JP6743939B2 - Nano thin film transfer sheet and transfer method - Google Patents

Description

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

2. Description of the Related Art In recent years, attention has been paid to nano thin films for application to organs, skin, etc. in the medical field or cosmetic field. For example, as a wound dressing material, a medical nano-thin film that is applied to the skin surface or the wound surface of an organ has been proposed (see Non-Patent Document 1, for example).

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

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

Fibroin has a long track record of being used as a surgical suture in addition to clothing applications, and is now also used as an additive for foods or cosmetics. It is sufficiently applicable to the field of use of thin films. On the other hand, a fibroin nano-thin film containing fibroin is required to have excellent sticking property to an object to be transferred such as an organ or skin.

The present invention has been made to solve the above problems, and an object of the present invention is to provide a fibroin nano thin film having excellent sticking properties. It is another object of the present invention to provide a nano thin film sheet using the fibroin nano thin film and a transfer method using the nano thin film sheet.

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

The fibroin nano-thin film according to the present invention contains fibroin, and has a contact angle to water of 30° or more, and thus has excellent sticking property to a transfer target such as an organ or skin.

The thickness of the fibroin nano thin film according to the present invention is preferably 1 to 300 nm. The fibroin nano-thin film according to the present invention may be applied to the skin or may be used for makeup.

A nano thin film sheet according to the present invention includes a base material and a fibroin nano thin film according to the present invention, and the fibroin nano thin film is laminated on the base material. The base material may be a mesh sheet, a non-woven sheet or a porous sheet.

The transfer method according to the present invention, the nano thin film sheet according to the present invention is arranged such that the fibroin nano thin film side faces the transfer target, and by pressing the base material side of the nano thin film sheet, the fibroin nano The method may include a step of transferring the thin film to the transfer target. The load for pressing the base material side of the nanothin film sheet is preferably 10 to 1000 g/cm ² .

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

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

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

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

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

The fibroin used in the present embodiment is not limited, and examples thereof include natural silkworms such as domestic silkworms, wild silkworms, and silkworms, and fibroin produced from transgenic silkworms. Fibroin (silk fibroin) can be expected to be stably supplied because the raw material is easily available, and the price is also stable, so that it can be industrially used easily.

The fibroin nanothin film according to the present embodiment can be formed using a fibroin aqueous solution containing fibroin. As a method for obtaining an aqueous solution of fibroin, any known method may be used, for example, a method of dissolving fibroin in a high-concentration aqueous solution of lithium bromide, desalting by dialysis, and concentration by air-drying is convenient. is there. As the solvent of the aqueous 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 thickness of the fibroin nano thin film is not particularly limited, but it is preferably within the following range when dried. The thickness of the fibroin nano-thin film is preferably 1 nm or more, and more preferably 40 nm or more from the viewpoint of further excellent properties such as self-adhesion, water absorption, and flexibility in a dry state. The 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-adhesiveness, water absorption, and flexibility in a dry state. More preferably, The film thickness of the fibroin nano thin film is preferably 1 to 300 nm, more preferably 40 to 300 nm, and more preferably 40 to 300 nm from the viewpoint of further excellent properties such as self-adhesiveness, water absorption, and flexibility in a dry state. ˜250 nm is more preferred, and 40 to 200 nm is particularly preferred.

The fibroin nano-thin 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. The functional substance may be used alone or in combination of two or more. The content of the functional substance in the fibroin nano thin film is, for example, 1 to 100 parts by mass with respect to 100 parts by mass of fibroin.

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

The fibroin nano thin film according to the present embodiment can contain a cosmetic such as a moisturizing cream. As a result, the cosmetic can be retained on the fibroin nano thin film, and when applied to the skin or the like (when in use), the cosmetic is gradually eluted from the fibroin nano thin film and gradually absorbed by the skin or the like. You can

As the cosmetics, it is possible to use general cosmetics used for skin care such as moisturizing creams, skin creams, whitening creams, emulsions, lotions, beauty essences and beauty gels. The cosmetic contains a cosmetic ingredient. The cosmetic ingredient is not particularly limited as long as it is a cosmetically acceptable ingredient effective for the skin and the like. As the cosmetic ingredient, for example, a moisturizing agent, a whitening ingredient, a stain removing ingredient, a wrinkle-preventing ingredient, vitamins, an anti-inflammatory ingredient, a blood flow promoting ingredient, a moistening ingredient, an oil component, a metal fine particle, etc. Can be used. The cosmetics and cosmetic ingredients can be used alone or in combination of two or more.

