WO2020111157A1 - Electroconductive material and method for manufacturing same - Google Patents

Electroconductive material and method for manufacturing same Download PDF

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Publication number
WO2020111157A1
WO2020111157A1 PCT/JP2019/046450 JP2019046450W WO2020111157A1 WO 2020111157 A1 WO2020111157 A1 WO 2020111157A1 JP 2019046450 W JP2019046450 W JP 2019046450W WO 2020111157 A1 WO2020111157 A1 WO 2020111157A1
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Prior art keywords
conductive polymer
monomer
carbon
base material
silk
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PCT/JP2019/046450
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French (fr)
Japanese (ja)
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英敏 寺本
恒徳 亀田
秀生 岡野
飛鳥 及川
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国立研究開発法人農業・食品産業技術総合研究機構
エーアイシルク株式会社
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Priority to JP2020557803A priority Critical patent/JP7064199B2/en
Publication of WO2020111157A1 publication Critical patent/WO2020111157A1/en

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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
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/63—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing sulfur in the main chain, e.g. polysulfones
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables

Definitions

  • the present invention relates to a conductive material having a conductive polymer film formed on the surface of a fiber or a thin film, and a method for producing the same.
  • Patent Document 3 describes that the durability of the conductive fiber is improved by adhesively bonding a compound having an azinyl group to the surface of the conductive fiber.
  • a conductive substance such as a metal is bonded to the surface of a polymer fiber, and a compound having an azinyl group is adhered and bonded to the surface of the polymer fiber.
  • the structure is completely different from that of the present invention in which the connection is made by a connecting portion having a specific structure.
  • Patent Document 4 in a conductive fiber in which a fiber carrying an electron acceptor and dyed with an electron donating dye is coated with a conductive polymer film, a conductive polymer precursor is brought into contact with the fiber. In this state, the fiber is irradiated with light to polymerize the conductive polymer precursor.
  • the electron-donating dye which is a dye of the fiber, acts as a polymerization initiator to form a conductive polymer film with a uniform thickness all around the fiber, whereby the conductive polymer is peeled off.
  • the structure is completely different from that of the present invention in which the base material and the conductive polymer film are bonded by a bonding portion having a specific structure.
  • Patent Document 5 in a conductive fiber in which a resin layer containing a conductive substance is formed on the surface of a thermoplastic synthetic fiber, an adhesive coating is formed between the thermoplastic synthetic fiber and the resin layer. , Improving the durability of conductivity.
  • Patent Document 5 uses an adhesive and has a completely different structure from the present invention in which the base material and the conductive polymer film are bonded by a bonding portion having a specific structure.
  • the present invention has been made based on such a problem, and an object thereof is to provide a conductive material capable of firmly fixing a conductive polymer.
  • the conductive material of the present invention has a conductive polymer film formed on the surface of a fiber or a thin film, and the fiber or thin film and the conductive polymer film are bonded to each other having a 1,2,3 triazole ring structure. Are connected by parts.
  • the method for producing a conductive material of the present invention is for producing a conductive material in which a conductive polymer film is formed on the surface of a fiber or a thin film, and a fiber or a thin film having a functional group having a carbon-carbon triple bond, A process of reacting a functional group having a carbon-carbon triple bond with an azido group for a conductive polymer monomer having an azido group to prepare a fiber or a thin film to which the conductive polymer monomer is bonded. And a step of applying a reaction liquid containing the monomer of the conductive polymer to the fiber or the thin film to which the monomer of the conductive polymer is bonded and polymerizing the monomer.
  • the fiber or thin film and the conductive polymer film are bonded to each other by the bonding portion having the 1,2,3 triazole ring structure.
  • it can be firmly fixed. Therefore, it is possible to prevent the conductive polymer film from peeling off due to repeated washing, friction, etc., and it is possible to suppress a decrease in conductivity.
  • a fiber or a thin film having a functional group having a carbon-carbon triple bond is allowed to react with a monomer of a conductive polymer having an azide group to form a conductive polymer.
  • the reaction liquid containing the monomer of the conductive polymer is applied thereto to polymerize the monomer, so that the functional group having a carbon-carbon triple bond is formed.
  • the conductive material of the present invention can be easily obtained by utilizing the reaction between the azido group and.
  • FIG. 1 conceptually shows the manufacturing process of the conductive material shown in FIG. 1.
  • 2 is a flowchart of a manufacturing process of the conductive material shown in FIG. 1.
  • It is a microscope picture showing the surface state of the silk which combined the monomer of electroconductive polymer.
  • It is a characteristic view showing the relationship between the monomer concentration of a conductive polymer and the amount of unreacted DBCO skeleton.
  • It is a microscope picture showing the surface state of the silk which combined the monomer of electroconductive polymer.
  • FIG. 4 is a characteristic diagram showing a comparison between Example 1 and Comparative Example 1 regarding changes in resistance value of a conductive material due to washing.
  • FIG. 6 is a characteristic diagram showing a change in resistance value of a conductive material due to washing, comparing Example 2 with Comparative Example 2-1 and Comparative Example 2-2.
  • FIG. 1 conceptually shows the structure of a conductive material 10 according to an embodiment of the present invention.
  • FIG. 2 conceptually shows the manufacturing process of the conductive material 10.
  • the conductive material 10 of the present invention is one in which a conductive polymer film 12 is formed on the surface of a base material 11 made of fibers or a thin film.
  • a base material 11 made of fibers or a thin film.
  • the material of the fiber or the thin film forming the base material 11 what kind of material can be used as long as it can be bonded to the conductive polymer film 12 by the bonding portion 13 having the 1,2,3 triazole ring structure 13A as described later.
  • silk or fibroin are preferable.
  • Silk is a natural fiber produced by the silkworm in the body, and may have any shape such as thread, cloth, film or sponge, and may be woven or non-woven. Fibroin is a type of protein and is the main component of silk, and may be extracted from silk and formed into a thin film.
  • Preferred examples of the conductive polymer film 12 include those containing at least one of poly 3,4-ethylenedioxythiophene (hereinafter referred to as PEDOT) and its derivative.
  • the base material 11 and the conductive polymer film 12 are bonded by the bonding portion 13 having the 1,2,3 triazole ring structure 13A.
  • the 1,2,3 triazole ring structure 13A is formed by an azide-alkyne cycloaddition reaction (so-called click reaction) between an azido group (—N 3 ) and a functional group 13B having a carbon-carbon triple bond, It is a 1,4-substitution product or a 1,5-substitution product of 1,2,3 triazole represented by Formula 1.
  • the bonding portion 13 is formed, for example, by reacting the base material 11 having the functional group 13B having a carbon-carbon triple bond with the conductive polymer monomer having an azide group. That is, the bonding portion 13 is bonded by forming a covalent bond between the base material 11 and the conductive polymer film 12. Specifically, for example, a base material 11 having an azido group and a base material 13B having a functional group 13B having a carbon-carbon triple bond are reacted with a linker 13C having functional groups 13B having a carbon-carbon triple bond at both ends. 11 is prepared and is reacted with a monomer of a conductive polymer having an azide group.
  • the binding part 13 has, for example, the 1,2,3 triazole ring structure 13A on both sides of the linker 13C, the base material 11 (for example, silk or fibroin), and the conductive polymer film 12 (specifically, The conductive polymer forming the conductive polymer film 12) is bound by a linker 13C via the 1,2,3 triazole ring structure 13A.
  • the linker is used when artificially binding a binding target such as a biomolecule and another molecule or macromolecules, and there are substituents at both ends of the binding molecule that binds the binding target.
  • the binding target is bonded by the substituent binding to the binding target.
  • the functional group 13B having a carbon-carbon triple bond may be any as long as it has reactivity with an azide group, and may be acyclic or cyclic.
  • the acyclic functional group include a monovalent substituent of alkyne or a derivative thereof. Specific examples include an ethynyl group (HC ⁇ C-).
  • the cyclic functional group include a group having a dibenzylcyclooctyne skeleton represented by Formula 2 (hereinafter referred to as DBCO) skeleton or a derivative thereof, and a difluorinated cyclooctyne represented by Formula 3.
  • BARAC a group having a biarylazacyclooctynone represented by Formula 4
  • BCN a group having a [6.1.0] nonine (bicyclo [6.1.0] nonyne; hereinafter referred to as BCN) skeleton or a derivative thereof.
  • the linker 13C may be any as long as it can bond the functional group 13B having a carbon-carbon triple bond at both ends.
  • polyethylene glycol represented by Formula 6 polyethylene glycol; hereinafter referred to as PEG
  • the degree of polymerization n of polyethylene glycol is preferably 1 to 10, for example.
  • the conductive material 10 can be manufactured, for example, as follows.
  • FIG. 3 shows a flow of manufacturing steps of the conductive material 10.
  • the base material 11 having an azide group is prepared (step 101).
  • Silk having an azido group is, for example, silk in which an unnatural amino acid having an azido group is incorporated into silk protein, and can be obtained as a cocoon by breeding a transgenic silkworm with an unnatural amino acid having an azido group.
  • This transgenic silkworm is an enzyme that selects an unnatural amino acid having an azido group by modifying the gene for phenylalanyl-tRNA synthetase, which is an enzyme that selects phenylalanine, which is one of the amino acids that make up part of silk protein. It was prepared and further genetically modified so that the modified gene works only in the silk gland, which is a tissue that synthesizes silkworm silk protein fibroin.
  • unnatural amino acids mean amino acids that do not form proteins.
  • Amino acids that make up proteins refer to the 20 standard natural amino acids, selenocysteine, and pyrrolidine. That is, the unnatural amino acid means an analog (modified amino acid) of these amino acids constituting the protein or any amino acid other than these amino acids constituting the protein.
  • this transgenic silkworm has a DNA sequence encoding a protein having an activity of binding a desired unnatural amino acid to a phenylalanine-specific tRNA. Therefore, the unnatural amino acid used is preferably a phenylalanine analog.
