker than the adhesion strength of the adherend. In this case, the fibroin nano thin film layer can be easily transferred to the adherend.

  The first permeable substrate and the second permeable substrate are preferably any one of a mesh sheet, a nonwoven fabric sheet, and a sheet having a porous structure. In this case, the solvent for dissolving the soluble support layer can be more reliably permeated or permeated.

  Both the first permeable substrate and the second permeable substrate are preferably mesh sheets. In this case, the solvent for dissolving the soluble support layer can be more reliably permeated or permeated.

  The first permeable substrate and the second permeable substrate preferably have different contact areas with the fibroin nanofilm layer. In this case, since the first permeable substrate and the second permeable substrate have different degrees of adhesion to the fibroin nano thin film layer, only the permeable substrate having the smaller contact area with the fibroin nano thin film layer is used. Can be easily peeled off from the fibroin nano thin film layer.

  In the fibroin nano thin film transfer sheet, either the first permeable substrate or the second permeable substrate is peeled from the fibroin nano thin film layer, and the permeable substrate of the fibroin nano thin film layer is peeled off. A laminated cover film can be provided. In this case, the fibroin nano thin film layer can be appropriately protected by the cover film.

  The thickness of the fibroin nano thin film layer is preferably 1 nm to 500 nm.

  The fibroin nano thin film layer is suitable for skin application. The fibroin nano thin film layer is suitable for cosmetic use.

  Moreover, the manufacturing method of the fibroin nano thin film transfer sheet which concerns on this invention is the fibroin nano thin film transfer formed by laminating | stacking the 1st permeable base material, the fibroin nano thin film layer, and the 2nd permeable base material in this order. A method for producing a sheet, wherein a laminate is formed by laminating a soluble support layer and a fibroin nano thin film layer between a first permeable substrate and a second permeable substrate, and A dissolution removal step of dissolving and removing the soluble support layer in the laminate by permeating or permeating a solvent that dissolves the soluble support layer in the first permeable substrate and the second permeable substrate; It is characterized by providing.

  In the manufacturing method of this fibroin nano thin film transfer sheet, after forming a laminate by laminating a soluble support layer and a fibroin nano thin film layer between a first permeable substrate and a second permeable substrate, The soluble support layer in the laminate is dissolved and removed by permeating or permeating the solvent that dissolves the soluble support layer in the first permeable substrate and the second permeable substrate. For this reason, the obtained fibroin nano thin film transfer sheet does not have a soluble support layer, and the fibroin nano thin film layer can be easily transferred to the adherend without the need to remove the final soluble support layer in use. it can.

  In the laminated body forming step, a first laminated body in which a first permeable substrate, a first soluble support layer, and a first fibroin nanothin film layer are laminated in this order, and a second permeable group A second laminated body in which a material, a second soluble support layer, and a second fibroin nanothin film layer are laminated in this order, a first fibroin nanothin film layer and a second fibroin nanothin film layer, It is preferable to form a laminated body by bonding so as to face each other. In this case, since the obtained fibroin nano thin film transfer sheet does not have a soluble support layer, the fibroin nano thin film layer can be easily transferred to the adherend without the need for removal of the final soluble support layer in use. .

  After the dissolution removal step, either the first permeable substrate or the second permeable substrate is peeled from the fibroin nano thin film layer, and the fibroin nano thin film layer is covered on the side where the permeable substrate is peeled off. A cover film laminating step for laminating the film can be further provided. In this case, the fibroin nano thin film layer can be appropriately protected by the cover film.

  ADVANTAGE OF THE INVENTION According to this invention, a fibroin nano thin film layer can be produced simply and a fibroin nano thin film layer can be simply transferred to a to-be-adhered body by using a permeable base material.

It is a schematic cross section which shows one Embodiment of the fibroin nano thin film transfer sheet which concerns on this invention. It is a schematic cross section which shows the manufacturing method of the fibroin nano thin film transfer sheet shown in FIG.

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings as necessary. However, the present invention is not limited to the following embodiments. In addition, the dimension ratio of drawing is not restricted to the illustrated ratio.

  FIG. 1 is a schematic cross-sectional view showing a fibroin nano thin film transfer sheet according to this embodiment. As shown in the figure, the fibroin nano thin film transfer sheet 1 is constituted by laminating a first permeable base material 2a, a fibroin nano thin film layer 3, and a second permeable base material 2b in this order. Has been.

[Fibroin nano thin film layer]
Examples of fibroin used in the present embodiment include fibroin produced from natural rabbits such as rabbits, wild silkworms, and tengu, and transgenic silkworms. For example, fibroin is used as an aqueous solution for producing the fibroin nanothin film layer used in the fibroin nanothin film transfer sheet of the present embodiment. However, fibroin is poorly soluble and difficult to dissolve directly in water. As a method for obtaining an aqueous fibroin solution, any known method may be used, but a method in which fibroin is dissolved in a high concentration lithium bromide aqueous solution, followed by desalting by dialysis and concentration by air drying is simple. Here, the concentration of the lithium bromide aqueous solution is preferably 8 to 10M, and more preferably 8.5 to 9.5M. When the concentration of the aqueous solution of lithium bromide is within the above range, the fibroin aqueous solution is less likely to gel, and there is a tendency that a fibroin nano thin film layer having a stable and uniform film thickness can be obtained.

