JP2009001724A - Electroconductive polymeric film and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a material which exhibits a variation in modulus of elasticity by a low driving voltage. <P>SOLUTION: An electroconductive polymeric film comprises 50-99 mass% electroconductive polymer and 50-1 mass% additive having a function of retaining a water molecule, and its manufacturing is disclosed. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a conductive polymer film and a method for producing the same, and more particularly to a conductive polymer film capable of exhibiting a change in elastic modulus at a low driving voltage and a method for producing the same.

  In the field of automobiles, there is an increasing need for materials that are small and lightweight and that enable actuator operation, and devices such as cushions and seats using the materials. Examples of conventional techniques include the following.

  Patent Document 1 discloses a material in which fine particles that are electrically polarized are dispersed in an electrically insulating polymer material, and when the electric field is applied, the particles are electrically polarized to change the elastic modulus.

Patent Document 2 discloses an electrorheological gel having dynamic mechanical properties that can obtain the performance of adjusting the storage elastic modulus and other properties of the composition by applying an electric field.
Japanese Patent Publication No. 6-41350 Japanese Patent Laid-Open No. 7-258212

  However, the materials described in Patent Documents 1 and 2 have a problem that a high voltage of several kV is required in order to develop a change in the elastic modulus of the material.

  Therefore, an object of the present invention is to provide a material that can exhibit a change in elastic modulus with a low driving voltage.

  In light of the above problems, the present inventors have conducted extensive research and, as a result, give a stimulus of voltage and humidity to a film containing a conductive polymer and an additive having the ability to retain water molecules. Thus, the elastic modulus of the film was found to change, and the present invention was completed.

  That is, the present invention is a conductive polymer film containing 50 to 99% by mass of a conductive polymer and 50 to 1% by mass of an additive having a function of retaining water molecules.

  The present invention also includes a first step of adding a conductive polymer and an additive to a solvent, stirring and mixing to obtain a mixture, and forming the mixture obtained in the first step by a solution casting method. And a second step of obtaining a conductive polymer film by drying the film so that the additive having a function of retaining water molecules is 50 to 1% by mass. It is a manufacturing method of a film.

  ADVANTAGE OF THE INVENTION According to this invention, the electroconductive polymer film which can change an elasticity modulus with a low drive voltage, and its manufacturing method can be provided.

  Hereinafter, the present invention will be described in detail.

  The first of the present invention is a conductive polymer film containing 50 to 99% by mass of a conductive polymer and 50 to 1% by mass of an additive having a function of retaining water molecules.

  The conductive polymer film of the present invention contains an additive having the ability to retain water molecules. Here, in the present invention, the “additive having the ability to retain water molecules” means an additive having a hydrophilic group, and more specifically, water of a compound per unit mass at 25 ° C. It means a compound in which the amount of adsorbing (adsorption ability) exceeds that of the conductive polymer.

  The adsorptive capacity can be calculated by the following method, for example.

  First, a film made of only a conductive polymer is prepared, and the film is left in an environment with a relative humidity of 30% and a relative humidity of 70% to adsorb water, and the mass of the film is determined. The obtained mass is plotted on a graph, and the obtained straight line is extrapolated to obtain the mass at 0% relative humidity. Since the mass represents the mass of only the conductive polymer, if the mass is removed from the mass of the film left in an environment with a relative humidity of 70%, for example, it can be understood how many g of water is adsorbed at the relative humidity of 70%. Then, when the amount of water is divided by the mass of the conductive polymer, the amount of water adsorbed per unit mass of the conductive polymer can be found.

  Next, a film is produced from a mixture of the additive and the conductive polymer, and the mass of the additive and the mass of the conductive polymer in the obtained film are determined by the same method as described above. For example, if the mass of the additive and the mass of the conductive polymer are removed from the mass of the film left in an environment with a relative humidity of 70%, it can be determined how many grams of water are adsorbed at the relative humidity of 70%. Then, when the amount of water is divided by the mass of the additive, the amount of water adsorbed per unit mass of the additive can be found. The amount of water adsorbed per unit mass of the additive thus obtained is compared with the amount of water adsorbed per unit mass of the conductive polymer obtained above.