  • the phenylalanine analog it is preferable that at least one hydrogen atom of the side chain of finylalanine is substituted with an azido group, and the hydrogen atom of the benzene ring of the finylalanine side chain is substituted. More preferably, the para position of the benzene ring is substituted. That is, as the unnatural amino acid, for example, the amino acid represented by the formula 7 is preferable.
  • the azido group of the base material 11 having an azido group is converted into the functional group 13B having a carbon-carbon triple bond (step S102).
  • a base material 11 having an azido group is reacted with a linker 13C having a functional group 13B having a carbon-carbon triple bond at both ends to form a functional group 13B having a carbon-carbon triple bond bonded to one end of the linker 13C.
  • the azido group bonded to the base material 11 is bonded by an azide-alkyne cycloaddition reaction.
  • the base material 11 having an azide group is immersed in a linker solution in which a linker 13C having functional groups 13B having a carbon-carbon triple bond at both ends is dissolved in a solvent to cause a reaction.
  • a linker 13C having functional groups 13B having a carbon-carbon triple bond at both ends is dissolved in a solvent to cause a reaction.
  • Examples of the linker 13C having a functional group 13B having a carbon-carbon triple bond at both ends include compounds represented by Formula 8.
  • the functional group 13B having a carbon-carbon triple bond is a group having a DBCO skeleton, and the linker 13C is PEG.
  • a compound in which the functional group 13B having a carbon-carbon triple bond is bonded to both ends of the linker 13C can be used.
  • the azido group and the functional group 13B having a carbon-carbon triple bond react, for example, as shown in Formula 9 to form a 1,2,3 triazole ring structure 13A.
  • Formula 9 shows a case where the functional group 13B having a carbon-carbon triple bond is a group having a DBCO skeleton.
  • the linker 13C having the functional group 13B having a carbon-carbon triple bond at its tip is bonded to the base material 11 via the 1,2,3 triazole ring structure 13A, and the functional group 13B having a carbon-carbon triple bond is bonded.
  • the base material 11 having is obtained.
  • the base material 11 having the functional group 13B having a carbon-carbon triple bond is reacted with the conductive polymer monomer having an azide group (step S103).
  • the base material 11 having the functional group 13B having a carbon-carbon triple bond is immersed in a monomer solution in which a monomer of a conductive polymer having an azide group is dissolved for reaction. .. In that case, you may use copper ion as a catalyst.
  • EDOT 3,4-ethylenedioxythiophene
  • PEDOT and its derivative, and its derivative are preferable.
  • FIG. 2 EDOT is shown as a monomer of a conductive polymer.
  • the functional group 13B having a carbon-carbon triple bond bonded to the base material 11 and the azido group bonded to the monomer of the conductive polymer are bonded by an azide-alkyne cycloaddition reaction,
  • the base material 11 in which the conductive polymer monomer is bonded is obtained.
  • the functional group 13B having a carbon-carbon triple bond is a group having a DBCO skeleton, it reacts with an azide group as shown in Formula 9 to form a 1,2,3 triazole ring structure 13A.
  • the concentration (normality) of the conductive polymer monomer in the monomer solution is preferably 10 ⁇ M or more. This is because if the normality is low, the azide-alkyne cycloaddition reaction does not proceed sufficiently and it is difficult to sufficiently bond the monomer of the conductive polymer to the base material 11.
  • the concentration (normality) of the monomer of the conductive polymer in the monomer solution is preferably 1000 ⁇ M (1 mM) or less. This is because if the concentration is too high, there is a concern that it will remain on the base material 11, and the subsequent coating process will be difficult.
  • a reaction liquid containing a conductive polymer monomer is applied to the base material 11 to which the conductive polymer monomer is bonded, and a single amount of the conductive polymer bonded to the base material 11 is obtained.
  • the conductive polymer monomer including the body is polymerized to form the conductive polymer film 12 (step S104).
  • the reaction liquid preferably contains, for example, a solvent and an oxidizing agent that accelerates polymerization of the monomer in addition to the conductive polymer monomer, and further causes the conductive polymer to exhibit conductivity. It may contain a dopant and a thickener.
  • an iron salt is preferably used as the oxidizing agent.
  • the dopant include p-toluenesulfonic acid, and an iron salt of p-toluenesulfonic acid, for example, a 60 mass% ethanol solution of ferric p-toluenesulfonic acid (hereinafter referred to as pTS) is used. It is more preferable if it is made possible because it can function as an oxidant and a dopant. Other examples of the dopant include trifluoroacetic acid and the like.
  • the thickener is for reducing the bleeding of the conductive polymer and for accelerating the polymerization reaction of the monomer.
  • the thickener is preferably one that does not react with the polymerization reaction of the conductive polymer, and preferred examples thereof include glycerol, polyethylene glycol, gelatin, and polysaccharides.
  • the base material 11 may have any shape in each of the above steps.
  • silk may be in the state of fibers as it is, or may be formed into a thread shape, a cloth shape, a film shape, a sponge shape, or the like.
  • fibroin may be extracted from silk and formed into a thin film. Further, it may be formed into a thread shape, a cloth shape, a film shape, a sponge shape or the like in an intermediate step.
  • the base material 11 and the conductive polymer film 12 are bonded by the bonding portion 13 having the 1,2,3 triazole ring structure 13A. 12 can be firmly fixed to the base material 11. Therefore, it is possible to prevent the conductive polymer film 12 from peeling off due to repeated washing, friction, etc., and it is possible to suppress a decrease in conductivity.
  • the base material 11 having the functional group 13B having a carbon-carbon triple bond and the conductive polymer monomer having an azide group are reacted to bond the conductive polymer monomer.
  • a reaction liquid containing a monomer of a conductive polymer was applied thereto to polymerize the monomer, so that the reaction between the functional group 13B having a carbon-carbon triple bond and the azide group was performed.
  • the conductive material 10 according to the present embodiment can be easily obtained by utilizing this.
  • transgenic silkworms were fed with an unnatural amino acid having an azido group and bred to prepare a filamentous silk having an azido group (step S101). Then, the silk (base material 11) having an azide group is immersed in a linker solution prepared by dissolving a compound having a functional group 13B having a carbon-carbon triple bond at both ends of the linker 13C shown in Formula 8 in a solvent to obtain an azide-alkyne.
  • the silk (base material 11) having the functional group 13B having a carbon-carbon triple bond was produced by binding the cycloaddition reaction (see Formula 9) (step S102).
  • silk (base material 11) having a functional group 13B having a carbon-carbon triple bond was used as a monomer of a conductive polymer having an azide group, and the derivative of EDOT shown in Formula 10 was dissolved in a solvent to obtain a unit amount. It was dipped in a body solution and bonded by an azide-alkyne cycloaddition reaction (see Formula 9) to prepare silk (base material 11) having EDOT which is a monomer of a conductive polymer (step S103).
  • FIG. 4 shows a micrograph of the obtained silk (base material 11).
  • the concentration (normality) of the derivative of EDOT, which is a monomer of the conductive polymer, in the monomer solution was changed to 0 ⁇ M, 5 ⁇ M, 10 ⁇ M, 25 ⁇ M, 50 ⁇ M to obtain a functional group 13B having a carbon-carbon triple bond.
  • the silk (base material 11) having the DBCO skeleton After reacting with the silk (base material 11) having the DBCO skeleton, the unreacted DBCO skeleton remaining on the silk (base material 11) was detected.
  • the silk (base material 11) used was processed into a film, and was immersed in a monomer solution for reaction. The obtained results are shown in FIG. As shown in FIG.
  • the ones obtained by reacting the conductive polymer monomer are both unreacted DBCO skeletons as compared with the ones obtained by not reacting the conductive polymer monomer. It was found that the azido-alkyne cycloaddition reaction was occurring. It was also found that the reaction can be almost completely advanced by setting the concentration (normality) of the monomer of the conductive polymer to 10 ⁇ M or more.
  • Step S104 The reaction liquid containing EDOT is applied to the thread-like silk (base material 11) to which EDOT is bound under the reaction conditions clarified in the previous section, and EDOT is polymerized to form the conductive polymer film 12.
  • the reaction solution was prepared by mixing ethanol, pTS, which is an oxidizing agent and a dopant, and EDOT.
  • the ratio of pTS to EDOT in the reaction solution was 40:1 to 1:1 in terms of volume ratio (pTS:EDOT).
  • the polymerization reaction was performed for 2 hours in an environment of a temperature of 25 degrees and a humidity of 60%. After the polymerization reaction, the product was washed with purified water for 10 minutes and dried.
  • FIG. 6 shows a micrograph of the obtained conductive material 10.
  • the silk (base material 11) having the conductive polymer monomer before forming the conductive polymer film 12 shown in FIG. 4 was white, while the conductive high film shown in FIG.
  • the conductive material 10 on which the molecular film 12 was formed was black, and it was confirmed that the conductive polymer film 12 was formed.
  • FIG. 7 shows the obtained results of Example 1 together with the results of Comparative Example 1.
  • a conductive material was produced in the same manner as in Example 1 except that ordinary silk to which no azido group was introduced was used. That is, in Comparative Example 1, the conductive polymer film was attached to the silk, and the silk and the conductive polymer film were not bonded. As shown in FIG. 7, the sheet resistance of Example 1 was lower than that of Comparative Example 1.
  • Example 1 the change in resistance value with the number of washings was examined. Washing was performed 10 times according to JIS 0217-103 method, and the resistance value was measured each time using a two-pole tester. The results of Example 1 obtained are shown in FIG. 8 together with the results of Comparative Example 1.