  The fibroin concentration in the solution containing fibroin is preferably 0.01 to 10.0% by mass, more preferably 0.05 to 5.0% by mass, and 0.1 to 1.0% by mass. More preferably it is.

  The fibroin aqueous solution may contain inorganic salts.

  The additive added to the fibroin aqueous solution is an additive having an effect of promoting insolubilization of fibroin. As the additive, water-soluble monoalcohol, diol, triol, polyol and the like can be used. For example, methanol, ethanol, butanol, isopropyl alcohol and glycerin are preferable. These alcohols can be used alone or in combination of two or more.

  The additive concentration in the aqueous fibroin solution containing the additive is preferably 0.05 to 10.0% by mass, more preferably 0.1 to 5.0% by mass, and 0.8 to 3.0. More preferably, it is mass%. When the content of the additive is within this range, insolubilization of the fibroin nano thin film layer tends to be promoted. Further, if the content of the additive is 3.0% by mass or less, when the fibroin aqueous solution in which alcohol is added to the fibroin aqueous solution is allowed to stand, the fibroin having a stable and uniform film thickness is difficult to gel. There is a tendency to obtain nano thin film layers. In addition, in order to prevent gelation that is likely to occur when adding alcohols to an aqueous fibroin solution, a fibroin aqueous solution having a concentration higher than the target fibroin concentration is prepared in advance, and a diluted aqueous solution of alcohols is added thereto. More preferably.

  The thickness of the fibroin nano thin film layer 3 is not particularly limited. Since the properties such as self-adhesion, water absorption, and flexibility in a dry state become more excellent, the thickness of the fibroin nano thin film layer 3 is preferably in the range of 1 to 500 nm, 40 to It is more preferably 300 nm, particularly preferably in the range of 40 to 250 nm, and most preferably in the range of 40 to 200 nm.

  The fibroin nano thin film layer 3 can be suitably used as a fibroin nano thin film layer for skin application, a cosmetic fibroin nano thin film layer, or a fibroin nano thin film layer for cosmetic skin application.

  The fibroin nano thin film layer 3 can also hold cosmetics such as moisturizing cream or cosmetic ingredients such as vitamin C. Thus, when applied to the skin (during use), the cosmetic and cosmetic ingredients are gradually eluted from the thin film and can be gradually absorbed by the skin.

  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. The cosmetic ingredient is not particularly limited as long as it is a cosmetically acceptable ingredient effective for the skin. Specifically, for example, humectants, whitening ingredients, stain-removing ingredients, antifungal ingredients, vitamins, anti-inflammatory ingredients, blood flow promoting ingredients, moistening ingredients, oils, metal fine particles, and other ingredients used in cosmetics alone Or in combination of two or more.

  Examples of such cosmetic ingredients include almond oil, alkyl acrylate copolymer, hemp cellulose, ashitaba extract, ascorbic acid, sodium ascorbate, xanthine, astaxanthin, asparagus extract, aspartic acid, azulene, acerola extract, adenosine three Phosphate 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 biloba extract, inositol, Turmeric extract, walrus extract, age extract, sodium chloride, oyster extract, gonon extract, duckweed extract, ginseng extract, licorice extract, orang Mustard extract, olive oil, oryzanol, sea salt, hydrolyzed keratin, collagen, hydrolyzed collagen, hydrolyzed conkylion, hydrolyzed silk, hydrolyzed egg shell membrane, hydrolyzed egg white, brown alga 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 ex , Coenzyme 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, 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, diphenyldimethylmecon, shimotake extract, tartaric acid, ginger extract , Camphor root extract, silk, silk extract, hydrogenated lecithin, squalane, stearyl alcohol, glyceryl stearate, Sucrose stearate, ivy extract, mint extract, sage extract, cetanol, ceramide 3, serine, cellulose gum, sow extract, sorbitol, soybean extract, soybean fermented extract, evening primrose oil, dodami extract, tocopherol, trehalose, niacinamide, nicotine Acid tocopherol, lactic acid, sodium lactate, urea, bakuga extract, honey, papain, hamamelis extract, retinol palmitate, panthenol, hyaluronic acid Na, biotin, cypress extract, castor oil, sunflower oil, pyridoxine HCl, loquat leaf extract, buccal extract , Butcher bloom extract, grape extract, grape seed oil, placenta extract, pullulan, betaine, loofah extract, button extract, hop extract, jojoba Ile, Meadowfoam oil, Methoxy cinnamon octyl, Melissa extract, Merilot extract, Menthol, Peach leaf extract, Cornflower extract, Palm oil, Eucalyptus extract, Eucalyptus oil, Yukinoshita extract, Yuzu extract, Lily extract, Iodized garlic extract, Folic acid, Yokuinin Extract, mugwort extract, raspberry ketone, lactoferrin, lanolin, lavender extract, lysine, lysine HCl, linoleic acid, riboflavin, 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 (deoxyribo) Nucleic acid), PCA (pyrrolidonecarboxylic acid) -Na, PCA-Na allantoin, PG (propylene glycol), PPG-28 butes-35 (polyoxyethylene (35) polyoxypropylene (28) butyl ether), RNA (ribonucleic acid) -Na, t-butylmethoxydibenzoylmethane, α-arbutin, mucopolysaccharide, creatine, diacetylbordin, vitamin A 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.

  The fibroin nano thin film layer 3 can also hold a dye. Thereby, the sticking position when sticking to the skin (during use) can be easily confirmed visually.