  The mechanism by which the elastic modulus of the conductive polymer film of the present invention is changed by an external stimulus is described in H.H. Okuzaki et al. , Macromolecules, 33, 8307-8311 (2000).

  The conductive polymer film of the present invention when a stimulus of humidity is applied and no voltage is applied is in a state in which water molecules are retained therein. It is thought that water molecules in the film act as a plasticizer and increase the mobility of the conductive polymer chain, thereby reducing the elastic modulus of the film. When voltage is applied to the film, Joule heat is generated in the conductive polymer. Water molecules in the film are expelled by the generated Joule heat. As a result, the elastic modulus is considered to increase.

  In order to develop a change in the elastic modulus of the conductive polymer film of the present invention due to an external stimulus, the conductive polymer is preferably used in an environment where the relative humidity is preferably 30 to 90% RH, more preferably 70 to 90% RH. The film is preferably left for 10 minutes to 1 hour to adsorb water molecules. The external stimulus is not particularly limited, and preferably includes light, a magnetic field, a voltage, etc. In order for the conductive polymer film of the present invention to cause a change in elastic modulus, the conductivity in the conductive polymer film is not limited. It is necessary for the water-soluble molecules to desorb due to the generation of Joule heat by the conducting polymer. In order to generate this Joule heat, the external stimulus is more preferably a voltage.

  When the external stimulus is voltage, the elastic modulus of the conductive polymer film of the present invention in which water molecules are adsorbed is preferably changed by applying a voltage of 1 to 10 V, more preferably 1 to 5 V.

  The conductive polymer film of the present invention contains 1 to 50% by mass of the additive having a function of retaining water molecules. By controlling the content of the additive within the above range, the resulting conductive polymer film can be prevented from increasing in volume without becoming a gel, and with a low driving voltage, the conductive polymer film A greater change in elastic modulus can be developed.

  Hereinafter, the material which comprises the conductive polymer film of this invention is demonstrated.

[Conductive polymer]
The conductive polymer used in the present invention is not particularly limited as long as it is a polymer exhibiting conductivity, and specific examples include polyacetylene, polymethylacetylene, polyphenylacetylene, polyfluoroacetylene, polybutylacetylene, Polyacetylene polymers such as polymethylphenylacetylene; polyphenylene polymers such as polyparaphenylene; polypyrrole, poly (3-methylpyrrole), poly (3-ethylpyrrole), poly (3-dodecylpyrrole), poly (3 , 4-dimethylpyrrole), poly (3-methyl-4-dodecylpyrrole), poly (N-methylpyrrole), poly (N-dodecylpyrrole), poly (N-methyl-3-methylpyrrole), poly (N -Ethyl-3-dodecylpyrrole), poly (3-carboxypyrrole) and other poly Roll polymer; Polythiophene polymer such as poly (3,4-ethylenedioxythiophene); Polyfuran; Polyselenophene; Polyisothianaphthene; Polyphenylene sulfide; Polyaniline; Polyphenylene vinylene; Polythiophene vinylene; Polyanthracene; polynaphthalene; polypyrene; polyazulene; or derivatives thereof are preferably exemplified, and these may be used alone or in combination of two or more. Among these, polypyrrole, poly (3,4-ethylenedioxythiophene), and polyaniline are more preferable from the viewpoints of stability, reliability, and availability.

  The method for producing the conductive polymer in the present invention is not particularly limited, and a conventionally known method can be employed. Specific examples of the production method include, for example, chemical polymerization, electrolytic polymerization, soluble precursor method, matrix (template) polymerization, vapor deposition such as CVD, or conductivity dispersed in water or an organic solvent. Examples thereof include a method in which a polymer dispersion is formed into a film by a spreading method (cast method), and the dispersion is evaporated and dried.