  • Comparative Example 1 a conductive material was produced in the same manner as in Example 1 except that ordinary silk to which no azido group was introduced was used. As shown in FIG. 8, according to Example 1, as compared with Comparative Example 1, the increase in sheet resistance was small even after repeated washing, and after 10 times of washing, Comparative Example 1 was compared with Example 1. The resistance value was 1.5 times higher. That is, according to this example, it was found that the decrease in conductivity due to washing can be suppressed and the washing resistance can be improved.
  • Example 2 In Example 2, after thread-like silk having an azido group was processed into a satin-woven cloth (ribbon shape), the cloth-like silk was provided with functional groups 13B having a carbon-carbon triple bond at both ends of the linker 13C. The compound is reacted to form a silk having a functional group 13B having a carbon-carbon triple bond, and then a derivative of EDOT having an azide group is made to react to form a silk having EDOT, followed by applying a reaction solution containing EDOT, The conductive polymer film 12 was formed by polymerizing EDOT to obtain the conductive material 10.
  • the conductive material 10 was produced in the same manner as in Example 1, and the obtained conductive material 10 was examined in the same manner as in Example 1 for the change in the resistance value depending on the number of times of washing.
  • the conductive material 10 was manufactured as follows.
  • transgenic silkworms are administered with an unnatural amino acid having an azide group and bred to prepare a thread-shaped silk having an azide group, which is processed into a satin-woven ribbon shape and cloth-shaped.
  • Silk was produced (step S101).
  • the cloth-shaped silk having an azide group (base material 11) is dipped in a linker solution in which a compound having a functional group 13B having a carbon-carbon triple bond at both ends of the linker 13C shown in Formula 8 is dissolved in a solvent.
  • An azide-alkyne cycloaddition reaction see Formula 9 to produce a silk (base material 11) having a functional group 13B having a carbon-carbon triple bond (step S102).
  • the cloth-like silk (base material 11) having the functional group 13B having a carbon-carbon triple bond is dissolved in a solvent as a derivative of EDOT shown in Formula 10 as a conductive polymer monomer having an azide group. It is dipped in the aforesaid monomer solution and bonded by an azide-alkyne cycloaddition reaction (see Formula 9) to produce a cloth-like silk (substrate 11) having EDOT which is a conductive polymer monomer. (Step S103). Next, the cloth-like silk (base material 11) was coated with a reaction solution containing EDOT and the EDOT was polymerized to form the conductive polymer film 12 (step S104). The conditions of the reaction solution and the polymerization reaction are the same as in Example 1.
  • a reaction solution containing EDOT was applied to a cloth-like (ribbon-like) silk which is a satin weave of a normal thread-like silk without introduction of an azide group, and EDOT was applied.
  • a conductive polymer film was attached to prepare a conductive material.
  • a reaction liquid containing EDOT is applied to a cloth-shaped (ribbon-shaped) silk in which a thread-shaped silk having an azide group is satin-woven, and EDOT is polymerized to conduct electricity.
  • a conductive polymer film was attached to prepare a conductive material.
  • Comparative Examples 2-1 and 2-2 the conductive polymer film was attached to the silk, and the silk and the conductive polymer film were not bonded.
  • the cloth-like silk which is the satin weave of the thread-like silk having an azide group used in Comparative Example 2-2 was prepared in the same manner as in Example 2.
  • the change in the resistance value depending on the number of times of washing was examined in the same manner as in the example 2.
  • Figure 9 shows the results obtained. As shown in FIG. 9, according to Example 2, as compared with Comparative Examples 2-1 and 2-2, the increase in sheet resistance was small even after repeated washing. That is, according to this example, it was found that the decrease in conductivity due to washing can be suppressed and the washing resistance can be improved.

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Abstract

[Problem] To provide an electroconductive material with which it is possible to firmly secure an electroconductive polymer. [Solution] In an electroconductive material 10, an electroconductive polymer film 12 is formed on the surface of a base material 11 configured from silk, etc. The base material 11 and the electroconductive polymer film 12 are bonded by a bonding part 13 having a 1,2,3 triazole ring structure. After the base material 11, which has a functional group having a carbon-carbon triple bond, and a monomer of an electroconductive polymer having an azide group are reacted to produce the base material 11 to which the monomer of the electroconductive polymer is bonded, a reaction fluid including the monomer of the electroconductive polymer is applied to the base material 11, and the electroconductive material is obtained by polymerizing the monomer.

Description

導電材料及びその製造方法Conductive material and manufacturing method thereof
　本発明は、繊維又は薄膜の表面に導電性高分子膜が形成された導電材料およびその製造方法に関する。 The present invention relates to a conductive material having a conductive polymer film formed on the surface of a fiber or a thin film, and a method for producing the same.
　近年、ＰＥＤＯＴ－ＰＳＳ｛ポリ(３．４－エチレンジオキシチオフェン)－ポリ（スチレンスルホン酸）｝等の導電性高分子をシルク等の基材繊維に付着させた導電材料が知られている（例えば、特許文献１参照）。この導電材料は、導電性、親水性、引っ張り強度、耐水強度を有しているので、特に、生体電極の材料として利用することができる。基材繊維に導電性高分子を付着させる方法としては、特許文献１では電気化学法を用いているが、より簡単な方法として、例えば、基材繊維に導電性高分子を塗布することにより付着させることが提案されている（例えば、特許文献２参照）。 In recent years, a conductive material in which a conductive polymer such as PEDOT-PSS {poly(3.4-ethylenedioxythiophene)-poly(styrenesulfonic acid)} is attached to a base fiber such as silk ( For example, see Patent Document 1). Since this conductive material has conductivity, hydrophilicity, tensile strength, and water resistance, it can be used particularly as a material for bioelectrodes. As a method for attaching the conductive polymer to the base fiber, the electrochemical method is used in Patent Document 1, but as a simpler method, for example, the conductive polymer is attached to the base fiber by applying the conductive polymer. It has been proposed to do so (see, for example, Patent Document 2).
特表２０１２－５３１９９０号公報Special Table 2012-531990 Publication 特許第６０３５６６２号公報Japanese Patent No. 6035662 特開２００１－１１７７６号公報Japanese Patent Laid-Open No. 2001-11776 特開２０１５－１８３３４８号公報JP, 2005-183348, A 特開平１－２６００５８号公報Japanese Patent Laid-Open No. 1-260058 特許第６３３２５８５号公報Japanese Patent No. 6332585
　しかしながら、塗布により付着させた場合、洗濯等により導電性高分子が基材繊維から脱落しやすく、繰り返しの洗濯等により導電性が低下してしまうという問題があった。特に、スポーツ等の厳しい環境下で着用するウェアラブル機器の電極等に利用するには、高頻度の洗濯や摩擦等に耐えつつ、心電・心拍等の生体情報を継続的に検出する性能が必要であり、基材繊維に導電性高分子をより強固に固定化する技術の開発が望まれていた。 However, when attached by application, there was a problem that the conductive polymer was easily dropped from the base fiber by washing and the conductivity was lowered by repeated washing and the like. In particular, in order to use it for electrodes of wearable devices worn in harsh environments such as sports, it is necessary to have the ability to continuously detect biological information such as electrocardiogram and heartbeat while enduring frequent washing and friction. Therefore, it has been desired to develop a technique for more firmly fixing the conductive polymer to the base fiber.
　なお、特許文献３には、導電性繊維の表面にアジニル基を有する化合物を付着結合させることにより、導電性繊維の耐久性を向上させることが記載されている。しかし、特許文献３は、高分子繊維の表面に金属等の導電性物質を結合させ、その表面にアジニル基を有する化合物を付着結合させたものであり、基材と導電性高分子膜とを特定の構造を有する結合部により結合する本発明とは構成が全く異なっている。 Note that Patent Document 3 describes that the durability of the conductive fiber is improved by adhesively bonding a compound having an azinyl group to the surface of the conductive fiber. However, in Patent Document 3, a conductive substance such as a metal is bonded to the surface of a polymer fiber, and a compound having an azinyl group is adhered and bonded to the surface of the polymer fiber. The structure is completely different from that of the present invention in which the connection is made by a connecting portion having a specific structure.
　また、特許文献４には、電子受容体を担持しかつ電子供与性色素で染色された繊維を導電性高分子膜で被覆した導電性繊維において、導電性高分子前駆体を繊維と接触させた状態で繊維に光を照射して導電性高分子前駆体を重合させたものが記載されている。しかし、特許文献４は、繊維の染料である電子供与性色素を重合開始剤として作用させ、繊維の全周に均一な厚みで導電性高分子膜を形成することにより、導電性高分子の剥がれを抑制するものであり、基材と導電性高分子膜とを特定の構造を有する結合部により結合する本発明とは構成が全く異なっている。 Further, in Patent Document 4, in a conductive fiber in which a fiber carrying an electron acceptor and dyed with an electron donating dye is coated with a conductive polymer film, a conductive polymer precursor is brought into contact with the fiber. In this state, the fiber is irradiated with light to polymerize the conductive polymer precursor. However, in Patent Document 4, the electron-donating dye, which is a dye of the fiber, acts as a polymerization initiator to form a conductive polymer film with a uniform thickness all around the fiber, whereby the conductive polymer is peeled off. The structure is completely different from that of the present invention in which the base material and the conductive polymer film are bonded by a bonding portion having a specific structure.
　更に、特許文献５には、熱可塑性合成繊維の表面に導電性物質を含有する樹脂層を形成した導電性繊維において、熱可塑性合成繊維と樹脂層との間に接着剤被膜を形成することにより、導電性の耐久性を向上させることが記載されている。しかし、特許文献５は接着剤を用いたものであり、基材と導電性高分子膜とを特定の構造を有する結合部により結合する本発明とは構成が全く異なっている。 Further, in Patent Document 5, in a conductive fiber in which a resin layer containing a conductive substance is formed on the surface of a thermoplastic synthetic fiber, an adhesive coating is formed between the thermoplastic synthetic fiber and the resin layer. , Improving the durability of conductivity. However, Patent Document 5 uses an adhesive and has a completely different structure from the present invention in which the base material and the conductive polymer film are bonded by a bonding portion having a specific structure.
