WO2017188214A1 - Film fin autoportant non soluble dans l'eau présentant une forte adhésivité - Google Patents

Film fin autoportant non soluble dans l'eau présentant une forte adhésivité Download PDF

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WO2017188214A1
WO2017188214A1 PCT/JP2017/016283 JP2017016283W WO2017188214A1 WO 2017188214 A1 WO2017188214 A1 WO 2017188214A1 JP 2017016283 W JP2017016283 W JP 2017016283W WO 2017188214 A1 WO2017188214 A1 WO 2017188214A1
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thin film
self
film
water
polyphenol
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PCT/JP2017/016283
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English (en)
Japanese (ja)
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俊宣 藤枝
健人 山岸
信孝 佐藤
高橋　功
武岡　真司
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学校法人早稲田大学
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Priority to JP2018514604A priority Critical patent/JP6908935B2/ja
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/056—Forming hydrophilic coatings

Definitions

  • the present invention relates to a self-supporting thin film made of a water-insoluble polymer, surface-modified, and having high adhesion to objects including organs and skin, and a method for producing the same.
  • a biocompatible thin film As a biocompatible thin film, a thin film having high adhesiveness to living skin and organs is required, and development of a polylactic acid thin film that is easy to thin and biodegradable as a biocompatible thin film is attempted.
  • Patent Document 1 a polylactic acid thin film that is easy to thin and biodegradable as a biocompatible thin film is attempted.
  • the polylactic acid thin film does not necessarily have sufficient stretchability, the polylactic acid thin film shows high utility for a part or organ that does not involve movement, but its application to a part or organ that involves movement is limited. Therefore, a biocompatible thin film having high binding properties to skin and organs and higher stretchability is required.
  • plastic films polyethylene terephthalate, polyethylene naphthalate, polyimide
  • a film thickness of several to several tens of ⁇ m have been developed and used.
  • PDMS polydimethylsiloxane
  • Patent Documents 2 to 4 since it has a track record as a water-insoluble polymer thin film for medical use, its application is expected.
  • Patent Document 4 Non-Patent Document 1
  • Non-patent Document 4 Use of n-alkanes such as n-hexane or n-heptane is recommended as a solvent for forming the PDMS self-supporting thin film.
  • Kang et al. Spin-coated PDMS diluted with n-hexane on a water-insoluble polymer layer made of photoresist, and collected a self-supporting PDMS sheet (film thickness 77-2000 nm) on a jig.
  • the aspect ratio can only be achieved up to 10 5 due to the vulnerability of the PDMS sheet (Non-patent Document 1).
  • a thin film made of a self-supporting water-insoluble polymer thin film manufactured by an area and process that can handle an industrial scale with an aspect ratio exceeding 10 6 has not yet been reported.
  • Patent Documents 1 and 5 improvement in adhesion by thinning a biocompatible film
  • Non-Patent Document 2 surface modification by a polymer compound having high adhesion such as a polyphenol compound
  • the present invention provides a self-supporting thin film made of a water-insoluble polymer thin film, surface-modified, and having high adhesion to an object including an organ or skin in a living body, and a method for producing the same. Let it be an issue.
  • the inventors of the present invention have made diligent efforts to use a solvent having a specific polarity for the solvent that dissolves the silicone thin film raw material composition (main agent) and the curing agent during the crosslinking and / or polymerization reaction in the production process of the silicone thin film.
  • a manufacturing method of a self-supporting thin film having high strength and high adhesion to an object was established.
  • a method for producing a surface-modified self-supporting thin film coated with polyphenol by coating a polyphenol compound on a water-insoluble self-supporting thin film such as a self-supporting thin film made of silicone and a polylactic acid self-supporting thin film was established. .
  • the present invention provides a polyphenol-coated self-supporting thin film in which at least one film surface of a water-insoluble polymer thin film having adhesion by thinning is coated with polyphenol.
  • the film thickness of the water-insoluble polymer self-supporting thin film is in the range of 30 to 800 ⁇ m, preferably in the range of 100 to 500 ⁇ m, more preferably in the range of 200 to 100 ⁇ m, and most preferably in the range of 300 to 30 ⁇ m. It may be a polyphenol-coated self-supporting thin film in the range of
  • the polyphenol-coated self-supporting thin film of the present invention may be made of silicone and have an aspect ratio of 10 6 or more or an area of 10 cm 2 or more.
  • the self-supporting thin film of the present invention may be a self-supporting thin film having a thickness of 1 ⁇ m or less and a maximum length on the thin film surface of 1 ⁇ m or more.
  • the self-supporting thin film of the present invention may be a self-supporting thin film that does not include pinholes.
  • the water-insoluble polymer film comprises silicone, polylactic acid (PLA), polyglycolic acid (PGA), glycolic acid / L-lactic acid copolymer, and glycolic acid / DL- Lactic acid copolymer selected from lactic acid copolymer, polylactone or lactone copolymer, poly (lactide-co-glycolide) copolymer (PLGA), PLGA converted into polyethylene glycol (PEG), PLGA-PLA-PEG It may be selected from alternating layers of copolymer or electrolyte polymer.
  • the silicone may be polydimethylsiloxane (PDMS).
  • the self-supporting thin film of the present invention may be a self-supporting thin film having high adhesion, high adhesion, high adhesion, high maximum tensile strength, low Young's modulus, and / or high permeability.
  • the adhesion when the self-supporting thin film has a thickness of 588 mm, the adhesion is 20 times higher than that of a PDMS thin film having a thickness of 1 mm, a maximum tensile strength of 0.5 mm or more, 158
  • the film is a self-supporting thin film having a stretchability of% or more, a Young's modulus of 0.76 MPa or less, and / or a transparency of 96% or more in the visible light region (wavelength: 360 to 830 nm).
  • the polyphenol compound is a flavonoid compound such as polydopamine, tannic acid, catechin, rutin, anthocyanin, isoflavone, quercetin, hesperidin, chlorogenic acid, ellagic acid, lignan, curculin, coumarin. Or at least one selected from the group consisting of epicatechin gallate, epigallocatechin, epigallocatechin gallate and gallocatechin gallate.
  • the polyphenol compound may be polydopamine.
  • the present invention also relates to a method for producing a self-supporting thin film comprising a water-insoluble polymer, wherein the water-insoluble polymer is used in an organic solvent having a solubility parameter (Hildebrand parameter) SP value in the range of 7.3 to 11.3.
  • a production method including a step of curing a thin film raw material composition (main agent) to form a film.
  • the water-insoluble polymer thin film may be selected from silicone or polylactic acid.
  • the main component of the water-insoluble polymer thin film raw material composition is selected from octamethylcyclotetrasiloxane, D-lactic acid and / or L-lactic acid. There may be at least one.
  • the step of curing the water-insoluble polymer thin film raw material composition (main agent) to form a film comprises curing the water-insoluble polymer thin film raw material composition (main agent).
  • the percentage by weight of the agent may be about 5% (20: 1) or more.
  • the present invention provides a method for producing a polyphenol-coated self-supporting thin film, the method comprising the step of coating the self-supporting thin film, further comprising a step of coating at least one film surface with polyphenol.
  • the method for producing a self-supporting thin film in which at least one film surface is coated with polyphenol includes laminating the self-supporting thin film on a support made of a water-soluble polymer film.
  • the step may include a step of immersing the laminated film in a solution containing polyphenol to coat the laminated film with polyphenol, and a step of peeling the self-supporting thin film coated with polyphenol from the laminated film coated with polyphenol.
  • the method for producing a self-supporting thin film having both surfaces coated with polyphenol includes laminating the self-supporting thin film on a support made of a water-soluble polymer film.