Examples of cosmetic ingredients include almond oil, alkyl acrylate copolymer, hemp cellulose, acitaba extract, ascorbic acid, sodium ascorbate, xanthine, astaxanthin, asparagus extract, aspartic acid, azulene, acerola extract, adenosine triphosphate 2Na. , Avocado oil, armature extract, aminobutyric acid, alanine, allantoin, arginine, sodium alginate, aldirrin, altea extract, arnica extract, albumin, aloe vera extract-2-kidachi aloe extract, benzoate Na, ginkgo biloba extract, inositol, turmeric extract, Steller's sea urchin extract, ages extract, sodium chloride, oyster extract, sardine extract, oyster extract, ginseng extract, sardine extract, Dutch mustard extract, olive oil, oryzanol, sea salt, hydrolyzed keratin, collagen, hydrolyzed collagen, hydrolyzed conkylion, hydrous Decomposed silk, Hydrolyzed egg shell membrane, Hydrolyzed egg white, Brown algae extract, Caffeine, Chamomile extract, Calamine, Karin extract, Carotene, Carrot extract, Kawamura mugwort 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, Gentiana Extract, tea extract, 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, dio extract, diglycerin, shikon extract, perilla extract, dihydrocholesterol, diphenyldimethylmecon, sycamore extract, tartaric acid , Ginger extract, ginger root extract, silk, silk extract, hydrogenated lecithin, squalane, stearyl alcohol, glyceryl stearate, stearin Acid sucrose, horseradish extract, horseradish extract, sage extract, cetanol, ceramide 3, serine, cellulose gum, sawakuhi extract, sorbitol, soybean extract, soybean fermented extract, evening primrose oil, dokudami extract, tocopherol, trehalose, niacinamide, nicotinic acid Tocopherol, Lactic acid, Na lactate, Urea, Bacuga extract, Honey, Papain, Hamamelis extract, Retinol palmitate, Panthenol, Na hyaluronate, Biotin, Hikiokoshi extract, Castor oil, Sunflower oil, Pyridoxine HCl, Loquat leaf extract, Bukuryo extract, Butcher Bloom Extract, Grape Extract, Grape Seed Oil, Placenta Extract, Pullulan, Betaine, Loofah Extract, Button Extract, Hop Extract, Jojoba Oil, Meadow Foam Oil, Methoxycaysan Octyl, Melissa Extract, Meliloth Extract, Menthol, Peach Leaf Extract. , Cornflower extract, coconut oil, eucalyptus extract, eucalyptus oil, yukinoshita extract, yuzu extract, lily extract, garlic iodide extract, folic acid, yokuinin extract, mugwort extract, raspberry ketone, lactoferrin, lanolin, lavender extract, ricin HCl, linoleic acid, Na sulphate, apple extract, litchi extract, lecithin, resorcin, lettuce extract, lemon extract, lemon oil, leucine, rose water, rosehip oil, rosemary extract, Roman chamomile extract, royal jelly, oleander extract, AHA (α-hydroxy acid ), BG (butylene glycol), DNA (deoxyribonucleic acid), PCA (pyrrolidone carboxylic 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, diacetylboldine, vitamin A and its derivatives, vitamin C and its derivatives, riboflavin phosphate. Examples thereof include sodium, hydroquinone, liponucleic acid and salts thereof, amino acids and derivatives thereof, various plant extracts, various animal-derived extracts and the like.

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 onto it. In this case, it is possible to obtain the effect that the cosmetic material is held and is hardly peeled off. In addition, after transferring the fibroin nano thin film to the skin or the like, a cosmetic can be applied on the thin film. In these cases, wrinkles, sagging, spots, bruise, freckles, pores, scars, acne scars, burn scars, or skin with discoloration due to skin disease can be made inconspicuous.

The fibroin nano-thin film according to the present embodiment can also be suitably used as a makeup sheet, a moisturizing sheet, a makeup-assisting patch sheet, and a makeup-protecting sheet that holds a cosmetic material.