  Examples of pigments include naphthol dyes (azo dyes), mauve, para red, fluorescein, fuchsin, phenolphthalein, neutral red, phenazine derivative pigments, methylene blue, dihydrointol, congo red, eosin, indanthrene, aniline black, acridine, azo Dyes, 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, cryptoxanthine, xanthophylls, carotene, carotene Id, genistein, chlorocruoline, chlorin, crocetin, curcumin, xanthone machin, cartamine, erythrocruoline, urobilin, indigo, anthraquinone, anthocyanin, alizarin, bilirubin, biliverdin, phytochrome, phycoerythrin, phycobilin, phycocyanin, myoglobin, Porphine, porphyrin, hemocyanin, hemovanadine, rhodomatine, rhodoxanthine, rhodopsin, litmus, leghemoglobin, laminaran, morindin, horbilin, mangosteen, berberine, betacyanin, purpurin, bradylin, pinnaglobin, hypericin, bixin, tussine, tansine, tussine, tancine, tansine Commerinine, gossypol, cochineal and the like. Among these, ionic dyes are preferable because they dissolve in water and alcohol.

  The fibroin nano thin film layer 3 can also hold metal ions. Thereby, when affixed to the skin (during use), the metal ions are gradually eluted from the fibroin nano thin film layer 3 and can be gradually absorbed by the skin. In addition, by using metal ions, a nano thin film layer having effects such as antibacterial, sterilizing, deodorizing, and antiperspiring can be formed.

  Examples of metal ions include alkaline 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, lead and tin ions Is mentioned. Among these, silver ions having antibacterial and deodorizing effects are more preferable.

  The fibroin nano thin film layer 3 can also hold a drug. This allows the drug to gradually elute from the fibroin nanothin film layer 3 when applied to the skin (during use) and be gradually absorbed by the skin. Moreover, it can be set as the fibroin nano thin film layer with the effect of wound healing.

  Examples of the drug include anti-inflammatory agents, hemostatic agents, vasodilators, thrombolytic agents, anti-arteriosclerotic agents and the like.

  Moreover, alkyl diimidates, acyl diazides, diisocyanates, bismaleimides, triazinyls, diazo compounds, glutaraldehyde, N-succinimidyl-3- (2-pyridyldithio) alkionate, bromocyan, etc. are used as a crosslinking agent. Then, the above-described component and a predetermined functional group in the fibroin nano thin film layer 3 may be cross-linked.

  Furthermore, when the drug / cosmetic is hydrophobic, it is bonded to the hydrophobic region of the fibroin nano thin film layer by hydrophobic interaction. When the drug / cosmetic is hydrogen bonding, the hydrogen bonding property of the fibroin nano thin film layer A method of bonding to a region by hydrogen bonding, or a method of bonding to an oppositely charged region of the fibroin nano thin film layer by electrostatic interaction when the drug / cosmetic material has a charge may be used.

[Penetration substrate]
The permeable base materials 2a and 2b are base materials that can permeate or permeate the solvent. Preferably, the fibroin nano thin film layer 3 is formed into the first permeable base material 2a or the second permeable base material 2b. It is a base material that can permeate or permeate a solvent that dissolves a soluble support layer (details will be described later). Moreover, the permeable base materials 2a and 2b are base materials that do not dissolve in the solvent that dissolves the soluble support layer.

  The film thicknesses of the permeable base materials 2a and 2b are preferably 1 to 500 μm, more preferably 3 to 300 μm, and still more preferably 5 to 200 μm, from the viewpoint of followability and handleability.

  The permeable base materials 2a and 2b are preferably in the form of a sheet (film) from the viewpoint of handleability and availability. Moreover, it is preferable that the permeable base materials 2a and 2b have pores that allow the solvent to permeate or permeate, and more preferably a mesh sheet, a nonwoven fabric sheet, or a sheet having a porous structure. The mesh sheet refers to, for example, a material in which a thread-like material having a diameter of 100 μm or less is knitted in a lattice shape.

  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 a polyester mesh sheet, a polyethylene terephthalate mesh sheet is mentioned as a preferable example, for example. In addition, you may use combining these mesh sheets and a nonwoven fabric.

From the viewpoint of transferability of the fibroin nano thin film layer 4, the mesh sheet is preferably 10 to 100,000 cm ³ / cm ² · sec in air permeability according to the fragile method described in JIS L 1096, It is more preferable that it is 100-50,000 cm < ³ > / cm < ² > / sec, and it is still more preferable that it is 1000-10,000 cm < ³ > / cm < ² > / sec. The difference in the gap between the first permeable substrate 2a and the second permeable substrate 2b is preferably 100 cm ³ / cm ² · sec or more, and more preferably 500 cm ³ / cm ² · sec or more. More preferably, it is more preferably 1000 cm ³ / cm ² · sec or more.

  The 1st permeable base material 2a and the 2nd permeable base material 2b may consist of the mutually same base material, and may consist of a mutually different base material. It is preferable that the first permeable substrate 2a and the second permeable substrate 2b have different adhesion strengths with the fibroin nano thin film layer 3. When the permeable substrate is peeled off, the fibroin nano thin film layer 3 remains on one of the permeable substrates, and the fibroin nano thin film layer 3 itself has no damage such as tearing or chipping. it can. Examples of means for changing the adhesion strength include adjusting the material of the mesh sheet used for the permeable base material, the state of weaving, the thickness of the fibers used, the mesh opening, the opening ratio, and the like.