  • the step may include a step of peeling the self-supporting thin film of the laminated film and the support, a step of immersing the self-supporting thin film peeled from the support in a solution containing polyphenol, and coating the polyphenol on both sides of the self-supporting thin film.
  • the water-insoluble polymer is silicone, polylactic acid (PLA), polyglycolic acid (PGA), glycolic acid / L-lactic acid copolymer, or glycolic acid / DL-lactic acid.
  • the silicone may be polydimethylsiloxane (PDMS).
  • the polyphenol is a flavonoid compound such as polydopamine, tannic acid, catechin, rutin, anthocyanin, isoflavone, quercetin, hesperidin, chlorogenic acid, ellagic acid, lignan, curculin, coumarin, It may be at least one selected from the group consisting of epicatechin gallate, epigallocatechin, epigallocatechin gallate and gallocatechin gallate.
  • the polyphenol may be polydopamine.
  • the present invention also includes a step of forming a film by curing the water-insoluble polymer thin film raw material composition (main agent) in an organic solvent having a solubility parameter (Hildebrand parameter) SP value in the range of 7.3 to 11.3.
  • a self-supporting thin film manufactured by the method of manufacturing a self-supporting thin film is provided.
  • the present invention provides a polyphenol-coated self-supporting thin film produced by a production method including a step of coating at least one of the membrane surfaces with polyphenol in the film-forming step.
  • the polyphenol-coated self-supporting thin film of the present invention may be a biocompatible thin film.
  • the self-supporting thin film of the present invention may be a self-supporting thin film in which at least one surface of the self-supporting thin film is surface-modified.
  • the present invention may be a self-supporting thin film in which only one surface of the self-supporting thin film or both surfaces are modified.
  • the film forming method of the laminated film may be a manufacturing method that further includes a process of forming a laminated film including a water-soluble polymer layer as an intermediate layer in the manufacturing process of the self-supporting thin film.
  • the step of forming the laminated film may be a manufacturing method by a roll-to-roll method.
  • the method of forming the laminated film is as follows: A step of laminating a water-soluble polymer layer on a substrate in a roll-to-roll method, Furthermore, in the roll-to-roll method, an organic solvent solution of the water-insoluble polymer thin film and a curing agent is further coated on the water-soluble polymer layer laminated on the substrate, and the coating is applied to the coating.
  • the manufacturing method may include
  • the substrate is polyethylene terephthalate (PET);
  • the water-soluble polymer layer is polyvinyl alcohol (PVA)
  • the main component of the water-insoluble polymer thin film raw material composition (main agent) of the water-insoluble polymer thin film is octamethylcyclotetrasiloxane
  • the solvent that dissolves the water-insoluble polymer thin film raw material composition (main agent) and the curing agent is a mixed solvent of hexane and a polar organic solvent having a hexane content of 80% or less
  • the rotation speed of the roller is 0.2 to 1.0 m / min, and the water-insoluble polymer thin film is cured at 80 ° C. for 3 hours or more.
  • the present invention is a method for producing a self-supporting thin film comprising a water-insoluble polymer thin film, the surface of which is at least one surface modified, and further comprising the surface modification during or after the production method.
  • the manufacturing method including the process of processing with an agent is provided.
  • a step of irradiating the self-supporting thin film or laminated film with plasma may be included before the step of treating with the surface modifier.
  • the method for producing a self-supporting thin film in which at least one surface of the present invention is surface-modified is as follows: A method for producing a self-supporting thin film comprising a water-insoluble polymer thin film, the surface of which is modified on both sides, and the surface modifier is immersed in a solution containing the surface modifier. It may be a manufacturing method including the process to process. Moreover, in this manufacturing method, the process of irradiating a plasma to the self-supporting thin film manufactured by the said manufacturing method may be included before the process of processing with a surface modifier.
  • the present invention is a method for producing a self-supporting thin film comprising a water-insoluble polymer thin film, wherein only one of the front and back surfaces is surface-modified, wherein the laminated film is contained in a solution containing a surface modifier.
  • the manufacturing method including the process of processing with a surface modifier by immersing in is provided.
  • the process of irradiating a plasma to the self-supporting thin film manufactured by the said manufacturing method may be included before the process of processing with a surface modifier.
  • the surface-modified self-supporting thin film manufacturing method of the present invention may be a manufacturing method in which the surface modifier is a silane coupling agent.
  • the silane coupling agent is vinylvinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3 -Glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacrylic Roxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, amino N-2- (amino Ethyl)
  • the manufacturing method of the self-supporting thin film of the present invention may be a manufacturing method in which the silane coupling agent is 3-aminopropyltriethoxysilane.
  • the self-supporting thin film of the present invention may be a self-supporting thin film including a step of forming a laminated film including a water-soluble polymer layer as an intermediate layer in the manufacturing process.
  • the step of forming the laminated film of the manufacturing method may be a self-supporting thin film by a roll-to-roll method.
  • the self-supporting thin film of the present invention in the manufacturing method, A step of laminating a water-soluble polymer layer on a substrate in a roll-to-roll method, Furthermore, in the roll-to-roll method, an organic solvent solution of the water-insoluble polymer thin film raw material composition (main agent) and a curing agent was coated on the water-soluble polymer layer laminated on the substrate.
  • the substrate is polyethylene terephthalate (PET);
  • the water-soluble polymer layer is polyvinyl alcohol (PVA),
  • the main component of the water-insoluble polymer thin film raw material composition (main agent) of the water-insoluble polymer thin film is octamethylcyclotetrasiloxane,
  • the solvent that dissolves the water-insoluble polymer thin film raw material composition (main agent) and the curing agent is a mixed solvent of hexane and a polar organic solvent having a hexane content of 80% or less
  • the rotation speed of the roller is 0.2 to 1.0 m / min, and the water-insoluble polymer thin film is cured at 80 ° C. for 3 hours or more.
  • the water-soluble polymer layer may be
  • the present invention is a self-supporting thin film having a high aspect ratio, comprising a water-insoluble polymer thin film with at least one surface modified.
  • a self-supporting thin film manufactured by a manufacturing method including a step of treating with a surface modifier during or after the process of manufacturing the self-supporting thin film.
  • the process of irradiating a plasma to the self-supporting thin film manufactured by the said manufacturing method may be included before the process of processing with a surface modifier.
  • the present invention is a self-surface modified standing thin film having a high aspect ratio, comprising a water-insoluble polymer thin film and having both surface modified on both sides.
  • a self-supporting thin film manufactured by a manufacturing method including a step of treating the self-supporting thin film with a surface modifier by immersing the film in a solution containing a surface modifier.
  • the process of irradiating a plasma to the self-supporting thin film manufactured by the said manufacturing method may be included before the process of processing with a surface modifier.
  • the present invention is a self-supporting thin film having a high aspect ratio, which is made of a water-insoluble polymer thin film and is surface-modified on only one of the front and back surfaces
  • a self-supporting thin film manufactured by a manufacturing method including a step of treating a laminated film with a surface modifier by immersing the laminated film in a solution containing the surface modifier is provided.
  • the process of irradiating a plasma to the self-supporting thin film manufactured by the said manufacturing method may be included before the process of processing with a surface modifier.
  • the self-supporting thin film manufactured by the manufacturing method including the step of treating with the surface modifier may be a self-supporting thin film in which the surface modifier is a silane coupling agent.
  • the silane coupling agent is vinylvinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl).
  • the self-supporting thin film manufactured by the manufacturing method including the step of treating with the surface modifier may be a self-supporting thin film in which the silane coupling agent is 3-aminopropyltriethoxysilane.
  • the self-supporting thin film whose surface is modified by at least one surface manufactured by the manufacturing method including the step of treating with the surface modifier may be a single layer film or a laminated film.