　本発明は、このような問題に基づきなされたものであり、導電性高分子を強固に固定することができる導電材料を提供することを目的とする。 The present invention has been made based on such a problem, and an object thereof is to provide a conductive material capable of firmly fixing a conductive polymer.
　本発明の導電材料は、繊維又は薄膜の表面に導電性高分子膜が形成されたものであって、繊維又は薄膜と導電性高分子膜とは、１，２，３トリアゾール環構造を有する結合部により結合されているものである。 The conductive material of the present invention has a conductive polymer film formed on the surface of a fiber or a thin film, and the fiber or thin film and the conductive polymer film are bonded to each other having a 1,2,3 triazole ring structure. Are connected by parts.
　本発明の導電材料の製造方法は、繊維又は薄膜の表面に導電性高分子膜が形成された導電材料を製造するものであって、炭素間三重結合を有する官能基をもつ繊維又は薄膜と、アジド基をもつ導電性高分子の単量体とについて、炭素間三重結合を有する官能基とアジド基とを反応させて、導電性高分子の単量体が結合した繊維又は薄膜を作製する工程と、導電性高分子の単量体が結合した繊維又は薄膜に導電性高分子の単量体を含む反応液を塗布し、単量体を重合させる工程とを含むものである。 The method for producing a conductive material of the present invention is for producing a conductive material in which a conductive polymer film is formed on the surface of a fiber or a thin film, and a fiber or a thin film having a functional group having a carbon-carbon triple bond, A process of reacting a functional group having a carbon-carbon triple bond with an azido group for a conductive polymer monomer having an azido group to prepare a fiber or a thin film to which the conductive polymer monomer is bonded. And a step of applying a reaction liquid containing the monomer of the conductive polymer to the fiber or the thin film to which the monomer of the conductive polymer is bonded and polymerizing the monomer.
　本発明の導電材料によれば、繊維又は薄膜と導電性高分子膜とを１，２，３トリアゾール環構造を有する結合部により結合するようにしたので、導電性高分子膜を繊維又は薄膜に対して強固に固定することができる。よって、繰り返しの洗濯や摩擦等により導電性高分子膜が剥離することを抑制することができ、導電性の低下を抑制することができる。 According to the conductive material of the present invention, the fiber or thin film and the conductive polymer film are bonded to each other by the bonding portion having the 1,2,3 triazole ring structure. In contrast, it can be firmly fixed. Therefore, it is possible to prevent the conductive polymer film from peeling off due to repeated washing, friction, etc., and it is possible to suppress a decrease in conductivity.
　本発明の導電材料の製造方法によれば、炭素間三重結合を有する官能基をもつ繊維又は薄膜と、アジド基を有する導電性高分子の単量体とを反応させて、導電性高分子の単量体が結合した繊維又は薄膜を作製したのち、それに導電性高分子の単量体を含む反応液を塗布し、単量体を重合させるようにしたので、炭素間三重結合を有する官能基をとアジド基との反応を利用して容易に本発明の導電材料を得ることができる。 According to the method for producing a conductive material of the present invention, a fiber or a thin film having a functional group having a carbon-carbon triple bond is allowed to react with a monomer of a conductive polymer having an azide group to form a conductive polymer. After the fiber or thin film in which the monomer is bonded is prepared, the reaction liquid containing the monomer of the conductive polymer is applied thereto to polymerize the monomer, so that the functional group having a carbon-carbon triple bond is formed. The conductive material of the present invention can be easily obtained by utilizing the reaction between the azido group and.
本発明の一実施の形態に係る導電材料の構造を概念的に表す図である。It is a figure which represents notionally the structure of the electroconductive material which concerns on one embodiment of this invention. 図１に示した導電材料の製造工程を概念的に表すものである。2 conceptually shows the manufacturing process of the conductive material shown in FIG. 1. 図１に示した導電材料の製造工程の流れ図である。2 is a flowchart of a manufacturing process of the conductive material shown in FIG. 1. 導電性高分子の単量体を結合したシルクの表面状態を表す顕微鏡写真である。It is a microscope picture showing the surface state of the silk which combined the monomer of electroconductive polymer. 導電性高分子の単量体濃度と、未反応のＤＢＣＯ骨格の量との関係を表す特性図である。It is a characteristic view showing the relationship between the monomer concentration of a conductive polymer and the amount of unreacted DBCO skeleton. 導電性高分子の単量体を結合したシルクの表面状態を表す顕微鏡写真である。It is a microscope picture showing the surface state of the silk which combined the monomer of electroconductive polymer. 導電材料のシート抵抗値について実施例１と比較例１とを比較して示す特性図である。It is a characteristic view which compares and compares Example 1 and Comparative Example 1 about the sheet resistance value of a conductive material. 洗濯による導電材料の抵抗値変化について実施例１と比較例１とを比較して示す特性図である。FIG. 4 is a characteristic diagram showing a comparison between Example 1 and Comparative Example 1 regarding changes in resistance value of a conductive material due to washing. 洗濯による導電材料の抵抗値変化について実施例２と比較例２－１及び比較例２－２とを比較して示す特性図である。FIG. 6 is a characteristic diagram showing a change in resistance value of a conductive material due to washing, comparing Example 2 with Comparative Example 2-1 and Comparative Example 2-2.
　以下、本発明の実施の形態について図面を参照して詳細に説明する。 Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.
　図１は、本発明の一実施の形態に係る導電材料１０の構造を概念的に表すものである。図２は、導電材料１０の製造工程を概念的に表すものである。本発明の導電材料１０は、繊維又は薄膜よりなる基材１１の表面に導電性高分子膜１２が形成されたものである。基材１１を構成する繊維又は薄膜の材料としては、後述するように、導電性高分子膜１２と１，２，３トリアゾール環構造１３Ａを有する結合部１３により結合することができればどのようなものでもよく、例えば、シルク又はフィブロインが好ましく挙げられる。シルクは蚕が体内で作り出す天然繊維であり、糸状、布状、フィルム状、又は、スポンジ状等、どのような形状でもよく、織物でも不織布でもよい。フィブロインはタンパク質の一種で、シルクの主成分であり、シルクから抽出して薄膜状に成形されていてもよい。導電性高分子膜１２としては、例えば、ポリ３，４－エチレンジオキシチオフェン（以下、ＰＥＤＯＴと記す）及びその誘導体のうちの少なくとも１種を含むものが好ましく挙げられる。 FIG. 1 conceptually shows the structure of a conductive material 10 according to an embodiment of the present invention. FIG. 2 conceptually shows the manufacturing process of the conductive material 10. The conductive material 10 of the present invention is one in which a conductive polymer film 12 is formed on the surface of a base material 11 made of fibers or a thin film. As the material of the fiber or the thin film forming the base material 11, what kind of material can be used as long as it can be bonded to the conductive polymer film 12 by the bonding portion 13 having the 1,2,3 triazole ring structure 13A as described later. However, silk or fibroin are preferable. Silk is a natural fiber produced by the silkworm in the body, and may have any shape such as thread, cloth, film or sponge, and may be woven or non-woven. Fibroin is a type of protein and is the main component of silk, and may be extracted from silk and formed into a thin film. Preferred examples of the conductive polymer film 12 include those containing at least one of poly 3,4-ethylenedioxythiophene (hereinafter referred to as PEDOT) and its derivative.
　基材１１と導電性高分子膜１２とは、１，２，３トリアゾール環構造１３Ａを有する結合部１３により結合されている。１，２，３トリアゾール環構造１３Ａは、アジド基（－Ｎ３）と炭素間三重結合を有する官能基１３Ｂとのアジド－アルキン付加環化反応（いわゆるクリック反応）により形成されるものであり、式１で表される１，２，３トリアゾールの１，４－置換体、又は、１，５－置換体である。 The base material 11 and the conductive polymer film 12 are bonded by the bonding portion 13 having the 1,2,3 triazole ring structure 13A. The 1,2,3 triazole ring structure 13A is formed by an azide-alkyne cycloaddition reaction (so-called click reaction) between an azido group (—N 3 ) and a functional group 13B having a carbon-carbon triple bond, It is a 1,4-substitution product or a 1,5-substitution product of 1,2,3 triazole represented by Formula 1.
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
　結合部１３は、例えば、炭素間三重結合を有する官能基１３Ｂをもつ基材１１と、アジド基をもつ導電性高分子の単量体とを反応させることにより形成される。すなわち、結合部１３は、基材１１と導電性高分子膜１２との間に共有結合を形成することにより結合している。具体的には、例えば、アジド基をもつ基材１１と、炭素間三重結合を有する官能基１３Ｂを両端にもつリンカー１３Ｃとを反応させて、炭素間三重結合を有する官能基１３Ｂをもつ基材１１を作製し、これにアジド基をもつ導電性高分子の単量体を反応させることにより形成される。よって、結合部１３は、例えば、リンカー１３Ｃの両側に１，２，３トリアゾール環構造１３Ａを有しており、基材１１（例えば、シルク又はフィブロイン）と、導電性高分子膜１２（具体的には導電性高分子膜１２を構成する導電性高分子）とは、１，２，３トリアゾール環構造１３Ａをそれぞれ介してリンカー１３Ｃにより結合されている。 The bonding portion 13 is formed, for example, by reacting the base material 11 having the functional group 13B having a carbon-carbon triple bond with the conductive polymer monomer having an azide group. That is, the bonding portion 13 is bonded by forming a covalent bond between the base material 11 and the conductive polymer film 12. Specifically, for example, a base material 11 having an azido group and a base material 13B having a functional group 13B having a carbon-carbon triple bond are reacted with a linker 13C having functional groups 13B having a carbon-carbon triple bond at both ends. 11 is prepared and is reacted with a monomer of a conductive polymer having an azide group. Therefore, the binding part 13 has, for example, the 1,2,3 triazole ring structure 13A on both sides of the linker 13C, the base material 11 (for example, silk or fibroin), and the conductive polymer film 12 (specifically, The conductive polymer forming the conductive polymer film 12) is bound by a linker 13C via the 1,2,3 triazole ring structure 13A.