  In this embodiment, both the 1st permeable base material 2a and the 2nd permeable base material 2b consist of a polyethylene terephthalate mesh sheet, for example. However, the opening of the polyethylene terephthalate mesh sheet constituting the first permeable base material 2a is smaller than, for example, the opening of the polyethylene terephthalate mesh sheet constituting the second permeable base material 2b. In other words, for example, the gap of the polyethylene terephthalate mesh sheet constituting the first permeable substrate 2a is smaller than the gap of the polyethylene terephthalate mesh sheet constituting the second permeable substrate 2b.

  As described above, the contact area between the permeable base materials 2a and 2b and the fibroin nano thin film layer 3 can be adjusted by adjusting the mesh openings and the opening ratios of the mesh sheets used for the permeable base materials 2a and 2b.

[Production method of fibroin nano thin film transfer sheet]
(Fibroin nano thin film layer formation process)
Examples of the method for applying the fibroin aqueous solution onto the support substrate include, but are not limited to, a cast method, a spin coat method, a spray coat method, and a die coat method.

  The support substrate 4 is not particularly limited as long as it has a smooth surface, and may be a sheet shape or a roll shape. The support substrate 4 may be either a thermoplastic resin or a thermosetting resin, such as polyethylene (high density, medium density or low density), polypropylene (isotactic or syndiotactic), polybutene, Polyolefins such as 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-methylbenten-1), ionomer, acrylic resin, polymethyl methacrylate, polybutyl (meth) acrylate, methyl (meth) acrylate-butyl (meth) acrylate copolymer, methyl (meta ) Acrylate-styrene copolymer, acrylic-styrene copolymer (AS resin), butadiene-styrene copolymer, polio copolymer (EVOH), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), ethylene-terephthalate- Polyester such as isophthalate copolymer, polyethylene naphthalate, 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, polyolefin Various types of thermoplastic elastomers such as vinyl, polyvinyl chloride, polyurethane, fluoro rubber, chlorinated polyethylene, epoxy resin, phenol resin, urea resin, melamine resin, unsaturated polyester, silicone resin, polyurethane, nylon, Cellulosic resins such as nitrocellulose, cellulose acetate, and cellulose acetate propionate, or copolymers, blends, and polymer alloys mainly composed of these may be mentioned, and one or more of these may be combined ( For example, it can be used as a laminate of two or more layers.

  Among these resin films, plastic films such as polyethylene terephthalate (PET), polyethylene (PE), polypropylene (PP), and polyvinyl chloride (PC) are preferably used. A polyethylene terephthalate (PET) film is more preferable because it is more excellent in the adhesion of the laminated film.

  Further, the surface of the support substrate 4 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 support substrate 4. The laminated structure consisting of these resin film layer, inorganic film layer, or organic-inorganic film layer 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 film thickness of the support base 4 is preferably in the range of 1 to 500 μm, more preferably in the range of 3 to 300 μm, and still more preferably in the range of 5 to 200 μm.

(Solubility support layer forming step)
Next, as shown in FIG.2 (b), the soluble support layer 5a is formed on the surface opposite to the support base material 4 of the fibroin nano thin film layer 3a.

  The soluble support layer 5a is not limited as long as it dissolves in a solvent. However, in consideration of irritation to the skin, the soluble support layer 5a is preferably a layer formed of a film formed from a polymer soluble in water or alcohol. . The soluble support layer 5a may be a layer that is soluble in a weakly alkaline or weakly acidic aqueous solution.

  Examples of polymers soluble in water or alcohol include polyelectrolytes such as polyacrylic acid and polymethacrylic acid; non-polyethylene glycol, polyacrylamide, polyvinyl alcohol, polyvinyl alcohol derivatives, starch, hydroxypropyl cellulose, cellulose acetate and the like. Examples include ionic water-soluble polymers; resins such as novolak or poly (N-alkylcyanoacrylate).

  The viscosity average molecular weight of the polymer is usually preferably 1 to 1,000,000, more preferably 5,000 to 500,000.

  The “viscosity average molecular weight” may be evaluated by a viscosity method which is a general measurement method. For example, Mν can be calculated from the intrinsic viscosity [η] measured based on JIS K 7367-3: 1999. That's fine.

  In the present embodiment, it is more preferable to use polyvinyl alcohol or a derivative thereof as a polymer that is soluble in water or alcohol. In the case of using polyvinyl alcohol, the average degree of polymerization is preferably 100 to 2000, and more preferably 200 to 1000, from the viewpoint of film formation and solubility in a solvent. Here, the average degree of polymerization can be measured based on a method defined in JIS K 6726.

  In addition, the film thickness of the soluble support layer 5a is preferably in the range of 1 μm to 100 μm, and preferably in the range of 2 μm to 50 μm, from the viewpoint of peelability from the fibroin nano thin film layer 3a and bonding properties. Is more preferable, and it is still more preferable that it exists in the range of 5 micrometers-20 micrometers.

  The soluble support layer 5a is formed by applying a polymer solution dissolved in, for example, water or alcohol on the fibroin nano thin film layer 3a formed on one side of the support substrate 4, and usually 10 minutes to 24 hours, preferably Is formed by drying for 1 to 12 hours to remove water or alcohol.

  Examples of the method for applying the polymer solution onto the fibroin nano thin film layer 3a include, but are not limited to, a casting method and a spin coating method. The soluble support layer 5a can also be formed using a bar coater or a roll coater.