  • a polyphenol-coated self-supporting thin film comprising a water-insoluble polymer thin film having adhesiveness, surface-modified, having high strength and adhesion to an object, and a method for producing them.
  • FIG. 3A A photograph of a self-supporting thin film supported by a tape frame (FIG. 3A) and a self-supporting thin film supported by a wire loop (FIG. 3B).
  • FIG. 3B A photograph of a self-supporting thin film supported by a tape frame (FIG. 3A) and a self-supporting thin film supported by a wire loop (FIG. 3B).
  • FIG. 3A A photograph of a self-supporting thin film supported by a tape frame
  • FIG. 3B A photograph of a self-supporting thin film supported by a wire loop (FIG. 3B).
  • the film thickness was measured with an atomic force microscope (AFM).
  • FIG. 5A A graph showing the results of measuring light transmittance in a visible light region (360-830 nm) in PDMS thin films having various film thicknesses (film thicknesses: 588 nm, 910 nm, and 1595 nm).
  • FIG. 5B is a diagram showing the average value of the results of measuring the light transmittance in the visible light region at various film thicknesses of the self-supporting thin film.
  • curing agent 10: 1) of various film thicknesses in the range of 275 to 1612 nm.
  • FIG. 8A is a diagram showing photographs of films before and after a peel test for each film thickness of a PDMS thin film.
  • FIG. 8B A diagram showing an average value ⁇ standard deviation of peeling rates at various film thicknesses.
  • FIG. 9A Polylactic acid (PDLLA) thin film (film thickness: 120 nm).
  • FIG. 9B PDMS thin film (film thickness: 588 nm).
  • FIG. 10A is a photomicrograph of a self-supporting thin film produced by dissolving PDMS and a curing agent in 100% n-hexane by a roll-to-roll method. Many pinholes were observed.
  • FIG. 10A is a photomicrograph of a self-supporting thin film produced by dissolving PDMS and a curing agent in 100% n-hexane by a roll-to-roll method. Many pinholes were observed.
  • FIG. 10A is a photomicrograph of a self-supporting thin film produced by dissolving PDMS and a curing agent in 100% n-hexane by a roll-to-roll method. Many pinholes were observed.
  • FIG. 10A is a photomicrograph of a self-supporting thin film produced by dissolving
  • FIG. 12A lower figure: no APTES treatment
  • Figure 12B Figure showing the change in contact angle over time with wettability of pure PDMS thin film (0.5 min) (upper surface in Fig. 13A: front surface, lower surface in Fig. 13A: back surface) when both front and back surfaces are modified with APTES (Fig. 13B).
  • Results of air bulge test on mechanical properties of PDMS self-supporting thin films with different main agent: hardener ratio (main agent: hardener 5: 1 (604 nm), 10: 1 (561 nm), 20: 1 (498 nm))
  • FIG. FIG. 14A Outline of air bulge test method for soot film.
  • FIG. 14B represents the change in elastic modulus given by the change in the proportion of the curing agent in the PDMS self-supporting thin film.
  • FIG. 14C Represents the change in modulus given by the change in the proportion of curing agent in PDMS self-supporting thin film coated with PDA.
  • FIG. 15A and 15B show FT-IR spectra of PDMS-modified or non-modified PDMS self-supporting thin films. Figure showing the results of surface analysis by XPS of PDMS free-standing thin film coated with polymer material polydopamine (PDA) (Fig. 16A), and comparing the signal intensity of N1s at coating time of 0, 2 or 24 hours Figure ( Figure 16B, C).
  • PDA polymer material polydopamine
  • FIG. 17A shows the correlation between PDMS film thickness and the energy of adhesion to the surface of a living tissue.
  • FIG. 17B shows the measurement results of the adhesion energy of the PDMS-supported thin film coated with PDA to the surface of the living tissue.
  • FIG. 18B shows the result of measuring the resonant frequency of an IC tag implanted in a rat using a network analyzer.
  • One embodiment of the present invention is a polyphenol-coated self-supporting thin film in which at least one film surface of a water-insoluble polymer thin film having adhesion by thinning is coated with polyphenol It is.
  • the polyphenol-coated self-supporting thin film exerts a synergistic effect on the object or article including a living organ or skin, etc., by the adhesion of the thin film and the adhesion by the polyphenol film. High adhesiveness can be expressed.
  • thin film means reducing the thickness of the thin film, or manufacturing a thin film having a small thickness, so that these thin films can be applied to the skin of a living body without using an adhesive.
  • a thin film is manufactured to such an extent that it has an adhesive force with respect to an object including an organ or the like, or a manufactured state.
  • adheresion means a state in which two materials interact with each other at an interface and are aligned by atomic bonding or mechanical action. This is the energy required to peel off (Eiji Iwamura, Surface Technology 5, 260-266: 2007). That is, in this specification, the “thin film having adhesion by thinning” means, for example, high followability due to the flexibility of the high molecular polymer forming the thin film, and between various substrates including the thin film surface and living tissue. A thin film capable of exhibiting high bonding properties on a substrate by van der Waals force bonding, hydrogen bonding or hydrophobic bonding.
  • adheresion refers to a state in which two surfaces are bonded by chemical or physical force or both through an adhesive
  • adheresion is the same or different. It refers to the force required to peel off two materials after bonding between the surfaces of the materials via an adhesive substance. That is, in this specification, adhering a self-supporting thin film coated with polyphenols containing polydopamine to an object or article means that the interface between the polyphenol film and the self-supporting thin film is in close contact with the polyphenol film. It means that an object or an article is in close contact.
  • the adhesion force and the adhesive force act synergistically to exert a strong binding force on an object or an article
  • the binding force is changed from “adhesion” to “adhesion strength”.
  • a synergistic effect of “adhesion strength” and “adhesion strength” it may be expressed as “adhesive strength”.
  • the film thickness that exhibits adhesion is 800 ⁇ m or less, preferably 500 ⁇ m or less, more preferably 100 ⁇ m or less, and most preferably 30 It is below ⁇ m.
  • the film thickness that exhibits adhesion is 200 nm or less, preferably 100 nm or less, more preferably 50 nm or less, and most preferably 30 nm or less.
  • the lower limit of the film thickness is not limited as long as it can be used as a self-supporting thin film, but is preferably 15 nm or more, more preferably 30 nm or more, and most preferably 100 nm or more. .
  • the film thickness may be a film thickness as a single layer film, or may be a film thickness of a laminated film obtained by laminating single layer films.
  • the laminated film may be the same kind of monolayer film, may be laminated with different kinds of monolayer films, or may be an alternately laminated film.
  • a silicone thin film has elasticity, when used as a biocompatible film, it can be applied to organs, skins, joints, and the like with movement.
  • Polylactic acid thin film on the other hand, can produce a thin film with a smaller film thickness than silicone thin film, and can improve adhesion by making it thinner, but it is inferior to silicone thin film in terms of stretchability.
  • a biocompatible thin film for example, it can be used as a thin film for application to an organ or the like that does not involve movement.
  • a thin film having a high aspect ratio is produced by adjusting the polarity of the solvent at the time of curing to a specific range described below. And it can be used as a self-supporting thin film.
  • self-standing means that the thin film or thin film is stable and capable of maintaining its properties and supports itself without the need for any support. Say what you can do.
  • the “aspect ratio” means a ratio obtained by dividing the maximum length on the thin film surface of the thin film of the present invention by the thickness.
  • the shape of the thin film of the present invention may be any shape, but the maximum length means, for example, the diameter in the case of a thin film having a circular surface, and the length of the long side in the case of a rectangular thin film. .
  • the aspect ratio of the thin film of the present invention is 10 6 or more. Accordingly, the aspect ratio of the thin film of the present invention is 2x10 6 or more, 3x10 6 or more, or may be 5x10 6 or more or 10x10 6 more.