　なお、リンカーは、生体分子と他の分子、又は、高分子同士等の結合対象を人為的に結合させるときに用いられるものであり、結合対象を結びつける結合分子の両端に置換基があり、この置換基が結合対象と結合することにより結合対象を結合するものである。 The linker is used when artificially binding a binding target such as a biomolecule and another molecule or macromolecules, and there are substituents at both ends of the binding molecule that binds the binding target. The binding target is bonded by the substituent binding to the binding target.
　炭素間三重結合を有する官能基１３Ｂは、アジド基との反応性を有すればどのようなものでもよく、非環式でも、環式でもよい。非環式の官能基としては、例えば、アルキン又はその誘導体の一価の置換基が挙げられる。具体的には、エチニル基（ＨＣ≡Ｃ－）が挙げられる。環式の官能基としては、例えば、式２で表されるジベンジルシクロオクチン（ｄｉｂｅｎｚｏｃｙｃｌｏｏｃｔｙｎｅ；以下、ＤＢＣＯと記す）骨格又はその誘導体を有する基、式３で表されるジフルオロ化シクロオクチン（ｄｉｆｌｕｏｒｉｎａｔｅｄ　ｃｙｃｌｏｏｃｔｙｎｅ；以下、ＤＩＦＯと記す）骨格又はその誘導体を有する基、式４で表されるビアリールアザシクロオクチノン（ｂｉａｒｙｌａｚａｃｙｃｌｏｏｃｔｙｎｏｎｅ；以下、ＢＡＲＡＣと記す）骨格又はその誘導体を有する基、式５で表されるビシクロ［６．１．０］ノニン（ｂｉｃｙｃｌｏ［６．１．０］ｎｏｎｙｎｅ；以下、ＢＣＮと記す）骨格又はその誘導体を有する基が挙げられる。 The functional group 13B having a carbon-carbon triple bond may be any as long as it has reactivity with an azide group, and may be acyclic or cyclic. Examples of the acyclic functional group include a monovalent substituent of alkyne or a derivative thereof. Specific examples include an ethynyl group (HC≡C-). Examples of the cyclic functional group include a group having a dibenzylcyclooctyne skeleton represented by Formula 2 (hereinafter referred to as DBCO) skeleton or a derivative thereof, and a difluorinated cyclooctyne represented by Formula 3. A group having a skeleton or a derivative thereof, a group having a biarylazacyclooctynone represented by Formula 4 (hereinafter, referred to as BARAC) skeleton or a derivative thereof, and a bicyclo group represented by Formula 5; Examples thereof include a group having a [6.1.0] nonine (bicyclo [6.1.0] nonyne; hereinafter referred to as BCN) skeleton or a derivative thereof.
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
　リンカー１３Ｃは、両端に炭素間三重結合を有する官能基１３Ｂを結合することができるものであればどのようなものでもよい。例えば、式６で表されるポリエチレングリコール（ｐｏｌｙｅｔｈｙｌｅｎｅ　ｇｌｙｃｏｌ；以下、ＰＥＧと記す）が好ましく挙げられる。ポリエチレングリコールの重合度ｎは、例えば、１～１０が好ましい。 The linker 13C may be any as long as it can bond the functional group 13B having a carbon-carbon triple bond at both ends. For example, polyethylene glycol represented by Formula 6 (polyethylene glycol; hereinafter referred to as PEG) is preferable. The degree of polymerization n of polyethylene glycol is preferably 1 to 10, for example.
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
　この導電材料１０は、例えば、次にようにして製造することができる。図３は導電材料１０の製造工程の流れを表すものである。 The conductive material 10 can be manufactured, for example, as follows. FIG. 3 shows a flow of manufacturing steps of the conductive material 10.
　まず、例えば、アジド基をもつ基材１１を作製する（ステップ１０１）。例えば、基材１１をシルク又はフィブロインにより構成する場合であれば、アジド基をもつシルクを作製する。アジド基をもつシルクは、例えば、アジド基をもつ非天然アミノ酸がシルクタンパク質に組み込まれたシルクであり、トランスジェニックカイコにアジド基をもつ非天然アミノ酸を投与して飼育することにより繭として得ることができる（例えば、特許文献６参照）。このトランスジェニックカイコは、シルクタンパク質の一部を構成するアミノ酸の一つであるフェニルアラニンを選び出す酵素であるフェニルアラニル－ｔＲＮＡ合成酵素の遺伝子を改変してアジド基をもつ非天然アミノ酸を選ぶ酵素がつくられるようにし、更に、カイコのシルクタンパク質であるフィブロインを合成する組織である絹糸腺でのみ改変遺伝子が働くように遺伝子組換えを行ったものである。 First, for example, the base material 11 having an azide group is prepared (step 101). For example, when the base material 11 is made of silk or fibroin, silk having an azide group is produced. Silk having an azido group is, for example, silk in which an unnatural amino acid having an azido group is incorporated into silk protein, and can be obtained as a cocoon by breeding a transgenic silkworm with an unnatural amino acid having an azido group. (For example, see Patent Document 6). This transgenic silkworm is an enzyme that selects an unnatural amino acid having an azido group by modifying the gene for phenylalanyl-tRNA synthetase, which is an enzyme that selects phenylalanine, which is one of the amino acids that make up part of silk protein. It was prepared and further genetically modified so that the modified gene works only in the silk gland, which is a tissue that synthesizes silkworm silk protein fibroin.
　なお、非天然アミノ酸とは、タンパク質を構成しないアミノ酸を意味する。タンパク質を構成するアミノ酸とは、２０種の標準天然アミノ酸、セレノシステイン、及びピロリジンを意味する。すなわち、非天然アミノ酸とは、タンパク質を構成するこれらアミノ酸の類縁体（修飾アミノ酸）、又は、タンパク質を構成するこれらアミノ酸以外の任意のアミノ酸を意味する。 Note that unnatural amino acids mean amino acids that do not form proteins. Amino acids that make up proteins refer to the 20 standard natural amino acids, selenocysteine, and pyrrolidine. That is, the unnatural amino acid means an analog (modified amino acid) of these amino acids constituting the protein or any amino acid other than these amino acids constituting the protein.
　また、このトランスジェニックカイコはフェニルアラニン特異的ｔＲＮＡに所望の非天然アミノ酸を結合させる活性を有するタンパク質をコードするＤＮＡ配列を有する。そのため、用いられる非天然アミノ酸はフェニルアラニン類縁体であることが好ましい。フェニルアラニン類縁体としては、フィニルアラニンの側鎖の少なくとも一つ以上の水素原子がアジド基によって置換されていることが好ましく、フィニルアラニン側鎖のベンゼン環の水素原子が置換されていることがより好ましく、前記ベンゼン環のパラ位が置換されていることが特に好ましい。すなわち、非天然アミノ酸としては、例えば、式７で表されるアミノ酸が好ましい。 Also, this transgenic silkworm has a DNA sequence encoding a protein having an activity of binding a desired unnatural amino acid to a phenylalanine-specific tRNA. Therefore, the unnatural amino acid used is preferably a phenylalanine analog. As the phenylalanine analog, it is preferable that at least one hydrogen atom of the side chain of finylalanine is substituted with an azido group, and the hydrogen atom of the benzene ring of the finylalanine side chain is substituted. More preferably, the para position of the benzene ring is substituted. That is, as the unnatural amino acid, for example, the amino acid represented by the formula 7 is preferable.
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
　次いで、アジド基をもつ基材１１のアジド基を、炭素間三重結合を有する官能基１３Ｂに変換する（ステップＳ１０２）。例えば、アジド基をもつ基材１１と、炭素間三重結合を有する官能基１３Ｂを両端にもつリンカー１３Ｃとを反応させ、リンカー１３Ｃの一端に結合されている炭素間三重結合を有する官能基１３Ｂと、基材１１に結合されているアジド基とをアジド－アルキン付加環化反応により結合させる。具体的には、例えば、炭素間三重結合を有する官能基１３Ｂを両端にもつリンカー１３Ｃを溶媒に溶解したリンカー溶液に、アジド基をもつ基材１１を浸漬して反応させる。その際、触媒として銅イオンを用いてもよい。 Next, the azido group of the base material 11 having an azido group is converted into the functional group 13B having a carbon-carbon triple bond (step S102). For example, a base material 11 having an azido group is reacted with a linker 13C having a functional group 13B having a carbon-carbon triple bond at both ends to form a functional group 13B having a carbon-carbon triple bond bonded to one end of the linker 13C. The azido group bonded to the base material 11 is bonded by an azide-alkyne cycloaddition reaction. Specifically, for example, the base material 11 having an azide group is immersed in a linker solution in which a linker 13C having functional groups 13B having a carbon-carbon triple bond at both ends is dissolved in a solvent to cause a reaction. In that case, you may use copper ion as a catalyst.
　炭素間三重結合を有する官能基１３Ｂを両端にもつリンカー１３Ｃとしては、例えば、式８に示した化合物が挙げられる。式８に示した化合物は、炭素間三重結合を有する官能基１３ＢがＤＢＣＯ骨格を有する基であり、リンカー１３ＣがＰＥＧのものである。式８に示した化合物以外にも、上述した炭素間三重結合を有する官能基１３Ｂをリンカー１３Ｃの両端に結合させたものを用いることができる。 Examples of the linker 13C having a functional group 13B having a carbon-carbon triple bond at both ends include compounds represented by Formula 8. In the compound shown in Formula 8, the functional group 13B having a carbon-carbon triple bond is a group having a DBCO skeleton, and the linker 13C is PEG. In addition to the compound represented by Formula 8, a compound in which the functional group 13B having a carbon-carbon triple bond is bonded to both ends of the linker 13C can be used.