  Although there is no restriction | limiting in particular in the density | concentration of the polymer melt | dissolved in the said water or alcohol, 1-40 mass% is preferable from a coating property viewpoint, 2-30 mass% is more preferable, 5-20 mass% is still more preferable. 5-10 mass% is especially preferable.

  The soluble support layer 5a can be peeled together with the fibroin nano thin film layer 3a from the support substrate 4 using tweezers or the like. At this time, the fibroin nanothin film layer 3a is dissolved at the same time as peeling by a secondary bonding force such as electrostatic interaction, hydrogen bonding, van der Waals force, etc. generated between the soluble support layer 5a and the fibroin nanothin film layer 3a. It becomes possible to transfer to the property support layer 5a.

(Penetration substrate forming process)
Subsequently, as shown in FIG. 2 (c), a permeable substrate 2a that permeates or permeates a solvent that dissolves the soluble support layer 5 is laminated on the soluble support layer 5a. Although it does not specifically limit as a lamination | stacking method of the permeable base material 2, Methods, such as a lamination, can be used. In addition, after peeling the support base material 4 from the fibroin nano thin film layer 3a, you may laminate | stack the permeable base material 2a on the soluble support layer 5a.

(Laminate formation process)
Subsequently, as shown in FIG. 2D, for example, the first stacked body 6a and the second stacked body 6b obtained in the above-described steps are prepared. The 1st laminated body 6a is comprised by laminating | stacking the 1st permeable base material 2a, the 1st soluble support layer 5a, and the 1st fibroin nano thin film layer 3a. On the other hand, the 2nd laminated body 6b is comprised by laminating | stacking the 2nd permeable base material 2b, the 2nd soluble support layer 5b, and the 2nd fibroin nano thin film layer 3b.

  Next, as shown in FIG.2 (e), the 1st laminated body 6a and the 2nd laminated body 6b oppose the 1st fibroin nano thin film layer 3a and the 2nd fibroin nano thin film layer 3b. Thus, the laminated body 7 is obtained by bonding them together. As a method of bonding, for example, a method such as laminating can be used. In addition, when laminating, it is preferable that the fibroin nano thin film layer 3 is not in a dry state but in a state containing moisture.

  In addition, when making the above-mentioned cosmetics, pigment | dye, etc. hold | maintain in the fibroin nano thin film layer 3 of the fibroin nano thin film transfer sheet 1 finally obtained, before the laminated body formation process, the 1st fibroin nano thin film layer 3a and 2nd Cosmetic material, a pigment | dye, etc. can be previously hold | maintained at any one or both of the fibroin nano thin film layer 3b. Alternatively, in the laminate formation step, cosmetics, pigments, and the like are arranged between the first fibroin nano thin film layer 3a and the second fibroin nano thin film layer 3b, and then the first fibroin nano thin film layer 3a and the first fibroin nano thin film layer 3a Two fibroin nano thin film layers 3b can be bonded together.

(Dissolution removal process)
Subsequently, as shown in FIG. 2F, for example, the laminate 7 is immersed in a solvent 8 (for example, water) in which the soluble support layers 5a and 5b are dissolved. Thereby, as schematically shown by arrows in FIG. 2 (f), the permeable base materials 2 a and 2 b permeate or permeate the solvent 8, so that the soluble support layers 5 a and 5 b are dissolved in the solvent 8. Therefore, the fibroin nano thin film transfer sheet 1 from which the soluble support layers 5a and 5b have been removed is obtained.

[Function and effect]
As described above, in this embodiment, the permeable base materials 2a and 2b are made of a mesh sheet that permeates or permeates the solvent that dissolves the soluble support layers 5a and 5b. Therefore, the soluble support layers 5a and 5b can be dissolved by the dissolution and removal step, and the fibroin nano thin film transfer sheet 1 from which the soluble support layers 5a and 5b have been removed is obtained. Therefore, according to the fibroin nano thin film transfer sheet 1, the fibroin nano thin film layer 3 can be easily transferred to the adherend without requiring removal of the final soluble support layer.

  Moreover, in this embodiment, the opening of the mesh sheet which comprises the 1st permeable base material 2a is smaller than the opening of the mesh sheet which comprises the 2nd permeable base material 2b. That is, the 2nd permeable base material 2b is contacting the fibroin nano thin film layer 3 with a contact area smaller than the 1st permeable base material 2a. Therefore, when the fibroin nano thin film transfer sheet 1 is attached to the adherend, the second permeable substrate 2b having a small contact area with the fibroin nano thin film layer 3 can be easily peeled from the fibroin nano thin film layer 3.

[Modification]
In the above embodiment, in the laminate forming step, the first laminate 6a in which the first permeable substrate 2a, the first soluble support layer 5a, and the first fibroin nanothin film layer 3a are laminated, The second laminated body 6b formed by laminating the second permeable substrate 2b, the second soluble support layer 5b, and the second fibroin nano thin film layer 3b is bonded to the first laminated body. Only the 6a and the second permeable base material 2b, or the second laminated body 6b and the first permeable base material 2a alone may be bonded together.

  In the above embodiment, the fibroin nano thin film transfer sheet 1 is formed by laminating the first permeable substrate 2a, the fibroin nano thin film layer 3, and the second permeable substrate 2b. The nano thin film transfer sheet may be formed by laminating a cover film in place of either the first permeable substrate 2a or the second permeable substrate 2b.