  • the aspect ratio of the thin film of the present invention is 10 6 or more. Therefore, when the thickness of the thin film of the present invention is 1 ⁇ m or less, the maximum length of the surface of the thin film of the present invention is 1 m or more. When the thickness of the thin film is 800 nm or less, the maximum length is 80 cm or more. When the thickness of the thin film is 600 nm or less, the maximum length is 60 cm or more. When the thickness of the thin film is 500 nm or less, the maximum length is 50 cm or more. When the thickness of the thin film is 400 nm or less, the maximum length is 40 cm or more. When the thickness of the thin film is 300 nm or less, the maximum length is 30 cm or more. When the thickness of the thin film is 200 nm or less, the maximum length is 20 cm or more. When the thickness of the thin film is 100 nm or less, the maximum length is 10 cm or more.
  • the self-supporting thin film used as the substrate of the present invention has high adhesion, light transmission, tensile strength, extensibility, and elastic modulus.
  • the elastic modulus has an elastic modulus of less than 1 GPa when the elastic modulus is measured by an air bulge test (Adv. Funct. Mater. 2009, 19, 2560-2568; Soft Matter, 2016, 12, 9202-9209).
  • it when used as a biocompatible membrane due to its high elastic modulus and high adhesion properties, it can be used by being attached to organs, skins, and joints in the vicinity of motion.
  • the above thinning has improved synergistically by coating a polyphenol compound on at least one surface of a self-supporting thin film having adhesion to an object such as an organ or skin without using an adhesive.
  • a polyphenol-coated self-supporting thin film having adhesiveness can be produced.
  • the film thickness of the polyphenol film ranges from 2 to 30 ⁇ m, preferably from 20 to 10 ⁇ m, more preferably from 30 to 3 ⁇ m.
  • the film thickness of the polydopamine film is 2 The range is from nm to 60 nm, preferably from 20 nm to 50 nm, and more preferably from 40 nm to 50 nm.
  • the polyphenol compound is tannin, the range is 2 to 30 ⁇ m, preferably 20 to 10 ⁇ m, more preferably 30 to 3 ⁇ m.
  • the “biocompatible thin film” refers to a thin film that can be used by being transplanted to a living body or attached to a biological tissue or organ such as skin or organ, a surgical wound, etc. And can be used as a coating for covering a device to be implanted in a living body in the living body.
  • the thin film of the present invention has high adhesion to living tissue.
  • adhesion (adhesion) energy the adhesion (adhesion) energy is 2 ⁇ J or more.
  • suitable water-insoluble polymer thin films include, for example, silicone water-insoluble polymer thin films, acrylonitrile-butadiene copolymer water-insoluble polymer thin films, acrylic water-insoluble polymer thin films, epichlorohydrin-free films.
  • Elastomers such as water-soluble polymer thin film, chlorosulfonated polyethylene, chlorinated polyethylene and urethane water-insoluble polymer thin film, and biocompatibility such as polylactic acid, lactic acid copolymer, polylactone, lactone copolymer, polypeptide Examples thereof include a polymer film.
  • the water-insoluble polymer thin film is composed of silicone, polylactic acid (PLA), polyglycolic acid (PGA), glycolic acid / L-lactic acid copolymer, and glycolic acid / DL-lactic acid.
  • it may be selected from alternating laminated films made of an electrolyte polymer such as chitosan-alginic acid alternating laminated films.
  • the water-insoluble polymer thin film is composed of silicone, polylactic acid (PLA), polyglycolic acid (PGA), glycolic acid / L-lactic acid copolymer, and glycolic acid / DL-lactic acid.
  • it may be selected from alternating laminated films made of an electrolyte polymer.
  • thermosetting resin-based water-insoluble polymer thin film and a photo-curable resin-based water-insoluble polymer thin film are preferable, but not limited thereto.
  • thermosetting water-insoluble polymer thin films examples include silicone water-insoluble polymer thin films, urethane water-insoluble polymer thin films, and fluorine water-insoluble polymer thin films.
  • Examples of the photocurable water-insoluble polymer thin film include a silicone water-insoluble polymer thin film and a urethane acrylate resin.
  • the “water-insoluble polymer thin film raw material composition” means a composition containing a monomer component and / or a prepolymer component before the polymerization and / or crosslinking reaction for forming the water-insoluble polymer thin film. It is generally called “main agent” and used.
  • a desired water-insoluble polymer thin film can be produced by adding a curing agent to the water-insoluble polymer thin film raw material composition (main agent) and performing a crosslinking reaction under predetermined reaction conditions.
  • the water-insoluble polymer thin film of organopolysiloxane is a polymer having a structural unit represented by the following general formula 1.
  • it can be obtained by polymerizing and / or cross-linking a water-insoluble polymer thin film raw material composition (main agent) containing a cyclic siloxane compound with a curing agent described in detail below.
  • -[Si (R 1 R 2 ) -O]- Formula 1 (In the formula, R 1 and R 2 are each independently a hydrogen atom, an unsubstituted or substituted alkyl group, an aryl group, an alkenyl group, or a hydrogen atom.)
  • alkyl group examples include a methyl group, an ethyl group, a propyl group, a butyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group. Furthermore, you may substitute a part by the substituent which does not have reactivity substantially.
  • R 1 is a substituted or unsubstituted alkenyl group, it can be used not only as a component of the water-insoluble polymer thin film raw material composition (main agent) of the organopolysiloxane of formula 1 but also as a curing agent.
  • organopolysiloxanes polydimethylsiloxane in which both R 1 and R 2 are methyl groups is preferable, and the structure thereof is represented by the following formula 2.
  • cyclic siloxane compound examples include hexamethylcyclotrisiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, and the like, among which octamethylcyclotetrasiloxane is preferable.
  • the curing agent can be properly used depending on the type of main reactive group of the polysiloxane derivative.
  • the polysiloxane derivative has a hydrosilyl group as the main reactive group
  • the compound having an alkenyl group can be used as the curing agent when the compound having an alkenyl group as the main reactive group.
  • the curing agent having an alkenyl group is not particularly limited as long as it is a compound having an alkenyl group, but preferably contains at least two alkenyl groups in one molecule, a linear polysiloxane having an alkenyl group, Particularly preferred are siloxane compounds such as polysiloxanes having alkenyl groups at the molecular ends and cyclic siloxanes containing alkenyl groups. These compounds having an alkenyl group may be used alone or in combination of two or more.
  • Preferred examples of the self-supporting thin film of the present invention include a single-layer film, that is, a self-supporting single-layer thin film that can be self-supporting without including a support film.
  • a pinhole means a hole existing in a thin film having a minimum diameter of 10 ⁇ m or more, preferably a minimum diameter of 5 ⁇ m or more, and most preferably a minimum diameter of 1 ⁇ m or more. It is. Pinholes are more likely to occur when manufacturing thinner films.
  • a water-insoluble polymer thin film raw material composition (main agent) for forming a thin film and a curing agent are dissolved in a solvent having a specific polarity, and a crosslinking reaction is performed.
  • the solvent having the polarity of this characteristic is a solvent having a solubility parameter (Hildebrand parameter) SP value in the range of 7.3 to 11.3.
  • Such a solvent can be obtained, for example, by mixing n-hexane with another polar solvent.
  • the other polar solvent mixed with n-hexane include ethyl acetate.
  • a solvent with a solubility parameter (Hildebrand parameter) SP value in the range of 7.3 to 11.3 by mixing a small amount of ethyl acetate with n-hexane (See M. G. side Whitesides et al., Anal. Chem., 75, 6544-6554 (2003)).
  • n-hexane / ethyl acetate 4: 1 (v / v) can be mentioned.