  The conductive polymer used in the present invention may further contain a dopant. By adding a dopant to the conductive polymer, higher conductivity can be exhibited.

  Specific examples of the dopant include halide ions such as chloride ion, bromide ion and iodide ion; perchlorate ion; tetrafluoroborate ion; hexafluoroarsenate ion; sulfate ion; nitrate ion; Acid ion; hexafluorosilicate ion; phosphate ion such as phosphate ion, phenyl phosphate ion, hexafluorophosphate ion; trifluoroacetate ion; alkylbenzene such as tosylate ion, ethylbenzenesulfonate ion, dodecylbenzenesulfonate ion Sulfonate ion; alkyl sulfonate ion such as methyl sulfonate ion and ethyl sulfonate ion; or polyacrylate ion, polyvinyl sulfonate ion, polystyrene sulfonate ion, poly (2-acrylamido-2-methylpropanesulfone) ) Such as high molecular ions such as ions can be mentioned preferably, it may be used in combination singly or two or more. Among these, polystyrene sulfonate ions are more preferable because they can easily adjust high conductivity and have a hydrophilic skeleton useful for retaining water molecules.

  The addition amount of the dopant is preferably 3 to 50% by mass, more preferably 10 to 30% by mass with respect to the conductive polymer.

  The form of the conductive polymer is not particularly limited, and may be any form such as solid, liquid, powder, granular, or solution.

[Additive]
The additive used in the present invention is selected from the group consisting of alcohol compounds, phenol compounds, aldehyde compounds, ketone compounds, carboxylic acid compounds, carboxylic acid ester compounds, ether compounds, sulfonic acid compounds, amine compounds, and amide compounds. At least one organic compound or surfactant. Since the organic compound and the surfactant have a hydrophilic group, the organic compound and the surfactant have a function of retaining water molecules, and can cause a larger change in elastic modulus to the conductive polymer film as described above.

  The organic compound and the surfactant may be used alone or in combination.

  Hereinafter, the organic compound and surfactant used in the present invention will be described.

<Organic compounds>
When an organic compound is used as the additive, it is selected from the group consisting of alcohol compounds, phenol compounds, aldehyde compounds, ketone compounds, carboxylic acid compounds, carboxylic acid ester compounds, ether compounds, sulfonic acid compounds, amine compounds, and amide compounds. Preferably, the organic compound is at least one organic compound.

  Specific examples of the alcohol compound include methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, 1-butanol, isobutyl alcohol, sec-butyl alcohol, tert-butyl alcohol, 1-pentanol, hexyl alcohol, octyl alcohol. 2-ethylhexyl alcohol, decyl alcohol, dodecyl alcohol, tetradecyl alcohol, hexadecyl alcohol, octadecyl alcohol, allyl alcohol, crotyl alcohol, benzyl alcohol, cyclopentyl alcohol, cyclohexyl alcohol, furfuryl alcohol, ethylene glycol monomethyl ether, ethylene glycol Monoethyl ether, ethylene glycol monopropyl ether, ethyl Monohydric alcohols such as glycol monobutyl ether, diethylene glycol monomethyl ether, or diethylene glycol monoethyl ether; ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8- Octanediol, 1,9-nonanediol, 1,10-decanediol, hydrobenzoin, benzpinacol, cyclopentane-1,2-diol, cyclohexane-1,2-diol Cyclohexane-1,4-diol, cyclohexane-1,2-dimethanol, cyclohexane-1,4-dimethanol, 1,9-nonanediol, glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, adamantanediol, adamantane Polyols such as triol, adamantanetetraol, 1,3-dimethyladamantane-5,7-diol, xylitol, sorbitol, glucose, scroll, polyethylene glycol, or polyvinyl alcohol are preferred.

  When using the said alcohol compound, it is more preferable to use a polyhydric alcohol. Since the polyhydric alcohol has many hydrophilic parts, it has the property of having a high ability to retain water molecules, and since the boiling point is high, the conductive polymer film of the present invention is formed. This is because it has the property of easily remaining in the conductive polymer.