  In this case, the manufacturing method of the fibroin nano thin film transfer sheet peels off one of the first permeable substrate 2a and the second permeable substrate 2b after the dissolution and removal step in the above embodiment, A cover film laminating step of laminating a cover film on the side of the thin film layer 3 from which the permeable substrate is peeled is further provided.

  The cover film is not particularly limited as long as it has a smooth surface, and may be a sheet shape or a roll shape. The cover film may be either a thermoplastic resin or a thermosetting resin, such as polyethylene (high density, medium density or low density), polypropylene (isotactic or syndiotactic), polybutene, ethylene- Polyolefin such as propylene copolymer, ethylene-vinyl acetate copolymer (EVA), ethylene-propylene-butene copolymer, cyclic polyolefin, modified polyolefin, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, polyimide, polyamideimide , Acrylic resins such as polycarbonate, poly- (4-methylbenten-1), ionomer, polymethyl methacrylate, polybutyl (meth) acrylate, methyl (meth) acrylate-butyl (meth) acrylate copolymer, methyl ( ) Acrylate-styrene copolymer, acrylic-styrene copolymer (AS resin), butadiene-styrene copolymer, ethylene-vinyl alcohol copolymer (EVOH), polyethylene terephthalate (PET), polybutylene terephthalate (PBT) , Ethylene-terephthalate-isophthalate copolymer, polyethylene naphthalate, precyclohexane terephthalate (PCT), etc. polyester, polyether, polyetherketone (PEK), polyetheretherketone (PEEK), polyetherimide, polyacetal (POM) ), Polyphenylene oxide, modified polyphenylene oxide, polyarylate, aromatic polyester (liquid crystal polymer), polytetrafluoroethylene, polyvinylidene fluoride, other fluorine-based Various thermoplastic elastomers such as fat, styrene, polyolefin, polyvinyl chloride, polyurethane, fluororubber, chlorinated polyethylene, ethoxy resin, phenol resin, urea resin, melamine resin, unsaturated polyester, silicone resin, Cellulose resins such as polyurethane, nylon, nitrocellulose, cellulose acetate, and cellulose acetate propionate, or copolymers, blends, and polymer alloys mainly containing these resins are included. One or two of them The above can be combined (for example, as a laminate of two or more layers).

  Among these resin films, plastic films such as polyethylene terephthalate (PET), polyethylene (PE), polypropylene (PP), and polyvinyl chloride (PC) are preferably used. A polyethylene terephthalate (PET) film is more preferable because it is more excellent in the adhesion of the laminated film.

  Further, the surface of the cover film 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.

  In the cover film, 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 cover film. The laminated structure consisting of these resin film layer, inorganic film layer, or organic-inorganic film layer 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 film thickness of the cover film is preferably in the range of 1 to 500 μm, more preferably in the range of 3 to 300 μm, and still more preferably in the range of 5 to 200 μm.

[Preservation of nano thin film transfer sheet]
Since it is desirable to store the fibroin nano thin film transfer sheet in an environment where there is little water vapor, it is desirable to store the fibroin nano thin film transfer sheet using a packaging material having a water vapor barrier property and a drying material. Even if the packaging material has a water vapor barrier property, it does not transmit 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 a packaging material having a water vapor barrier property is represented by a water vapor transmission rate. The smaller this value is, the better the water vapor barrier property is, and it is suitable for packing a nano thin film transfer sheet. However, on the other hand, a packaging material having a low water vapor transmission rate is expensive. Taking these into consideration, the water vapor barrier property of the packaging material is packed with a water vapor barrier packaging material having a water vapor permeability of 1.5 g / m ² · day (temperature 40 ° C., humidity 90% RH) or less. If the water vapor transmission rate is larger than this, water penetration into the packing material increases, the burden on the desiccant becomes large, and the economic efficiency deteriorates.

As a 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) Transmittance 0.1 to 0.7 g / m ² · day (temperature 40 ° C., humidity 90% RH)), alumina vapor deposition film (water vapor permeability 1.5 g / m ² · day (temperature 40 ° C., humidity 90%) RH) grade).

In addition, as a packaging material having a water vapor barrier property, a substrate film (for example, a polyethylene film (water vapor permeability of 10 to 20 g / m ² · day (temperature 40 ° C., humidity 90% RH))), barrier layer, heat seal layer A laminate film formed by laminating can be used. As the barrier layer, aluminum, nickel, titanium, magnesium or the like is used.

  It is preferable that the fibroin nano thin film transfer sheet is packed in a plurality of layers with a plurality of packing materials, and a packing material having a water vapor barrier property is used in at least one layer other than the innermost layer.

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

  As the desiccant to be put inside the packing material, there are calcium chloride, quicklime, silica gel, aluminosilicate and the like, but silica gel and aluminosilicate which do not cause deliquescence (liquefaction due to moisture absorption) are preferable from the viewpoint of guaranteeing the quality of the product.

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

  The operation of packing the fibroin nano thin film transfer sheet in a packaging material is preferably performed in a low temperature and low humidity atmosphere, and the initial atmosphere in the packaging material is preferably kept at a low temperature and low humidity. A preferred atmosphere is specifically a temperature of 18 to 22 ° C. and a humidity of 30 to 50% RH. This is especially important when no desiccant is used.