  • polylactic acid, lactic acid copolymer, polylactone, lactone copolymer, polypeptide, and the like can be used as specific material substances of the self-supporting thin film material, and biocompatibility using these material substances
  • the polymer thin film having can be produced according to a known method (Japanese Patent Laid-Open No. 2014-140977).
  • the water-insoluble polymer thin film can stably obtain a water-insoluble polymer thin film having a more uniform film thickness by containing these compounds as material substances.
  • polylactic acid when polylactic acid is used as a material substance, for example, L-lactic acid, D-lactic acid, or a polymer of lactic acid containing both of them can be used.
  • a polymer of lactide which is a cyclic dimer of lactic acid such as L-lactide, D-lactide, and meso-lactide may also be used.
  • a polymer of lactic acid and other monomer components can be used.
  • the other monomer components include glycolic acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 4-hydroxyvaleric acid, 6-hydroxycaproic acid and the like; ethylene glycol, propylene glycol, butanediol, neo Compounds containing a plurality of hydroxyl groups in the molecule such as pentyl glycol, polyethylene glycol, glycerin, pentaerythritol or derivatives thereof; succinic acid, adipic acid, sebacic acid, fumaric acid, terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic Examples thereof include compounds having a plurality of carboxylic acid groups in the molecule, such as acid, 5-sodium sulfoisophthalic acid, and 5-tetrabutylphosphonium sulf
  • lactone polymers such as ⁇ -caprolactone, ⁇ -butyrolactone, ⁇ -methyl- ⁇ valerolactone, and ⁇ -propiolactone can be used.
  • the polymer of a lactone and another monomer component can be used, for example.
  • the other monomer components include glycolic acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 4-hydroxyvaleric acid, 6-hydroxycaproic acid and the like; ethylene glycol, propylene glycol, butanediol, neo Compounds having a plurality of hydroxyl groups in the molecule such as pentyl glycol, polyethylene glycol, glycerin, pentaerythritol or derivatives thereof; succinic acid, adipic acid, sebacic acid, fumaric acid, terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic Examples thereof include compounds having a plurality of carboxylic acid groups in the molecule, such as acid, 5-sodium sulfoisophthalic acid, and 5-tetrabutylphosphonium sul
  • polypeptide for example, polylysine, polyglutamine, polyasparagine, polyarginine, polyglutamic acid, polyaspartic acid, polyglycine, polyphenylalanine, polyalanine, polyleucine, polyisoleucine, polyvaline, Polyproline, polyserine, polythreonine, polytyrosine and the like can be used.
  • Biopolymers other than polypeptides such as polysaccharides and nucleic acids can also be used.
  • the self-supporting thin film of the present invention may be expressed as a self-supporting thin film specified by these manufacturing methods because the self-supporting thin film cannot be clearly defined only by a chemical structural formula.
  • the water-insoluble polymer thin film of the present invention comprises a filler, a pigment, a dye, a plasticizer, an adhesion promoter, an impact resistance agent, a curing agent (for example, a scratch resistance agent), a coupling agent, an antioxidant, and An additive such as a light stabilizer can be contained.
  • Another embodiment of the present invention is hydrophilic, hydrophobic, water repellency, improved tensile strength, improved flexibility, improved adhesion and peel resistance, impact resistance Self-supporting, in which at least one surface of the thin film has been surface-modified to improve durability, weather resistance, heat resistance, oxidation resistance, improved compatibility, increase surface smoothness, reduce volume expansion coefficient, etc. It is a thin film.
  • the surface to be surface modified may be a single surface.
  • a thin film having different characteristics between the front surface and the back surface is also included in the self-supporting thin film of the present invention.
  • a self-supporting film can be provided in which one surface is hydrophilic and the other surface is hydrophobic.
  • An example of a surface modifier for surface modification is treatment with a silane coupling agent.
  • silane coupling agent examples include, but are not limited to, vinylvinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacrylic Roxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, amino N-2- (aminoethyl) -3-aminopropylmethyldimethoxy Silane
  • 3-aminopropyltriethoxysilane can be used as a silane coupling agent.
  • the treatment with the silane coupling agent can be performed after activating the thin film surface by plasma irradiation.
  • a self-supporting thin film surface-treated with a silane coupling agent can be used for surface modification, adsorption suppression of cells / proteins, dye modification, etc., because the film surface has hydrophilicity.
  • the surface-modified self-supporting thin film can be provided as a self-supporting thin film whose surface is modified with a polyphenol compound.
  • the polyphenol compound is preferably polydopamine, tannic acid, catechin, rutin, anthocyanin, isoflavone, quercetin, hesperidin, flavonoid compounds, chlorogenic acid, ellagic acid, lignan, curculin, coumarin, epicatechin gallate, epigallocatechin , Epigallocatechin gallate, and one or more selected from the group consisting of gallocatechin gallate, more preferably a self-supporting thin film that is polydopamine.
  • the polydopamine used in the present invention is a polymer obtained by oxidative polymerization of dopamine or a salt thereof in an aqueous solvent by air oxidation or the like, and its reaction, structure and properties are described in Liebscher J et al., Langmuir 2013, 29. , 10539-10548.
  • tannic acid When tannic acid is used, a known method (D. Payra et al., Chem. Commun., which becomes soluble in an organic solvent by introducing an alkyl group into tannic acid and can be applied to various coating techniques. According to 2016, 52, 2016312), the polymer can be produced and used. About the said other polyphenol compound, a polymer can be produced and used according to the usage method of dopamine and tannic acid.
  • Method for producing self-supporting thin film Another embodiment of the present invention is a method for producing the self-supporting thin film.
  • the method for producing a self-supporting thin film is a method for producing a self-supporting thin film comprising a water-insoluble polymer thin film having a high aspect ratio, and an organic compound having a solubility parameter (Hildebrand parameter) SP value in the range of 7.3 to 11.3. It is a manufacturing method including the process of hardening and forming a water-insoluble polymer thin film raw material composition (main ingredient) in a solvent solution.
  • the water-insoluble polymer thin film is formed by performing a curing treatment under predetermined conditions in a mixed solvent of a water-insoluble polymer thin film raw material composition (main agent) and a curing agent.
  • the “curing agent” is used in the same meaning as the meaning of the “curing agent” generally known in the art, and is added to the water-insoluble polymer thin film raw material composition (main agent).
  • a composition comprising a component for polymerizing and / or crosslinking a monomer or prepolymer which is a component of a water-insoluble polymer thin film raw material composition (main agent) under a predetermined condition in a solvent to form a polymer; It is also referred to as “polymerization initiator” or “crosslinking agent” or may contain these.
  • the curing agent is selected from curing agents well known to those skilled in the art.
  • these curing agents for example, heat curing type organic peroxides, addition reaction type organohydrogenpolysiloxanes, condensation reaction curing types and hydrolyzable organosilicon compounds, photocuring agents and the like can be used.
  • organic peroxides include di-t-butyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 2,5-dimethyl-2,5-dioxide.
  • the compounding amount of the organic peroxide varies depending on the type of the water-insoluble polymer thin film, but is usually 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of the water-insoluble polymer thin film. .
  • an organic peroxide is not always necessary.
  • the photocuring agent used in the present invention is a reactive functional group of a polysiloxane compound by irradiating active energy rays such as visible light, ultraviolet rays, infrared rays, X rays, ⁇ rays, ⁇ rays or ⁇ rays.
  • active energy rays such as visible light, ultraviolet rays, infrared rays, X rays, ⁇ rays, ⁇ rays or ⁇ rays.