  Specific examples of the phenol compound include phenol, o-cresol, m-cresol, p-cresol, hydroquinone, methylhydroquinone, dimethylhydroquinone, trimethylhydroquinone, di-tert-butylhydroquinone, resorcinol, methylresorcinol, catechol, Preferable examples include methylcatechol, dihydroxynaphthalene, dihydroxymethylnaphthalene, and dihydroxydimethylnaphthalene.

  Specific examples of the aldehyde compound include acetaldehyde, propionaldehyde, butyraldehyde, capronaldehyde, pyrubinaldehyde, glyoxylic acid, benzaldehyde, 2-methoxybenzaldehyde, salicylaldehyde, 4-hydroxybenzaldehyde, p-diphenylaldehyde, or croton. Preferred are aldehydes and the like.

  Specific examples of the ketone compound include acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-iso-butyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone, Preferable examples include methyl-n-hexyl ketone, di-iso-butyl ketone, trimethylnonanone, cyclohexanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, diacetone alcohol and the like.

  Specific examples of the carboxylic acid compound include formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, caproic acid, pivalic acid, acrylic acid, methacrylic acid, crotonic acid and other aliphatic monocarboxylic acids, malon Acids, succinic acid, glutaric acid, adipic acid, sebacic acid, maleic acid, fumaric acid and other aliphatic dicarboxylic acids, tartaric acid and other aliphatic oxycarboxylic acids, cyclohexane monocarboxylic acid, cyclohexene monocarboxylic acid, cis-1,2 -Cycloaliphatic carboxylic acids such as cyclohexanedicarboxylic acid, cis-4-methylcyclohexene-1,2-dicarboxylic acid, benzoic acid, toluic acid, anisic acid, p- (tert-butyl) benzoic acid, naphthoic acid, cinnamon Aromatic monocarboxylic acids such as acids, phthalic acid, isophthalic acid, terephthalic acid, naphthalic acid, trimelli , Hemimellitic acid, trimesic acid, pyromellitic acid, and aromatic polycarboxylic acids such as trimellitic acid and the like. In addition, carboxylic acid anhydrides can also be suitably used, and specific examples thereof include acid anhydrides of the above carboxylic acids.

  As the carboxylic acid ester compound, mono- or polyvalent esters of the above carboxylic acid compounds can be used. Specific examples thereof include butyl formate, ethyl acetate, butyl acetate, isobutyl isobutyrate, propyl pivalate, and pivalin. Isobutyl acid, ethyl acrylate, methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, diethyl malonate, diisobutyl malonate, diethyl succinate, dibutyl succinate, diisobutyl succinate, diethyl glutarate, dibutyl glutarate, diisobutyl glutarate Diisobutyl adipate, dibutyl sebacate, diisobutyl sebacate, diethyl maleate, dibutyl maleate, diisobutyl maleate, monomethyl fumarate, diethyl fumarate, diisobutyl fumarate, tartaric acid Ethyl, dibutyl tartrate, diisobutyl tartrate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, methyl p-toluate, ethyl p-tert-butylbenzoate, ethyl p-anisate, ethyl α-naphthoate, α -Isobutyl naphthoate, ethyl cinnamate, monomethyl phthalate, monobutyl phthalate, dibutyl phthalate, diisobutyl phthalate, dihexyl phthalate, dioctyl phthalate, di-2-ethylhexyl phthalate, diallyl phthalate, diphenyl phthalate, isophthalate Diethyl acetate, diisobutyl isophthalate, diethyl terephthalate, dibutyl terephthalate, diethyl naphthalate, dibutyl naphthalate, triethyl trimellitic acid, tributyl trimellitic acid, tetramethyl pyromellitic acid, tetrapyromellitic acid tetra Chill, or pyromellitic acid tetrabutyl are preferably exemplified.