[Use of fibroin nano thin film transfer sheet]
When the fibroin nano thin film transfer sheet is used on the skin, cosmetics such as a moisturizing cream or cosmetic ingredients such as vitamin C can be applied to the skin, and the fibroin nanolayer can be transferred thereon. In this case, the effect that the cosmetic and cosmetic ingredients are retained and is not easily peeled off can be obtained. Further, after transferring the fibroin nano thin film layer to the skin, a cosmetic or a cosmetic ingredient can be applied thereon. In this case, it is possible to make the skin with wrinkles, sagging, spots, bruises, freckles, pores, scars, acne scars, thermal scars, or discoloration due to skin diseases inconspicuous.

  Moreover, the fibroin nano thin film transfer sheet of this 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 cosmetics or cosmetic ingredients are held.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.

[Example 1]
(Preparation of aqueous fibroin solution)
The fibroin aqueous solution was obtained by dissolving 150 g of high-pressure smelted slag (manufactured by Nagasuna Coffee Co., Ltd.) in 1000 mL of 9M lithium bromide aqueous solution and stirring at room temperature (25 ° C.) for 6 hours. Subsequently, after centrifuging (revolution: 12,000 min ⁻¹ , 5 minutes) and removing the precipitate by decantation, a dialysis tube (trade name: Spectra / Por1 Dialysis Membrane, MWCO 6,000-8,000, Injected into Spectrum Laboratories, Inc. and subjected to dialysis for 12 hours against 5 L of ultrapure water collected from ultrapure water production equipment (PRO-0500 and FPC-0500 (model number), manufactured by Organo Corporation). Repeated 5 times to obtain an aqueous fibroin solution.
2 mL of the obtained fibroin aqueous solution was dispensed into a polystyrene container and weighed, and then the non-fluorocarbon refrigerated refrigerator (R-Y370 (model number), manufactured by Hitachi, Ltd.) whose internal temperature was adjusted to about −20 ° C. in advance. ) In the freezer room for 12 hours, and freeze-dried for 7 hours in a freeze dryer (FDU-1200 (model number), manufactured by Tokyo Rika Kikai Co., Ltd.). The obtained dried product was taken out from the freeze dryer and weighed within 30 seconds, and the fibroin concentration (% by mass) in the fibroin aqueous solution was determined from the mass reduction.

(Preparation of fibroin nano thin film layer)
Glycerin and ultrapure water were added to the fibroin aqueous solution whose concentration was measured to prepare a fibroin aqueous solution having a fibroin concentration of 1% by mass and glycerin of 1% by mass. The fibroin aqueous solution was applied onto a polyethylene terephthalate film (manufactured by Toyobo Co., Ltd., trade name: A4100, length 150 mm × width 100 mm × thickness 100 μm) using an applicator. Thereafter, drying was performed at 100 ° C. for 1 hour. As a result of measuring the film thickness of the formed fibroin nano thin film layer by using model number F20 manufactured by Filmetris Co., Ltd., the film thickness of the fibroin nano thin film layer was 100 nm.

  Subsequently, a fibroin nano thin film layer is formed using a 10% by mass aqueous solution in which polyvinyl alcohol 500 (manufactured by Kanto Chemical Co., Ltd., average polymerization degree = 500) is dissolved in ultrapure water so that the film thickness after drying becomes 5 μm. It was applied by a bar coater on top to form a soluble support layer.

Thereafter, as a permeable substrate, a polyethylene terephthalate mesh sheet (PET mesh, manufactured by Daiki Shoji Co., Ltd., trade name: OKILON HYBRID (“OKILON HYBRID” is a registered trademark)), according to the fragile method described in JIS L 1096. Air permeability 3600 cm ³ / cm ² · sec) was laminated on the soluble support layer, and water was evaporated at room temperature (25 ° C.). As a result, a laminate A was obtained in which a fibroin nano thin film layer, a soluble support layer (polyvinyl alcohol), and a permeable substrate (polyethylene terephthalate mesh sheet) were sequentially laminated on a support substrate (polyethylene terephthalate film).

Next, a polyethylene terephthalate mesh sheet (PET mesh, manufactured by Daiki Shoji Co., Ltd., trade name: OKILON-SHA 2516, air permeability 5850 cm ³ / cm ² · sec according to the fragile method described in JISL 1096) was used as the permeable base material. A layered product B was obtained in the same manner as the layered product A, except for changing to.

  The support base material was peeled off from the laminated body A and the laminated body B, the fibroin nano thin film layers of the laminated bodies A and B were bonded together, and immersed in water for 24 hours with the ends fixed. Thereafter, water was evaporated at room temperature (25 ° C.).

  As a result, a fibroin nano thin film transfer sheet was obtained in which a fibroin nano thin film layer and a permeable base material (OKILON-SHA 2516) were sequentially laminated on the permeable base material (OKILON HYBRID). These permeable substrates are both polyethylene terephthalate mesh sheets, and have different adhesion strengths with the fibroin nano thin film layer. Further, the mesh states (openings) are different, and the contact areas with the fibroin nano thin film layer are different from each other.