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
　アジド－アルキン付加環化反応において、アジド基と炭素間三重結合を有する官能基１３Ｂとは、例えば、式９に示したように反応し、１，２，３トリアゾール環構造１３Ａを形成する。なお、式９では、炭素間三重結合を有する官能基１３ＢがＤＢＣＯ骨格を有する基である場合を示している。これにより、基材１１に、１，２，３トリアゾール環構造１３Ａを介して、炭素間三重結合を有する官能基１３Ｂを先端にもつリンカー１３Ｃが結合されて、炭素間三重結合を有する官能基１３Ｂをもつ基材１１が得られる。 In the azide-alkyne cycloaddition reaction, the azido group and the functional group 13B having a carbon-carbon triple bond react, for example, as shown in Formula 9 to form a 1,2,3 triazole ring structure 13A. Note that Formula 9 shows a case where the functional group 13B having a carbon-carbon triple bond is a group having a DBCO skeleton. Thus, the linker 13C having the functional group 13B having a carbon-carbon triple bond at its tip is bonded to the base material 11 via the 1,2,3 triazole ring structure 13A, and the functional group 13B having a carbon-carbon triple bond is bonded. The base material 11 having is obtained.
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
　続いて、炭素間三重結合を有する官能基１３Ｂをもつ基材１１と、アジド基をもつ導電性高分子の単量体とを反応させる（ステップＳ１０３）。具体的には、例えば、炭素間三重結合を有する官能基１３Ｂをもつ基材１１を、アジド基をもつ導電性高分子の単量体を溶媒に溶解した単量体溶液に浸漬して反応させる。その際、触媒として銅イオンを用いてもよい。 Subsequently, the base material 11 having the functional group 13B having a carbon-carbon triple bond is reacted with the conductive polymer monomer having an azide group (step S103). Specifically, for example, the base material 11 having the functional group 13B having a carbon-carbon triple bond is immersed in a monomer solution in which a monomer of a conductive polymer having an azide group is dissolved for reaction. .. In that case, you may use copper ion as a catalyst.
　導電性高分子の単量体としては、例えば、上述した導電性高分子、ＰＥＤＯＴ及びその誘導体の単量体である３，４－エチレンジオキシチオフェン（以下、ＥＤＯＴと記す）及びその誘導体が好ましく挙げられる。なお、図２では、導電性高分子の単量体としてＥＤＯＴを記載している。これにより、基材１１に結合されている炭素間三重結合を有する官能基１３Ｂと、導電性高分子の単量体に結合されているアジド基とがアジド－アルキン付加環化反応により結合し、導電性高分子の単量体が結合した基材１１が得られる。例えば、炭素間三重結合を有する官能基１３ＢがＤＢＣＯ骨格を有する基である場合には、式９に示したようにアジド基と反応し、１，２，３トリアゾール環構造１３Ａを形成する。 As the monomer of the conductive polymer, for example, 3,4-ethylenedioxythiophene (hereinafter referred to as EDOT) which is a monomer of the above-described conductive polymer, PEDOT and its derivative, and its derivative are preferable. Can be mentioned. In addition, in FIG. 2, EDOT is shown as a monomer of a conductive polymer. As a result, the functional group 13B having a carbon-carbon triple bond bonded to the base material 11 and the azido group bonded to the monomer of the conductive polymer are bonded by an azide-alkyne cycloaddition reaction, The base material 11 in which the conductive polymer monomer is bonded is obtained. For example, when the functional group 13B having a carbon-carbon triple bond is a group having a DBCO skeleton, it reacts with an azide group as shown in Formula 9 to form a 1,2,3 triazole ring structure 13A.
　なお、単量体溶液における導電性高分子の単量体の濃度（規定度）は、１０μＭ以上とすることが好ましい。規定度が低いと、アジド－アルキン付加環化反応が十分に進まず、導電性高分子の単量体を基材１１に十分に結合することが難しいからである。また、単量体溶液における導電性高分子の単量体の濃度（規定度）は、１０００μＭ（１ｍＭ）以下とすることが好ましい。濃度が高すぎると、基材１１上への残存が懸念され、その後の塗布工程が困難となるからである。 The concentration (normality) of the conductive polymer monomer in the monomer solution is preferably 10 μM or more. This is because if the normality is low, the azide-alkyne cycloaddition reaction does not proceed sufficiently and it is difficult to sufficiently bond the monomer of the conductive polymer to the base material 11. The concentration (normality) of the monomer of the conductive polymer in the monomer solution is preferably 1000 μM (1 mM) or less. This is because if the concentration is too high, there is a concern that it will remain on the base material 11, and the subsequent coating process will be difficult.
　そののち、導電性高分子の単量体が結合した基材１１に、導電性高分子の単量体を含む反応液を例えば塗布し、基材１１に結合された導電性高分子の単量体を含めて、導電性高分子の単量体を重合反応させ、導電性高分子膜１２を形成する（ステップＳ１０４）。反応液は、例えば、導電性高分子の単量体に加えて、溶媒及び単量体の重合を促進させる酸化剤を含んでいることが好ましく、更に、導電性高分子に導電性を発現させるためのドーパント及び増粘剤を含んでいてもよい。 After that, for example, a reaction liquid containing a conductive polymer monomer is applied to the base material 11 to which the conductive polymer monomer is bonded, and a single amount of the conductive polymer bonded to the base material 11 is obtained. The conductive polymer monomer including the body is polymerized to form the conductive polymer film 12 (step S104). The reaction liquid preferably contains, for example, a solvent and an oxidizing agent that accelerates polymerization of the monomer in addition to the conductive polymer monomer, and further causes the conductive polymer to exhibit conductivity. It may contain a dopant and a thickener.
　導電性高分子としてＰＥＤＴを用いる場合、酸化剤としては、例えば、鉄塩が好ましく挙げられる。ドーパントとしては、例えば、ｐ－トルエンスルホン酸が好ましく挙げられ、ｐ－トルエンスルホン酸の鉄塩、例えば、パラトルエンスルホン酸第二鉄の６０質量％エタノール溶液（以下、ｐＴＳと記す）を用いるようにすれば、酸化剤及びドーパントとして機能させることができるのでより好ましい。ドーパントとしては、他にも、トリフルオロ酢酸などが挙げられる。増粘剤は、導電性高分子のにじみを小さくすると共に、単量体の重合反応を促進させるためのものである。増粘剤としては、導電性高分子の重合反応に反応しないものが好ましく、例えば、グルセロール、ポリエチレングリコール、ゼラチン、又は、多糖類が好ましく挙げられる。 When PEDT is used as the conductive polymer, an iron salt is preferably used as the oxidizing agent. Preferable examples of the dopant include p-toluenesulfonic acid, and an iron salt of p-toluenesulfonic acid, for example, a 60 mass% ethanol solution of ferric p-toluenesulfonic acid (hereinafter referred to as pTS) is used. It is more preferable if it is made possible because it can function as an oxidant and a dopant. Other examples of the dopant include trifluoroacetic acid and the like. The thickener is for reducing the bleeding of the conductive polymer and for accelerating the polymerization reaction of the monomer. The thickener is preferably one that does not react with the polymerization reaction of the conductive polymer, and preferred examples thereof include glycerol, polyethylene glycol, gelatin, and polysaccharides.
　なお、上記各工程において基材１１はどのような形態とされていてもよい。例えば、シルクであれば、繊維のままの状態でもよく、糸状、布状、フィルム状、スポンジ状等に成形されていてもよい。また、シルクからフィブロインを抽出し、薄膜に成形してもよい。更に、途中の工程において糸状、布状、フィルム状、スポンジ状等に成形してもよい。 The base material 11 may have any shape in each of the above steps. For example, silk may be in the state of fibers as it is, or may be formed into a thread shape, a cloth shape, a film shape, a sponge shape, or the like. Alternatively, fibroin may be extracted from silk and formed into a thin film. Further, it may be formed into a thread shape, a cloth shape, a film shape, a sponge shape or the like in an intermediate step.
　このように本実施の形態によれば、基材１１と導電性高分子膜１２とを１，２，３トリアゾール環構造１３Ａを有する結合部１３により結合するようにしたので、導電性高分子膜１２を基材１１に対して強固に固定することができる。よって、繰り返しの洗濯や摩擦等により導電性高分子膜１２が剥離することを抑制することができ、導電性の低下を抑制することができる。 As described above, according to the present embodiment, the base material 11 and the conductive polymer film 12 are bonded by the bonding portion 13 having the 1,2,3 triazole ring structure 13A. 12 can be firmly fixed to the base material 11. Therefore, it is possible to prevent the conductive polymer film 12 from peeling off due to repeated washing, friction, etc., and it is possible to suppress a decrease in conductivity.
　また、炭素間三重結合を有する官能基１３Ｂをもつ基材１１と、アジド基を有する導電性高分子の単量体とを反応させて、導電性高分子の単量体が結合した基材１１を作製したのち、それに導電性高分子の単量体を含む反応液を塗布し、単量体を重合させるようにしたので、炭素間三重結合を有する官能基１３Ｂをとアジド基との反応を利用して容易に本実施の形態に係る導電材料１０を得ることができる。 Further, the base material 11 having the functional group 13B having a carbon-carbon triple bond and the conductive polymer monomer having an azide group are reacted to bond the conductive polymer monomer. Was prepared, and then a reaction liquid containing a monomer of a conductive polymer was applied thereto to polymerize the monomer, so that the reaction between the functional group 13B having a carbon-carbon triple bond and the azide group was performed. The conductive material 10 according to the present embodiment can be easily obtained by utilizing this.