  • photocuring agent examples include, for example, photoradical initiators such as acetophenone, propiophenone, and benzophenone; 1,10-diaminodecane, 4,4′-trimethylenedipiperazine, carbamates and derivatives thereof, or cobalt Photoanion initiators such as amine complexes; near infrared photopolymerization initiators such as near infrared light absorbing cationic dye-borate anion complexes; photoacids such as sulfonic acid derivatives, onium salts or carboxylic acid esters Generators; or photocationic initiators such as metal fluoroboron complex salts and boron trifluoride complex compounds or bis (perfluoroalkylsulfonyl) methane metal salts.
  • photoradical initiators such as acetophenone, propiophenone, and benzophenone
  • the content of the curing initiator in the composition of the present invention is not particularly limited, but is preferably 0.01 to 10 parts by weight with respect to 100 parts by weight of the polysiloxane from the viewpoint of curability.
  • the amount is more preferably 0.05 to 5.0 parts by weight from the viewpoint of balance of physical properties.
  • the amount of the curing initiator is small, it may take a long time to cure, or a sufficiently cured product may not be obtained. Moreover, when there are many hardening initiators, since a color remains in hardened
  • a sensitizer can be added in order to promote liberation of active species.
  • the type of sensitizer is not particularly limited, and widely known sensitizers can be used.
  • the addition amount of the sensitizer is not particularly limited, but is preferably 0.01 to 10 parts by weight, and more preferably 0.02 to 5 parts by weight with respect to 100 parts by weight of the polysiloxane.
  • the thin film of the present invention a self-supporting thin film having a specific function or application
  • the type of additive is not particularly limited, and examples thereof include fillers, pigments, dyes, plasticizers, adhesion promoters, impact resistance agents, curing agents, coupling agents, antioxidants, and / or light stability. It is done.
  • organohydrogenpolysiloxane when used as a curing agent, a platinum compound may be required as an addition reaction catalyst.
  • organohydrogen diene polysiloxane examples include methyl hydrogen polysiloxane, tetramethyl tetrahydrogen cyclotetrasiloxane, a copolymer of methyl hydrogen siloxane and dimethyl siloxane.
  • it is not limited to these, and may contain an alkyl group other than a methyl group or a phenyl group.
  • platinum-based catalysts include chloroplatinic acid, alcohol-modified chloroplatinic acid, platinum and olefin or vinylsiloxane complexes, finely divided platinum adsorbed on a carrier such as alumina and silica, palladium catalyst, and rhodium catalyst. Is preferably a platinum compound.
  • these water-insoluble polymer thin film raw material compositions (main ingredients) and their curing agent kits are commercially available and can be obtained and used for the production of the thin film of the present invention.
  • these commercially available silicone water-insoluble polymer thin films and their curing agent kits include DOW CORNING R TORAY R SILPOT 184 W / C, SYLGARD R 184 SILICONE ELASTOMER KIT, DOW CORNING R QP1-20 LIQUID SILICONE RUBBER KIT, DOW CORNING R QP1-30 LIQUID SILICONE RUBBER KIT, DOW CORNING R QP1-40 LIQUID SILICONE RUBBER KIT, DOW CORNING R QP1-45 LIQUID SILICONE RUBBER KIT, DOW CORNING R QP1-50 LIQUID SILICONE RUB COR R QP1-60 LIQUID SILICONE RUBBER KIT, DOW CORNING R QP1-70 LIQUID SILICONE RUBBER KIT,
  • condensation curable type water-insoluble polymer thin film raw material composition examples include KE-12, KE-14, KE-17, KE-24, KE-26, KE-1414, KE-1415 and Examples of KE-1416 (Shin-Etsu Chemical Co., Ltd., Tokyo) and addition reaction curable water-insoluble polymer thin film raw material compositions (main ingredients) include KE-1300T, KE-1314-2, KE-1316, KE-1600, KE-1603-A / B, KE-1606, KE-1222-A / B and KE-1241 (Shin-Etsu Chemical Co., Ltd., Tokyo) are commercially available. It can be used for the production of the self-supporting thin film of the present invention.
  • photocurable water-insoluble polymer thin film raw material composition examples include: Hitaloid 7909-1, Hitaroid 7902-1, Hitaroid 7100, Hitaroid 7200, Hitaroid UV028, Hitaroid 7902A, There are Hitaroid 7975, Hitaroid 7903-B, Hitaroid 7663, Hitaroid UV251, Hitaroid UV222, Hitaroid 7927, Hitaroid 7927, and Hitaroid 7927-15 (Hitachi Chemical Co., Ltd., Tokyo). Can be used for manufacturing.
  • the water-soluble polymer layer is used as a sacrificing layer or a supporting layer. Both mean layers formed on the assumption that they will be removed in a later step.
  • the former mainly refers to a polymer film that is removed by dissolving with water, including the use of the manufactured thin film, in the thin film or film manufacturing process.
  • a laminated film including a water-soluble sacrificial layer or a water-soluble support film as an intermediate layer is formed in the production process, and the sacrificial layer or the support film is dissolved to form a laminated film. A step of peeling the intended self-supporting thin film from the film.
  • the water-soluble sacrificial layer and the water-soluble polymer layer of the water-soluble support film are not limited as long as they are soluble in water, but usually a polyvinyl alcohol film, a polyacrylic acid film, a polymethacrylic acid film, Sodium alginate film, polyethylene oxide film, polyacrylamide film, polyvinylpyrrolidone film, starch film, carboxymethylcellulose film, collagen film, pullulan film, agar film, silicone film, poly-2-methacryloyloxyethyl phosphorylcholine (MPC) film, poly (N -Isopropylacrylamide) (PNIPAM) membrane, polyethylene glycol (PEG) membrane, etc., preferably polyvinyl alcohol membrane, polyacrylic acid membrane, starch membrane, collagen membrane, agar membrane, poly-2-methacryloyloxyethyl phosphorylcholine (MPC) Membrane, poly (N-isopropyl Le acrylamide) (PN
  • the film thickness of the water-soluble polymer film is usually 5 nm to 1000 nm, preferably 5 nm to 500 nm, more preferably 10 nm to 300 nm, and still more preferably 10 nm to 200 nm, particularly preferably 10 nm to 100 nm.
  • the film thickness of the water-soluble support membrane is usually 50 nm to 20000 nm, preferably 100 nm to 10000 nm, more preferably 200 nm to 5000 nm, and still more preferably 500 nm to 5000 nm. nm, particularly preferably 700 nm to 5000 nm.
  • the self-supporting thin film of the present invention is a sheet shape in which the self-supporting thin film of the present invention is laminated on a release sheet having flexibility for the purpose of improving the handleability when the thin film of the present invention is applied to an application target. It can also be used by producing a laminate. More specifically, for example, based on a known method (Japanese Patent Laid-Open No.
  • the alicyclic olefin of a release sheet of a single layer or clothes having flexibility and including an alicyclic olefin-based resin layer The self-supporting thin film of the present invention having a predetermined thickness is laminated on the resin-based resin layer with a water-soluble polymer film having a thickness of 20 to 500 ⁇ m stacked thereon.
  • a water-soluble polymer film having a thickness of 20 to 500 ⁇ m stacked thereon.
  • examples of the base material for forming the laminated film may be other than silicone or polylactic acid, and the whole or a part of the base material may be a metal or an oxide film thereof, silicon, silicon rubber, silica.
  • carbon materials such as glass, mica, graphite, polyethylene, polypropylene, cellophane, elastomer, alginic acid, pullulan, polyvinyl alcohol, polyimide, polyolefin, polyacrylic acid, starch, gelatin, cellulose, poly-2-methacryloyloxyethyl phosphorylcholine (MPC)
  • a film a polymer material such as poly (N-isopropylacrylamide) (PNIPAM) film or polyethylene glycol (PEG) film, and a calcium compound such as apatite.