The fibroin nano thin film according to the present embodiment may contain a dye. As a result, the dye can be retained on the fibroin nano-thin film, and the application position when applied to the skin or the like (when in use) can be easily confirmed visually.

Examples of dyes include azo dyes (naphthol dyes, etc.), mauve, para red, fluorescein, fuchsin, phenolphthalein, neutral red, phenazine derivative dyes, methylene blue, dihydrointol, congo red, eosin, indanthrene, aniline black, acridine, Azoic dye, neocyanine, cryptocyanine, indocyanine green, hemoglobin, hemeerythrin, pheoporphyrin, pheophorbide, cytochrome, bacteriochlorophyll, chlorophyllide, chlorophyll, melanin, catechin, anthocyan, antochlor, flavanone, flavones, flavonoid, lutein, lycopene , Fucoxanthin, zeaxanthin, cryptoxanthin, xanthophyll, carotene, carotenoid, genistein, chlorocurorin, chlorin, crocetin, curcumin, xanthonematin, cartamine, erythrocurorin, urobilin, indigo, anthraquinone, anthocyan, alizarin, bilirubin, biliverdin , Phytochrome, phycoerythrin, phycobilin, phycocyanin, myoglobin, porphine, porphyrin, hemocyanin, hemovanazine, rhodomatine, rhodoxanthin, rhodopsin, litmus, leghemoglobin, laminaran, purinjina, purinjapina, navelin, berberine, betaline, berberine, bettaline, bettalin , Hypericin, bixin, thuracin, tannin, stercopilin, shikonin, commelinin, gossypol, cochineal and the like. Among the dyes, an ionic dye is preferable from the viewpoint of excellent solubility in water and alcohol. The dyes may be used alone or in combination of two or more.

The fibroin nanothin film according to the present embodiment may contain metal ions. This allows metal ions to be retained on the fibroin nano thin film, and when applied to the skin (when in use), the metal ions are gradually eluted from the fibroin nano thin film and gradually absorbed into the skin, etc. You can Further, by using metal ions, a fibroin nano thin film having effects such as antibacterial, sterilization, deodorization and antiperspirant can be obtained.

Examples of the metal ions include alcal 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 the metal ions, silver ions are preferable from the viewpoint of having an antibacterial effect and a deodorizing effect. The metal ions can be used alone or in combination of two or more.

The fibroin nano thin film according to the present embodiment may contain a drug. As a result, the drug can be retained on the fibroin nano thin film, and when applied to the skin or the like (when in use), the drug can be gradually eluted from the fibroin nano thin film and gradually absorbed by the skin or the like. .. In addition, a fibroin nano thin film having an effect such as wound healing can be obtained.

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

When the cosmetic or drug is hydrophobic, a method may be used in which the cosmetic or drug is bound to the hydrophobic region of the fibroin nanofilm by hydrophobic interaction. When the cosmetic or drug is hydrogen-bonding, a method of bonding the cosmetic or drug to the hydrogen-bonding region of the fibroin nanothin film by hydrogen bond may be used. When the cosmetic or drug has an electric charge, a method of binding the cosmetic or drug to the oppositely charged region of the fibroin nanofilm by electrostatic interaction may be used.

As the cross-linking agent, using alkyldiimidates, acyldiazides, diisocyanates, bismaleimides, triazinyl compounds, diazo compounds, glutaraldehyde, N-succinimidyl-3-(2-pyridyldithio)alkionate, bromocyanide, etc., You may bridge|crosslink the said component and the predetermined functional group in a fibroin nano thin film. The crosslinking agent may be used alone or in combination of two or more.

FIG. 1 is a schematic cross-sectional view showing an embodiment of a nano thin film sheet. As shown in FIG. 1, the nano thin film sheet 1 according to the present embodiment includes a support base 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 supporting 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 supporting base material 2, a supporting base material having a smaller adhesive force to the fibroin nanothin film 3 than the transfer target is used.