（実施例１）
　まず、基材１１として、トランスジェニックカイコにアジド基をもつ非天然アミノ酸を投与して飼育し、アジド基をもつ糸状のシルクを作製した（ステップＳ１０１）。次いで、アジド基をもつシルク（基材１１）を、式８に示したリンカー１３Ｃの両端に炭素間三重結合を有する官能基１３Ｂをもつ化合物を溶媒に溶解したリンカー溶液に浸漬し、アジド－アルキン付加環化反応（式９参照）により結合させて、炭素間三重結合を有する官能基１３Ｂをもつシルク（基材１１）を作製した（ステップＳ１０２）。 (Example 1)
First, as the base material 11, transgenic silkworms were fed with an unnatural amino acid having an azido group and bred to prepare a filamentous silk having an azido group (step S101). Then, the silk (base material 11) having an azide group is immersed in a linker solution prepared by dissolving a compound having a functional group 13B having a carbon-carbon triple bond at both ends of the linker 13C shown in Formula 8 in a solvent to obtain an azide-alkyne. The silk (base material 11) having the functional group 13B having a carbon-carbon triple bond was produced by binding the cycloaddition reaction (see Formula 9) (step S102).
　続いて、炭素間三重結合を有する官能基１３Ｂをもつシルク（基材１１）を、アジド基をもつ導電性高分子の単量体として式１０に示したＥＤＯＴの誘導体を溶媒に溶解した単量体溶液に浸漬し、アジド－アルキン付加環化反応（式９参照）により結合させて、導電性高分子の単量体であるＥＤＯＴをもつシルク（基材１１）を作製した（ステップＳ１０３）。図４に、得られたシルク（基材１１）の顕微鏡写真を示す。 Subsequently, silk (base material 11) having a functional group 13B having a carbon-carbon triple bond was used as a monomer of a conductive polymer having an azide group, and the derivative of EDOT shown in Formula 10 was dissolved in a solvent to obtain a unit amount. It was dipped in a body solution and bonded by an azide-alkyne cycloaddition reaction (see Formula 9) to prepare silk (base material 11) having EDOT which is a monomer of a conductive polymer (step S103). FIG. 4 shows a micrograph of the obtained silk (base material 11).
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010
　なお、導電性高分子の単量体であるＥＤＯＴの誘導体の単量体溶液における濃度（規定度）を０μＭ、５μＭ、１０μＭ、２５μＭ、５０μＭと変化させて、炭素間三重結合を有する官能基１３ＢであるＤＢＣＯ骨格をもつシルク（基材１１）と反応させたのち、シルク（基材１１）に残存する未反応のＤＢＣＯ骨格を検出した。シルク（基材１１）はフィルム状に加工したものを用い、単量体溶液に浸漬して反応させた。得られた結果を図５に示す。図５に示したように、導電性高分子の単量体を反応させたものは、導電性高分子の単量体を反応させていない０μＭのものに比べて、いずれも、未反応ＤＢＣＯ骨格の量が減少しており、アジド－アルキン付加環化反応が起こっていることが分かった。また、導電性高分子の単量体の濃度（規定度）を１０μＭ以上とすれば、反応をほぼ完全に進行させることができることが分かった。 The concentration (normality) of the derivative of EDOT, which is a monomer of the conductive polymer, in the monomer solution was changed to 0 μM, 5 μM, 10 μM, 25 μM, 50 μM to obtain a functional group 13B having a carbon-carbon triple bond. After reacting with the silk (base material 11) having the DBCO skeleton, the unreacted DBCO skeleton remaining on the silk (base material 11) was detected. The silk (base material 11) used was processed into a film, and was immersed in a monomer solution for reaction. The obtained results are shown in FIG. As shown in FIG. 5, the ones obtained by reacting the conductive polymer monomer are both unreacted DBCO skeletons as compared with the ones obtained by not reacting the conductive polymer monomer. It was found that the azido-alkyne cycloaddition reaction was occurring. It was also found that the reaction can be almost completely advanced by setting the concentration (normality) of the monomer of the conductive polymer to 10 μM or more.
　次に、前項で明らかにした反応条件を用いてＥＤＯＴを結合させた糸状のシルク（基材１１）に、ＥＤＯＴを含む反応液を塗布し、ＥＤＯＴを重合させて導電性高分子膜１２を形成した（ステップＳ１０４）。反応液は、エタノールと、酸化剤及びドーパントであるｐＴＳと、ＥＤＯＴとを混合して作成した。反応液におけるｐＴＳとＥＤＯＴとの割合は、体積比（ｐＴＳ：ＥＤＯＴ）で、４０：１～１：１とした。重合反応は、温度２５度、湿度６０％の環境下において、２時間行った。重合反応の後、精製水で１０分間、水洗処理を行い、乾燥させた。図６に、得られた導電材料１０の顕微表写真を示す。図４に示した導電性高分子膜１２を形成する前の導電性高分子の単量体をもつシルク（基材１１）は白色であったのに対して、図６に示した導電性高分子膜１２を形成した導電材料１０は黒色であり、導電性高分子膜１２が形成されていることが確認された。 Next, the reaction liquid containing EDOT is applied to the thread-like silk (base material 11) to which EDOT is bound under the reaction conditions clarified in the previous section, and EDOT is polymerized to form the conductive polymer film 12. (Step S104). The reaction solution was prepared by mixing ethanol, pTS, which is an oxidizing agent and a dopant, and EDOT. The ratio of pTS to EDOT in the reaction solution was 40:1 to 1:1 in terms of volume ratio (pTS:EDOT). The polymerization reaction was performed for 2 hours in an environment of a temperature of 25 degrees and a humidity of 60%. After the polymerization reaction, the product was washed with purified water for 10 minutes and dried. FIG. 6 shows a micrograph of the obtained conductive material 10. The silk (base material 11) having the conductive polymer monomer before forming the conductive polymer film 12 shown in FIG. 4 was white, while the conductive high film shown in FIG. The conductive material 10 on which the molecular film 12 was formed was black, and it was confirmed that the conductive polymer film 12 was formed.
　得られた導電材料１０を用いて布を作製し、シート抵抗を測定した。図７に、得られた実施例１の結果を比較例１の結果と共に示す。なお、比較例１は、アジド基を導入していない通常のシルクを用いたことを除き、他は実施例１と同様にして導電材料を作製したものである。すなわち、比較例１は、シルクに導電性高分子膜を付着させたものであり、シルクと導電性高分子膜とは結合されていない。図７に示したように、実施例１の方が、比較例１に比べて、シート抵抗を低くすることができた。 A cloth was made using the obtained conductive material 10 and the sheet resistance was measured. FIG. 7 shows the obtained results of Example 1 together with the results of Comparative Example 1. In Comparative Example 1, a conductive material was produced in the same manner as in Example 1 except that ordinary silk to which no azido group was introduced was used. That is, in Comparative Example 1, the conductive polymer film was attached to the silk, and the silk and the conductive polymer film were not bonded. As shown in FIG. 7, the sheet resistance of Example 1 was lower than that of Comparative Example 1.
　また、作製した実施例１及び比較例１の導電材料１０について、洗濯回数による抵抗値の変化を調べた。洗濯はＪＩＳ０２１７－１０３法に従って１０回行い、１回毎に、抵抗値を２極のテスターを用いて測定した。図８に得られた実施例１の結果を比較例１の結果と共に示す。比較例１は、アジド基を導入していない通常のシルクを用いたことを除き、他は実施例１と同様にして導電材料を作製したものである。図８に示したように、実施例１によれば、比較例１に比べて、洗濯を繰り返してもシート抵抗の上昇が小さく、１０回洗濯後には、実施例１に比べて比較例１の方が１．５倍ほど抵抗値が高くなった。すなわち、本実施例によれば、洗濯による導電性の低下を抑制できることができ、洗濯耐性を向上させることができることが分かった。 Also, with respect to the produced conductive materials 10 of Example 1 and Comparative Example 1, the change in resistance value with the number of washings was examined. Washing was performed 10 times according to JIS 0217-103 method, and the resistance value was measured each time using a two-pole tester. The results of Example 1 obtained are shown in FIG. 8 together with the results of Comparative Example 1. In Comparative Example 1, a conductive material was produced in the same manner as in Example 1 except that ordinary silk to which no azido group was introduced was used. As shown in FIG. 8, according to Example 1, as compared with Comparative Example 1, the increase in sheet resistance was small even after repeated washing, and after 10 times of washing, Comparative Example 1 was compared with Example 1. The resistance value was 1.5 times higher. That is, according to this example, it was found that the decrease in conductivity due to washing can be suppressed and the washing resistance can be improved.
（実施例２）
　実施例２では、アジド基をもつ糸状のシルクをサテン織の布状（リボン状）に加工した後、布状のシルクに対し、リンカー１３Ｃの両端に炭素間三重結合を有する官能基１３Ｂをもつ化合物を反応させて炭素間三重結合を有する官能基１３Ｂをもつシルクとし、次いで、アジド基をもつＥＤＯＴの誘導体を反応させてＥＤＯＴをもつシルクとし、続いて、ＥＤＯＴを含む反応液を塗布し、ＥＤＯＴを重合させて導電性高分子膜１２を形成して導電材料１０とした。他は実施例１と同様にして導電材料１０を作製し、得られた導電材料１０について、実施例１と同様にして洗濯回数による抵抗値の変化を調べた。具体的には、次のようにして導電材料１０を作製した。 (Example 2)
In Example 2, after thread-like silk having an azido group was processed into a satin-woven cloth (ribbon shape), the cloth-like silk was provided with functional groups 13B having a carbon-carbon triple bond at both ends of the linker 13C. The compound is reacted to form a silk having a functional group 13B having a carbon-carbon triple bond, and then a derivative of EDOT having an azide group is made to react to form a silk having EDOT, followed by applying a reaction solution containing EDOT, The conductive polymer film 12 was formed by polymerizing EDOT to obtain the conductive material 10. Other than that, the conductive material 10 was produced in the same manner as in Example 1, and the obtained conductive material 10 was examined in the same manner as in Example 1 for the change in the resistance value depending on the number of times of washing. Specifically, the conductive material 10 was manufactured as follows.