  • PNIPAM poly (N-isopropylacrylamide)
  • PEG polyethylene glycol
  • spin coating method spin coating method, dipping method, spray coating method, electric field polymerization method, vapor deposition method, vapor deposition polymerization method, brush coating method, blade coating method, roller coating method, and the like as coating methods for film formation
  • a known method such as a roll-to-roll method can be used, but in terms of manufacturing a thin film having a high aspect ratio, that is, a self-supporting water-insoluble polymer thin film having a long thin side having a rectangular shape, A roll-to-roll method is preferred.
  • a commercially available apparatus such as a gravure coater can be used.
  • the self-supporting thin film manufactured by the manufacturing method has high stretchability and transparency
  • the insulating film and the sealing film of the electronic device, the transparent protective film of the display, the wound dressing, the catheter protective film, and the contact lens It can be used as a pacemaker protective film, an endoscope protective film, a wearable implantable device substrate, a cell culture substrate, and the like.
  • Method for producing surface-modified self-supporting thin film is a method for producing a surface-modified self-supporting thin film by subjecting the self-supporting thin film to surface modification treatment.
  • the surface modification includes the case where the front and back surfaces of the self-supporting thin film are surface-modified and the case where only one surface is modified.
  • a thin film that becomes a self-supporting thin film can be laminated using a PET film or the like as a supporting film, and surface modification can be performed using this laminated film.
  • Examples of surface modification methods include, for example, polyphenols for the purpose of surface activation by silane coupling agent treatment after plasma irradiation for the purpose of imparting hydrophilicity, and improvement of adhesive strength, tensile strength and elastic force Examples of the surface modification method are described below.
  • the surface-treated PDMS thin film is immersed in a 3-aminopropyltriethoxysilane (APTES) solution that is a silane coupling agent.
  • APTES 3-aminopropyltriethoxysilane
  • the water-soluble polymer layer is dissolved, and the surface-modified PDMS thin film is peeled off to selectively make one surface of the self-supporting thin film hydrophilic. You can quality.
  • the surface opposite to the water-soluble polymer layer of the thin film of the three-layer laminate of support layer-water-soluble polymer layer-thin film layer which is an intermediate step of the production method described in the method for producing a self-supporting thin film, After the surface modification, it can be produced by dissolving and separating the water-soluble polymer layer, and peeling and collecting the self-supporting thin film whose surface is modified only on one side.
  • polyphenol compounds for surface modification of the present invention include flavonoid compounds such as polydopamine, tannic acid, catechin, rutin, anthocyanin, isoflavone, quercetin, hesperidin, chlorogenic acid, ellagic acid, lignan, curculin. , Coumarin, epicatechin gallate, epigallocatechin, epigallocatechin gallate and gallocatechin gallate, and at least one selected from these can be selected and used.
  • flavonoid compounds such as polydopamine, tannic acid, catechin, rutin, anthocyanin, isoflavone, quercetin, hesperidin, chlorogenic acid, ellagic acid, lignan, curculin.
  • Coumarin epicatechin gallate, epigallocatechin, epigallocatechin gallate and gallocatechin gallate, and at least one selected from these can be selected and used.
  • a thin film whose surface has been modified with a polyphenol compound can be produced by dissolving these polyphenol compounds in a solvent, using this as a raw material solution for polymerization, and coating the thin film made of PDMS.
  • polydopamine can be selected as a polyphenol compound, and polydopamine can be coated on the surface of a PDMS free-standing thin film or a polylactic acid free-standing thin film by dipping.
  • PDMS self-supporting thin film and polylactic acid self-supporting thin film coated with polydopamine have improved adhesive strength, tensile strength and elastic force at each stage compared to the case of non-coating. To do. Therefore, a thin film coated with polydopamine and surface-modified can be used as a biocompatible thin film.
  • the surface treatment of the self-supporting thin film described above has further improved adhesion, tensile strength and elastic modulus in addition to high stretchability and transparency, the insulating film and the sealing film of the electronic device , Transparent protective films for displays, wound dressings, catheter protective films, contact lenses, pacemaker protective films, endoscope protective films, wearable implantable device substrates, and cell culture substrates, and more Is useful.
  • SILPOT 184 W / C and CATALYST SILPOT were used as siloxane monomer compositions for producing polydimethylsiloxane polymer thin films and their curing agents.
  • Polyvinyl alcohol (PVA, Kanto Chemical Co., Tokyo) is used as the water-insoluble polymer layer, which is a sacrificial layer, and polyethylene terephthalate (PET) film (Lumirror 25T60, Panac Co., Ltd., Tokyo) is used as the base material for the laminated film.
  • PET polyethylene terephthalate
  • BIO SKIN PLATE (Buelux Co., Ltd., Saitama) was used as the skin model, and 3-aminopropyltriethoxysilane (APTES) solution (Tokyo Chemical Industry Co., Ltd., Tokyo) was used as the silane coupling agent.
  • APTES 3-aminopropyltriethoxysilane
  • the organic solvent used was a grade higher than the commercially available special grade.
  • the gravure coater (ML-120 type, Yasui Seiki Co., Ltd., Tokyo) was used as the gravure coater used for film formation by the roll-to-roll method.
  • the stress-strain curve is measured using a tensile tester (EZ-S type, Shimadzu Corporation, Kyoto), and the UV-visible spectrophotometer (V-670 type, JASCO Corporation, Tokyo) for visible light transmission tests.
  • VN-8000 type Keyence, Tokyo
  • VE-9800 type (Keyence) was used for the scanning electron microscope.
  • plasma irradiation a PBI-20 type irradiation apparatus manufactured by Vacuum Device Co., Ltd. (Ibaraki) was used.
  • FIG. 1 shows the above process
  • FIG. 2 shows a PET film on which PVA and PDMS are formed.
  • the stress-strain curves of the PDMS self-supporting thin film (film thickness: 588 nm) and the PDMS film (film thickness: 135 ⁇ m, formed by the casting method) were measured with a tensile tester (FIG. 7).
  • the nanosheet made of polylactic acid used as a biocompatible polymer has a film thickness of about 100 nm and a Young's modulus of about 2 GPa.
  • PDMS self-supporting thin film (film thickness: 588 nm) is about 60 compared with thin film (thickness: 212 ⁇ nm, Young's modulus: about 45 MPa) made of non-thermosetting water-insoluble polymer thin film (example: SBS) Double (Young's modulus ratio: 45 MPa / 0.76 MPa) was shown to be flexible.
  • the adhesion of the prepared PDMS self-supporting thin film was measured by the cross-cut method according to JIS K5600-5-6 (ISO2409).
  • a square grid pattern (25 squares) was formed with a cutter on a PDMS self-supporting thin film affixed on a SUS substrate, and a peel test was performed with a cellophane tape with an adhesive strength of 4.0 mm / cm. The rate increased (Fig. 8A, B). From this result, it was shown that a PDMS thin film with a film thickness of 588 nm has about 20 times higher adhesion than a PDMS film with a film thickness of 1 ⁇ m or more.
  • a polylactic acid (PDLLA) nanosheet (film thickness: 120 nm), which is a biocompatible polymer, was prepared according to a known method (Miyazaki et al., Wound Rep Rep Reg 20 573-579 (2012)).
  • This polylactic acid thin film and PDMS thin film (film thickness: 588 nm) were attached to an artificial skin model, and scanning electron microscope (SEM) images were acquired (FIGS. 9A and 9B).
  • SEM scanning electron microscope
  • the formation of numerous pinholes was observed (FIG. 10A).
  • PDMS whose elastic modulus was improved by increasing the proportion of the curing agent was subjected to surface treatment by PDA modification described in detail below.