The supporting substrate is not particularly limited as long as it has a smooth surface, and may be in the form of a film (sheet) or roll. The supporting substrate may be a permeable substrate capable of penetrating or permeating a solvent. The permeable substrate has, for example, pores that allow the solvent to permeate or permeate. The permeable substrate is a mesh sheet, a non-woven fabric sheet, or a porous structure having a porous structure from the viewpoint that the fibroin nanothin film can be easily suppressed from remaining on the substrate side when the substrate is peeled from the nanothin film sheet. It may be a property sheet. The mesh sheet is, for example, a sheet in which a thread-like material having a diameter of 100 μm or less is woven in a lattice shape. When using a permeable substrate, after forming a fibroin nano thin film on the permeable substrate via a soluble support layer that dissolves in a solvent, etc., a soluble support layer is formed by a solvent that penetrates or permeates the permeable substrate. By dissolving, a structure in which the permeable base material 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 the non-woven sheet.

A substrate film such as a resin film can also be used as the supporting substrate. 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 type or syndiotactic type), Polybutene, ethylene-prepylene copolymer, ethylene-vinyl acetate copolymer (EVA), polyolefin such as 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, polymethylmethacrylate, polybutyl(meth)acrylate, methyl(meth)acrylate-butyl(meth)acrylate copolymer, Methyl (meth)acrylate-styrene copolymer, acrylic-styrene copolymer (AS resin), butadiene-styrene copolymer, polio copolymer (EVOH), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), Polyethylene such as ethylene-terephthalate-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 fluorine-based resin, styrene-based, polyolefin-based, polyvinyl chloride-based, polyurethane-based, fluororubber-based , Various thermoplastic elastomers such as chlorinated polyethylene, epoxy resin, phenol resin, urea resin, melamine resin, unsaturated polyester, silicone resin, polyurethane, nylon, nitrocellulose, cellulose acetate, cellulose acetate propionate, etc. Examples thereof include resins, copolymers, blends, and polymer alloys containing them as a main component. One or a combination of two or more of these may be used (for example, as a laminate having two or more layers).

Among these resin films, plastic films such as polyethylene terephthalate, polyethylene, polypropylene and polyvinyl chloride are preferable, and polyethylene terephthalate film is more preferable from the viewpoint of further excellent adhesiveness in a laminated film containing 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 composed of these resin film, inorganic film, or organic-inorganic film may cover a part of the surface of the base material. Further, in the laminated structure, the film not located at the outermost surface layer does not need to have a polar group.

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

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

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

The method for producing a nanothin film sheet (for example, a nanothin film transfer sheet) according to the present embodiment includes, for example, a step of forming a fibroin nanothin film on a supporting base material (base material) using a fibroin aqueous solution. The nanothin film sheet according to the present embodiment may be obtained, for example, by forming a fibroin nanothin film by applying a fibroin aqueous solution onto a supporting substrate, and supporting the fibroin nanothin film formed using the fibroin aqueous solution. It may be obtained by pasting on a substrate.

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

In the transfer method according to the present embodiment, the nano thin film sheet is arranged so that the fibroin nano thin film side faces the transfer target, and the fibroin nano thin film is transferred to the transfer target by pressing the base side of the nano thin film sheet. The process may be provided. In such a transfer method, since the fibroin nano thin film is transferred to the transfer target by pressing the base side of the nano thin film sheet with the base covering the fibroin nano thin film, the transfer target and the nano thin film layer are transferred. The followability with and the adhesiveness are improved. Therefore, in such a transfer method, for example, as compared with a method of transferring the fibroin nano thin film to the transferred object after peeling the substrate in advance, or a method of transferring the fibroin nano thin film to the transferred object without pressing. Thus, the fibroin nano thin film can be appropriately transferred to the transfer target.

When the base material side of the nanothin film sheet is pressed, 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 base material side of the nano thin film sheet is 10 g/cm ² or more from the viewpoint that the fibroin nano thin film can be easily suppressed from remaining on the base material side when peeling the base material from the nano thin film sheet. Is preferable, 30 g/cm ² or more is more preferable, and 50 g/cm ² or more is further preferable. 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 material such as skin. Is more preferable. From these viewpoints, the load is preferably 10 to 1000 g / cm ^2, more preferably 30~900g / cm ^2, further preferably 50 to 800 g / cm ^2.