[Comparative Example 1]
A fibroin nano thin film layer was formed on a supporting substrate (polyethylene terephthalate film) in the same manner as in Example 1 (production of fibroin nano thin film layer). Subsequently, a fibroin nano thin film layer is formed using a 10% by mass aqueous solution in which polyvinyl alcohol 500 (manufactured by Kanto Chemical Co., Ltd., average polymerization degree = 500) is dissolved in ultrapure water so that the film thickness after drying becomes 5 μm. It was applied by a bar coater on top to form a soluble support layer. Thus, a fibroin nano thin film transfer sheet was prepared in which a fibroin nano thin film layer and a soluble support layer (polyvinyl alcohol) were sequentially laminated on a support substrate (polyethylene terephthalate film).

(Evaluation of transferability)
The fibroin nano thin film layer of the fibroin nano thin film transfer sheet of Example and Comparative Example was exposed, and the fibroin nano thin film layer was attached to the skin surface moistened with water and lotion. Thereafter, the permeable substrate was peeled off, and the fibroin nano thin film layer was transferred to the skin.
In Example 1, when exposing the fibroin nano thin film layer of the fibroin nano thin film transfer sheet, the fibroin nano thin film layer did not adhere to the permeable substrate to be peeled off. In addition, by removing the soluble support layer in advance, it is not necessary to remove the final soluble support layer in use, and the fibroin nano thin film layer can be easily attached to the skin surface. The skin was evenly attached to the skin without breakage or dropout.
On the other hand, in Comparative Example 1, when the fibroin nano thin film layer was applied to the skin, it was necessary to remove the soluble support layer, and the fibroin nano thin film layer was dropped, making transfer difficult.

  DESCRIPTION OF SYMBOLS 1 ... Fibroin nano thin film transfer sheet, 2a, 2b ... Permeable base material, 3, 3a, 3b ... Fibroin nano thin film layer, 4 ... Support base material, 5a, 5b ... Dissolvable support layer, 6a ... 1st laminated body , 6b ... second laminate, 7 ... laminate, 8 ... solvent.

Claims (14)

  The first permeable substrate, the fibroin nano thin film layer, and the second permeable substrate are laminated in this order, and the first permeable substrate and the second permeable substrate are: A fibroin nano thin film transfer sheet, which is a substrate capable of permeating or transmitting a solvent.   2. The solvent according to claim 1, wherein the solvent dissolves a soluble support layer that supports the fibroin nano thin film layer on the first permeable substrate or the second permeable substrate. 3. Fibroin nano thin film transfer sheet.   The fibroin nanothin film according to claim 1 or 2, wherein the first permeable substrate and the second permeable substrate have different adhesion strengths with the fibroin nanothin film layer. Transfer sheet.   The adhesion strength between any one of the first permeable base material and the second permeable base material and the fibroin nano thin film layer is the fibroin nano nanometer when the fibroin nano thin film is bonded to an adherend. 4. The fibroin nano thin film transfer sheet according to claim 3, which is weaker than the adhesion strength between the thin film and the adherend.   The said 1st permeable base material and the said 2nd permeable base material are either the sheet | seat which has a mesh sheet, a nonwoven fabric sheet, and a porous structure, The any one of Claims 1-4 characterized by the above-mentioned. The fibroin nano thin film transfer sheet according to Item.   The fibroin nano thin film transfer sheet according to claim 5, wherein each of the first permeable substrate and the second permeable substrate is a mesh sheet.   The contact area with the said fibroin nano thin film layer mutually differs between the said 1st permeable base material and the said 2nd permeable base material, The Claim 1 characterized by the above-mentioned. Fibroin nano thin film transfer sheet.   Either one of the first permeable substrate and the second permeable substrate provided in the fibroin nanothin film transfer sheet according to any one of claims 1 to 7 is peeled from the fibroin nanothin film layer, A fibroin nano thin film transfer sheet, wherein a cover film is laminated on the side of the fibroin nano thin film layer from which the permeable substrate is peeled off.   The fibroin nano thin film transfer sheet according to any one of claims 1 to 8, wherein the thickness of the fibroin nano thin film layer is 1 nm to 500 nm.   The fibroin nano thin film transfer sheet according to claim 1, wherein the fibroin nano thin film layer is for skin application.   The fibroin nano thin film transfer sheet according to any one of claims 1 to 10, wherein the fibroin nano thin film layer is for cosmetic use. A method for producing a fibroin nano thin film transfer sheet in which a first permeable substrate, a fibroin nano thin film layer, and a second permeable substrate are laminated in this order,
A laminate forming step of forming a laminate by laminating a soluble support layer and the fibroin nano thin film layer between the first permeable substrate and the second permeable substrate;
The soluble support layer in the laminate is dissolved and removed by permeating or permeating a solvent that dissolves the soluble support layer in the first permeable substrate and the second permeable substrate. A method for producing a fibroin nano-thin film transfer sheet.   In the laminate forming step, a first laminate in which a first permeable substrate, a first soluble support layer, and a first fibroin nanothin film layer are laminated in this order, and a second permeable property A first laminate of the first fibroin nanothin film layer and the second fibroin nanothin film comprising a base material, a second soluble support layer, and a second laminate formed by laminating a second fibroin nanothin film layer in this order. The method for producing a fibroin nano-thin film transfer sheet according to claim 12, wherein the laminate is formed by bonding so that the layers face each other.   After the dissolution and removal step, one of the first permeable substrate and the second permeable substrate is peeled from the fibroin nano thin film layer, and the permeable substrate of the fibroin nano thin film layer is removed. The method for producing a fibroin nano thin film transfer sheet according to claim 12 or 13, further comprising a cover film laminating step of laminating a cover film on the peeled side.

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