  • the elastic modulus more than doubled was recognized, and the elastic modulus further increased by PDA modification (FIG. 14C).
  • the effect of changing the immersion time of the PDMS thin film in the PDA solution on the thickness of the PDA coating was investigated. Specifically, regarding the PDMS-modified PDMS self-supporting film having a film thickness of 600 nm, the film thickness before and after the modification was measured, and the difference is shown in Table 2 as the layer thickness of the PDA coating layer. . As a result, there was no difference in PDA film thickness between 24 hours (44 nm) and 48 hours (43 nm), indicating that the polymerization reaction of dopamine was saturated in 24 hours.
  • the film thickness becomes less than 50 nm when the PDA modification is performed for 24 hours on the SiO 2 substrate (Haeshin Lee et al., SCIENCE 19, 318, 426-430, (2007)). . Therefore, in the case of PDA modification by the dipping method, the film thickness is considered to be about this in the case of 24-hour modification regardless of the base material.
  • the amount of work required for the thin film to peel off from the muscle layer when it was pulled up by a tensile tester after being attached to (chicken muscle layer) was calculated as the adhesive energy.
  • the adhesion (adhesion) energy to the surface of living tissue increases as the film thickness decreases, and the thin film (film thickness: 561 mm, adhesion energy: 10.5 mm) is bulk (film thickness: 800 mm, adhesion energy: 2.2 mm) ) Was about 5 times more sticky (adhesiveness) than 4 times (FIG. 17A). Furthermore, the PDMS thin film (film thickness: 561 nm, adhesion energy: 50.6 ⁇ J) surface-modified with PDA (approx. 24 hours) showed about 5 times the adhesion (adhesion) energy before modification (FIG. 17B).
  • this result shows that, due to the increase in adhesion due to thin film formation and the increase in adhesion due to PDA modification, they exert a synergistic effect and show strong adhesive strength (adhesion strength) overall. It is a thing.
  • the IC tag could be stably fixed to the abdominal wall for 30 days or more.
  • the micro-CT for small animals (6) This was confirmed by Yamato Science, TDM1300-IS (FIG. 18B).
  • the resonant frequency of the IC tag implanted in the rat was measured with a network analyzer, the resonant frequency (13.56 MHz) was detectable only for the IC tag sealed with a PDA-modified PDMS thin film and attached to the abdominal wall. On the other hand, since the IC tag sealed with the bulk film was peeled off from the abdominal wall, the resonance frequency could not be detected (FIG. 18C).

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Abstract

La présente invention concerne un film fin autoportant présentant une forte adhésivité dans lequel une augmentation de l'adhérence en raison de l'amincissement et une augmentation de la force adhésive en raison du revêtement de polyphénol agit de manière synergique par revêtement d'un film fin autoportant doté de polyphénol. Le film fin autoportant peut être utilisé comme film fin biocompatible. La présente invention concerne également un procédé de production d'un film fin autoportant comprenant de la silicone avant le revêtement de polyphénol, dans lequel le procédé de production d'un film fin autoportant en silicone présentant un rapport d'aspect, un module élastique, et un pouvoir adhésif élevés, utilise un solvant présentant une polarité spécifique en tant que le solvant qui dissout l'agent principal et l'agent de durcissement pendant une réaction de réticulation en vue de former un film fin de polymère non soluble dans l'eau.
PCT/JP2017/016283 2016-04-25 2017-04-25 Film fin autoportant non soluble dans l'eau présentant une forte adhésivité WO2017188214A1 (fr)

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CN108286126A (zh) * 2018-01-24 2018-07-17 上海理工大学 一种快速止血复合纤维膜的制备方法
CN110885665A (zh) * 2019-12-02 2020-03-17 四川大学 一种高稳定的用于医疗器械表面亲水性涂层的制备方法
TWI694122B (zh) * 2018-10-03 2020-05-21 明基材料股份有限公司 用於著色矽水膠隱形眼鏡之色料組合物、含此色料組合物的著色矽水膠隱形眼鏡、以及改質用於著色矽水膠隱形眼鏡之色料的方法
JP2020084171A (ja) * 2018-11-30 2020-06-04 サムソン エレクトロ−メカニックス カンパニーリミテッド． 表面処理用組成物及びこれを用いた表面処理方法
KR20200090910A (ko) * 2017-12-18 2020-07-29 도쿄엘렉트론가부시키가이샤 리소그래피를 위한 표면 접착력을 강화하기 위한 플라즈마 처리 방법
US11027462B2 (en) * 2016-11-09 2021-06-08 The Board Of Trustees Of Western Michigan University Polydimethylsiloxane films and method of manufacture
WO2022201616A1 (fr) 2021-03-24 2022-09-29 株式会社朝日Ｆｒ研究所 Feuille d'élastomère ultramince et procédé pour sa production
CN115487361A (zh) * 2022-09-16 2022-12-20 四川大学 一种亲水抗菌抗炎水凝胶薄膜及其制备方法与应用
CN115591007A (zh) * 2022-09-19 2023-01-13 南京理工大学（Cn） 一种修复半月板撕裂的组织粘附剂的制备方法
WO2023248620A1 (fr) * 2022-06-21 2023-12-28 株式会社朝日Ｆｒ研究所 Récipient de culture cellulaire et son procédé de fabrication

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CN114307679B (zh) * 2022-01-07 2023-03-24 江南大学 一种新型高通量染料脱盐膜及其制备方法

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US11027462B2 (en) * 2016-11-09 2021-06-08 The Board Of Trustees Of Western Michigan University Polydimethylsiloxane films and method of manufacture
KR102632799B1 (ko) * 2017-12-18 2024-02-01 도쿄엘렉트론가부시키가이샤 리소그래피를 위한 표면 접착력을 강화하기 위한 플라즈마 처리 방법
KR20200090910A (ko) * 2017-12-18 2020-07-29 도쿄엘렉트론가부시키가이샤 리소그래피를 위한 표면 접착력을 강화하기 위한 플라즈마 처리 방법
CN108286126A (zh) * 2018-01-24 2018-07-17 上海理工大学 一种快速止血复合纤维膜的制备方法
TWI694122B (zh) * 2018-10-03 2020-05-21 明基材料股份有限公司 用於著色矽水膠隱形眼鏡之色料組合物、含此色料組合物的著色矽水膠隱形眼鏡、以及改質用於著色矽水膠隱形眼鏡之色料的方法
JP2020084171A (ja) * 2018-11-30 2020-06-04 サムソン エレクトロ−メカニックス カンパニーリミテッド． 表面処理用組成物及びこれを用いた表面処理方法
JP7230305B2 (ja) 2018-11-30 2023-03-01 サムソン エレクトロ－メカニックス カンパニーリミテッド． 表面処理用組成物及びこれを用いた表面処理方法
CN110885665B (zh) * 2019-12-02 2021-01-29 四川大学 一种高稳定的用于医疗器械表面亲水性涂层的制备方法
CN110885665A (zh) * 2019-12-02 2020-03-17 四川大学 一种高稳定的用于医疗器械表面亲水性涂层的制备方法
WO2022201616A1 (fr) 2021-03-24 2022-09-29 株式会社朝日Ｆｒ研究所 Feuille d'élastomère ultramince et procédé pour sa production
WO2023248620A1 (fr) * 2022-06-21 2023-12-28 株式会社朝日Ｆｒ研究所 Récipient de culture cellulaire et son procédé de fabrication
CN115487361A (zh) * 2022-09-16 2022-12-20 四川大学 一种亲水抗菌抗炎水凝胶薄膜及其制备方法与应用
CN115591007A (zh) * 2022-09-19 2023-01-13 南京理工大学（Cn） 一种修复半月板撕裂的组织粘附剂的制备方法

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