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

<Preparation of nano thin film>
(Example 1)
First, 150 g of high-pressure-refined cocoon (silk fibroin, manufactured by Nagasuna Cocoon Co., Ltd.) was added to 1000 mL of 9M lithium bromide aqueous solution, and stirred at room temperature (25° C.) for 6 hours to dissolve. Then, after performing centrifugation (rotation speed: 12000 rpm, 5 minutes) to remove the precipitate by decantation, a dialysis tube (Spectra/Por (registered trademark) 1 Dialysis Membrane, MWCO 6000-8000, manufactured by Spectrum Laboratories, Inc.) was used. ), and dialysis for 12 hours was repeated 5 times for 5 L of ultrapure water taken from the ultrapure water production device (PRO-0500 and FPC-0500 (model number), manufactured by Organo Co., Ltd.) to obtain a solution. It was

2 mL of the obtained solution was dispensed into an aluminum container and weighed. Then, the dried product obtained by drying at 100° C. for 2 hours with a dryer was air-cooled and weighed. The silk fibroin concentration in the solution (unit: g/L) was quantified from the mass reduction.

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

On a polyethylene terephthalate film (PET film, manufactured by Toyobo Co., Ltd., trade name “A4100”, 150 mm×100 mm×100 μm thick) which is a supporting substrate, an aqueous silk fibroin solution was applied using an applicator. Then, it dried at 100 degreeC for 1 hour, and formed the silk fibroin nano thin film. As a result of measuring the film thickness of the silk fibroin nano thin film with a model number: F20 manufactured by Filmet Risk Co., Ltd., the film thickness of the silk fibroin nano thin film was 100 nm.

Then, a polyvinyl alcohol 500 (manufactured by Kanto Chemical Co., Inc., average degree of polymerization: 500) dissolved in ultrapure water was used to prepare a 10 mass% aqueous solution, and a bar coater was applied on the nanothin film so that the film thickness after drying was 5 μm. Coated to form a soluble support layer.

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

The permeable base material is a polyethylene terephthalate mesh sheet (PET mesh, manufactured by Taiki Shoji Co., Ltd., trade name “OKILON-SHA 2516”, air permeability 5850 cc/cm ² ·sec according to the Frazier method described in JIS L1096, thickness: A layered product A2 was obtained in the same manner as the layered product A1 except that the thickness was changed to 80 μm.

The supporting base material was peeled off from each of the laminate A1 and the laminate A2, the nanothin films of the laminates A1 and A2 were attached to each other, and the soluble support layer was formed by immersing in water for 24 hours with the ends fixed. Dissolved. Then, the water was evaporated at room temperature (25°C).

As a result, a nano thin film transfer sheet was obtained in which a silk fibroin nano thin film and a permeable substrate (“OKILON-SHA 2516”) were laminated in this order on a permeable substrate (“OKILON HYBRID”). Both of these permeable substrates are polyethylene terephthalate mesh sheets, but they have different adhesion strength with the nano thin film. Further, since the mesh state (opening) is different, the contact areas with the nano thin film are different from each other.

<Example 2>
In the same manner as in Example 1, glycerin and ultrapure water were added to the solution whose concentration was measured to prepare an aqueous silk fibroin solution having a silk fibroin concentration of 1% by mass and a glycerin concentration of 1% by mass. Further, a nano thin film transfer sheet was obtained in the same manner as in Example 1 except that 0.1% by mass of Silface SAG503A was added as a surface conditioner to the silk fibroin aqueous solution.

<Comparative Examples 1 and 2>
As a solution A containing a polycation, an aqueous solution containing 0.3% by mass of chitosan (manufactured by Kimika Co., Ltd., viscosity average molecular weight: 90,000) was prepared. As the solution B containing a polyanion, 100 parts by mass of an aqueous solution of sodium alginate (manufactured by Kimika Co., viscosity average molecular weight: 100000, viscosity: 6.7 mPa·s, concentration: 0.1% by mass) and malic acid (Wako Pure Chemical Industries, Ltd. (Manufactured by Co., Ltd.) to prepare a solution obtained by mixing with 1 part by mass.

A polyethylene terephthalate film (PET film, manufactured by Toyobo Co., Ltd., trade name “A4100”, 150 mm×100 mm×100 μm thick) was prepared as a supporting substrate. (A) a step of immersing the supporting substrate in the solution A containing a polycation for 1 minute and then immersing it in ultrapure water for rinsing (specific resistance: 18 MΩ·cm) for 1 minute; and (b) a solution B containing a polyanion. The step of alternately immersing the support substrate in 1 minute for 1 minute and then immersing it in ultra-pure water for rinsing (specific resistance: 18 MΩ·cm) for 1 minute was set as one cycle, and this cycle was repeated 18 times. As a result, a nano thin film composed of a layer derived from chitosan and a layer derived from sodium alginate was formed on the polyethylene terephthalate film (supporting substrate). As a result of measuring the film thickness of the formed nano thin film by the model number: F20 manufactured by Filmet Risk Co., Ltd., the film thickness of the nano thin film was 100 nm.