　まず、基材１１として、トランスジェニックカイコにアジド基をもつ非天然アミノ酸を投与して飼育し、アジド基をもつ糸状のシルクを作製し、これをサテン織のリボン状に加工して布状のシルクを作製した（ステップＳ１０１）。次いで、布状としたアジド基をもつシルク（基材１１）を、式８に示したリンカー１３Ｃの両端に炭素間三重結合を有する官能基１３Ｂをもつ化合物を溶媒に溶解したリンカー溶液に浸漬し、アジド－アルキン付加環化反応（式９参照）により結合させて、炭素間三重結合を有する官能基１３Ｂをもつシルク（基材１１）を作製した（ステップＳ１０２）。 First, as a base material 11, transgenic silkworms are administered with an unnatural amino acid having an azide group and bred to prepare a thread-shaped silk having an azide group, which is processed into a satin-woven ribbon shape and cloth-shaped. Silk was produced (step S101). Next, the cloth-shaped silk having an azide group (base material 11) is dipped in a linker solution in which a compound having a functional group 13B having a carbon-carbon triple bond at both ends of the linker 13C shown in Formula 8 is dissolved in a solvent. , An azide-alkyne cycloaddition reaction (see Formula 9) to produce a silk (base material 11) having a functional group 13B having a carbon-carbon triple bond (step S102).
　続いて、炭素間三重結合を有する官能基１３Ｂをもつ布状のシルク（基材１１）を、アジド基をもつ導電性高分子の単量体として式１０に示したＥＤＯＴの誘導体を溶媒に溶解した単量体溶液に浸漬し、アジド－アルキン付加環化反応（式９参照）により結合させて、導電性高分子の単量体であるＥＤＯＴをもつ布状のシルク（基材１１）を作製した（ステップＳ１０３）。次に、布状のシルク（基材１１）に、ＥＤＯＴを含む反応液を塗布し、ＥＤＯＴを重合させて導電性高分子膜１２を形成した（ステップＳ１０４）。反応液及び重合反応の条件は実施例１と同様である。 Subsequently, the cloth-like silk (base material 11) having the functional group 13B having a carbon-carbon triple bond is dissolved in a solvent as a derivative of EDOT shown in Formula 10 as a conductive polymer monomer having an azide group. It is dipped in the aforesaid monomer solution and bonded by an azide-alkyne cycloaddition reaction (see Formula 9) to produce a cloth-like silk (substrate 11) having EDOT which is a conductive polymer monomer. (Step S103). Next, the cloth-like silk (base material 11) was coated with a reaction solution containing EDOT and the EDOT was polymerized to form the conductive polymer film 12 (step S104). The conditions of the reaction solution and the polymerization reaction are the same as in Example 1.
　また、実施例２に対する比較例２－１として、アジド基を導入していない通常の糸状のシルクをサテン織とした布状（リボン状）のシルクに、ＥＤＯＴを含む反応液を塗布し、ＥＤＯＴを重合させて導電性高分子膜を付着させて、導電材料を作製した。更に、実施例２に対する比較例２－２として、アジド基をもつ糸状のシルクをサテン織とした布状（リボン状）のシルクに、ＥＤＯＴを含む反応液を塗布し、ＥＤＯＴを重合させて導電性高分子膜を付着させて、導電材料を作製した。すなわち、比較例２－１，２－２は、シルクに導電性高分子膜を付着させたものであり、シルクと導電性高分子膜とは結合されていない。なお、比較例２－２で用いたアジド基をもつ糸状のシルクをサテン織とした布状のシルクは、実施例２と同様にして作製したものである。作製した比較例２－１，２－２についても、実施例２と同様にして洗濯回数による抵抗値の変化を調べた。 Further, as Comparative Example 2-1 with respect to Example 2, a reaction solution containing EDOT was applied to a cloth-like (ribbon-like) silk which is a satin weave of a normal thread-like silk without introduction of an azide group, and EDOT was applied. Was polymerized and a conductive polymer film was attached to prepare a conductive material. Further, as Comparative Example 2-2 with respect to Example 2, a reaction liquid containing EDOT is applied to a cloth-shaped (ribbon-shaped) silk in which a thread-shaped silk having an azide group is satin-woven, and EDOT is polymerized to conduct electricity. A conductive polymer film was attached to prepare a conductive material. That is, in Comparative Examples 2-1 and 2-2, the conductive polymer film was attached to the silk, and the silk and the conductive polymer film were not bonded. The cloth-like silk which is the satin weave of the thread-like silk having an azide group used in Comparative Example 2-2 was prepared in the same manner as in Example 2. With respect to the manufactured comparative examples 2-1 and 2-2, the change in the resistance value depending on the number of times of washing was examined in the same manner as in the example 2.
　図９に得られた結果を示す。図９に示したように、実施例２によれば、比較例２－１，２－２に比べて、洗濯を繰り返してもシート抵抗の上昇が小さかった。すなわち、本実施例によれば、洗濯による導電性の低下を抑制できることができ、洗濯耐性を向上させることができることが分かった。 Figure 9 shows the results obtained. As shown in FIG. 9, according to Example 2, as compared with Comparative Examples 2-1 and 2-2, the increase in sheet resistance was small even after repeated washing. That is, according to this example, it was found that the decrease in conductivity due to washing can be suppressed and the washing resistance can be improved.
　以上、実施の形態及び実施例を挙げて本発明を説明したが、本発明は上記実施の形態及び実施例に限定されるものではなく、種々変形可能である。例えば、上記実施の形態及び実施例では、各構成要素についても具体的に説明したが、全ての構成要素を備えていなくてもよく、他の構成要素を備えていてもよい。 Although the present invention has been described above with reference to the exemplary embodiments and examples, the present invention is not limited to the above-described exemplary embodiments and examples, and various modifications can be made. For example, in the above-described embodiment and examples, each component has been specifically described, but not all the components may be provided, and other components may be provided.
　心拍や筋電等の生体情報を計測するスマートウェアの世界市場は、２０２３年には全体で３，１８８億ドルに拡大し、特に健康・スポーツ市場で５３６億ドル、医療・ヘルスケア市場では１，２４３億ドルに拡大すると予測されている（ｃｎ－ｔｅｃｈ Ｒｅｓｅａｒｃｈ・２０１５より）。プロスポーツや医療等の特殊用途のみならず、一般スポーツや健康維持等の幅広い用途への展開を図るには、繰り返し洗濯に耐える優れた耐久性をもつ導電材料の開発が必須である。したがって、本願発明は産業上の利用可能性を有する。 The global market for smart wear, which measures biometric information such as heartbeat and myoelectricity, will expand to $318.8 billion in total by 2023, with $53.6 billion in the health and sports market and one in the medical and healthcare market. Is expected to grow to $24.3 billion (from cn-tech Research 2015). In order to expand not only for special applications such as professional sports and medical treatment but also for a wide range of applications such as general sports and health maintenance, it is essential to develop a conductive material with excellent durability that can withstand repeated washing. Therefore, the present invention has industrial applicability.
　１０…導電材料、１１…基材、１２…導電性高分子膜、１３…結合部、１３Ａ…１，２，３トリアゾール環構造、１３Ｂ…炭素間三重結合を有する官能基、１３Ｃ…リンカー 10... Conductive material, 11... Base material, 12... Conductive polymer film, 13... Bonding part, 13A... 1,2,3 triazole ring structure, 13B... Functional group having carbon-carbon triple bond, 13C... Linker

Claims (4)

  1. 　繊維又は薄膜の表面に導電性高分子膜が形成された導電材料であって、
    　前記繊維又は薄膜と前記導電性高分子膜とは、１，２，３トリアゾール環構造を有する結合部により結合されていることを特徴とする導電材料。     A conductive material having a conductive polymer film formed on the surface of a fiber or a thin film,
    The conductive material, wherein the fiber or thin film and the conductive polymer film are bonded by a bonding portion having a 1,2,3 triazole ring structure.
  2. 　前記導電性高分子膜は、ポリ３，４－エチレンジオキシチオフェン及びその誘導体のうちの少なくとも１種を含むことを特徴とする請求項１記載の導電材料。 The conductive material according to claim 1, wherein the conductive polymer film contains at least one of poly 3,4-ethylenedioxythiophene and its derivatives.
  3. 　繊維又は薄膜の表面に導電性高分子膜が形成された導電材料の製造方法であって、
    　炭素間三重結合を有する官能基をもつ繊維又は薄膜と、アジド基をもつ導電性高分子の単量体とについて、前記炭素間三重結合を有する官能基と前記アジド基とを反応させて、前記導電性高分子の単量体が結合した繊維又は薄膜を作製する工程と、
    　前記導電性高分子の単量体が結合した繊維又は薄膜に前記導電性高分子の単量体を含む反応液を塗布し、前記単量体を重合させる工程と
    　を含むことを特徴とする導電材料の製造方法。     A method for producing a conductive material in which a conductive polymer film is formed on the surface of a fiber or a thin film,
    For a fiber or thin film having a functional group having a carbon-carbon triple bond and a conductive polymer monomer having an azido group, the functional group having a carbon-carbon triple bond and the azido group are reacted to each other, A step of producing a fiber or a thin film in which a monomer of a conductive polymer is bonded,
    A step of applying a reaction liquid containing the monomer of the conductive polymer to the fiber or the thin film to which the monomer of the conductive polymer is bound, and polymerizing the monomer. Material manufacturing method.
  4. 　前記単量体として、３，４－エチレンジオキシチオフェン及びその誘導体のうちの少なくとも１種を含むことを特徴とする請求項３記載の導電材料の製造方法。 The method for producing a conductive material according to claim 3, wherein the monomer contains at least one of 3,4-ethylenedioxythiophene and its derivative.
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