Then, a polyvinyl alcohol 500 (manufactured by Kanto Chemical Co., Inc., average degree of polymerization: 500) dissolved in ultrapure water was used to prepare a 10 mass% aqueous solution, and a bar coater was applied on the nanothin film so that the film thickness after drying was 5 μm. Coated to form a soluble support layer.

Then, as a permeable base material, a polyethylene terephthalate mesh sheet (PET mesh, manufactured by Taiki Shoji Co., Ltd., trade name “OKILON HYBRID”, breathability 3600 cc/cm ² ·sec by the Frazier type method described in JIS L1096, thickness : 90 μm) was laminated on the soluble support layer, and water was evaporated at room temperature (25° C.). As a result, on the supporting base material (polyethylene terephthalate film), a nano thin film (alternating laminated film of layers derived from chitosan and sodium alginate), a soluble supporting layer (polyvinyl alcohol), and a permeable base material (polyethylene terephthalate). A laminate B1 in which the mesh sheets) were laminated in this order was obtained.

The permeable base material is polyethylene terephthalate mesh sheet (PET mesh, manufactured by Taiki Shoji Co., Ltd., trade name “OKILON-SHA 2516”, breathability 5850 cc/cm ² ·sec by Frazier type method described in JISL 1096, thickness: A laminated body B2 was obtained in the same manner as the laminated body B1 except that the thickness was changed to 80 μm).

The supporting base material was peeled off from each of the laminate B1 and the laminate B2, the nanothin films of the laminates B1 and B2 were attached to each other, and the soluble support layer was formed by immersing in water for 24 hours with the ends fixed. Dissolved. Then, the water was evaporated at room temperature (25°C).

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

In performing the steps (a) and (b), in Comparative Example 1, the surface of the laminate formed on the polyethylene terephthalate film (exposed when the permeable base material of the nanothin film transfer sheet is peeled off). The surface was adjusted so that the layer derived from chitosan was exposed. Further, in Comparative Example 2, adjustment was made so that the layer derived from sodium alginate was exposed on the surface of the laminate formed on the polyethylene terephthalate film (the surface exposed when the permeable substrate of the nanothin film transfer sheet was peeled off). did.

<Measurement of contact angle>
When measuring the contact angle with respect to water, ultrapure water (electrical resistivity: 18 MΩ·cm or more) sampled from an ultrapure water producing device (PRO-0500 (model number), manufactured by Organo Co., Ltd.) was used as water.

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

<Evaluation of stickability>
On the skin surface moistened with water and lotion, the permeable base material (“OKILON-SHA 2516”) of the nano thin film transfer sheet was peeled off and the exposed nano thin film was attached. After that, the permeable substrate (“OKILON HYBRID”) was peeled off and the nano thin film was transferred to the skin. In Examples 1 and 2, it was possible to apply without pressing at the time of applying. On the other hand, in Comparative Examples 1 and 2, attachment was difficult without pressing.

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

Claims (6)

A substrate and a fibroin nano thin film laminated on the substrate,
The fibroin nano thin film contains fibroin,
A nano thin film transfer sheet, wherein the contact angle of the fibroin nano thin film with water is 30° or more. The nano thin film transfer sheet according to claim 1, wherein the fibroin nano thin film has a thickness of 1 to 300 nm. The nanothin film transfer sheet according to claim 1 or 2, which is for sticking on the skin. The base mesh sheet, a nonwoven sheet or porous sheet, nano thin film transfer sheet according to any one of claims 1-3. By arranging the nano thin film transfer sheet according to any one of claims 1 to 4 such that the fibroin nano thin film side faces a transfer target, and pressing the base side of the nano thin film transfer sheet, A transfer method comprising a step of transferring the fibroin nano thin film to the transfer target. The transfer method according to claim 5 , wherein the load when pressing the base material side of the nanothin film transfer sheet is 10 to 1000 g/cm ² .

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