  Specific examples of the ether compound include diethyl ether, diisopropyl ether, dibutyl ether, diisobutyl ether, diisoamyl ether, di-2-ethylhexyl ether, diallyl ether, ethyl allyl ether, butyl allyl ether, diphenyl ether, anisole, and ethyl. Phenyl ether, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, 1,3,5-trioxane, methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol dibutyl ether, Propylene glycol dimethyl ether, propylene glycol methyl ether acetate, B propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol dimethyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate or propylene glycol propyl ether acetate, and the like preferably.

  Specific examples of the sulfonic acid compound include methanesulfonic acid, benzenesulfonic acid, and p-toluenesulfonic acid.

  Specific examples of the amine compound include methylamine, ethylamine, propylamine, isopropylamine, butylamine, amylamine, hexylamine, octylamine, 2-ethylhexylamine, nonylamine, decylamine, laurylamine, pentadecylamine, cetylamine, Aliphatic primary amines such as stearylamine and cyclohexylamine; dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, diamylamine, dioctylamine, di (2-ethylhexyl) amine, didecylamine, dilaurylamine, dicetylamine, Aliphatic secondary amines such as distearylamine, methylstearylamine, ethylstearylamine, butylstearylamine; Aliphatic tertiary amines such as rehexylamine and trioctylamine; Aliphatic unsaturated amines such as triallylamine and oleylamine; Aromatic amines such as laurylaniline, stearylaniline and triphenylamine; Monoethanolamine and diethanolamine , Triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, ethylenediamine, hexamethylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2,4,6-tris (dimethyl) Aminomethyl) phenol, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole, or 1,8-diazabicyclo Etc. 5,4,0) undecene -7 (DBU) are preferably mentioned.

  Specific examples of the amide compound include N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-di-n-propylacetamide, N, N-dimethylpropionamide. N, N-diethylpropionamide, N, N-di-n-propylpropionamide, N, N-dimethylbutanamide, N, N-diethylbutanamide, N, N-di-n-propylbutanamide, N -Acetylpyrrolodiline, N-propionylpyrrolidine, N-butyrylpyrrolidine, N-acetylpiperidine, N-propionylpiperidine, N-butyrylpyrrolidine, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N- Methyl-2-piperidone, N-ethyl-2-piperidone, N-methyl-ε-caprolactam, N Ethyl -ε- caprolactam, N, N, N ', N'- tetramethylurea, N, N'- dimethylethylene urea or N, such as N'- dimethylpropyleneurea are preferably exemplified.

  Among these organic compounds, at least one selected from the group consisting of 1-butanol, 1-pentanol, ethylene glycol, polyethylene glycol, methyl ethyl ketone, and N-methyl-2-pyrrolidone is more preferable as an additive. And ethylene glycol is particularly preferable.

  Content of the said organic compound in the conductive polymer film of this invention is 1-50 mass%, More preferably, it is 5-30 mass%, More preferably, it is 5-20 mass. When the content of the organic compound is less than 1% by mass, the ability of the conductive polymer film to retain water molecules decreases, and the elastic modulus of the film may not be changed when an external stimulus is applied. . If the content of the organic compound exceeds 50% by mass, the resulting film may be gelled, and the conductivity of the film may be reduced.

<Surfactant>
The surfactant used as the additive of the present invention is not particularly limited, and conventionally known surfactants can be used. Specific examples include a cationic surfactant, an anionic surfactant, a nonionic surfactant, and an amphoteric surfactant. These may be used alone or in combination of two or more. Good.

  Examples of the cationic surfactant include alkylamine salts, quaternary ammonium salts, polyoxyethylene alkylamine salts, and polyethylene polyamine derivatives.

  Examples of the anionic surfactant include, for example, fatty acid salts, abietic acid salts, hydroxyalkanesulfonic acid salts, alkanesulfonic acid salts, dialkylsulfosuccinic acid ester salts, linear alkylbenzenesulfonic acid salts, branched alkylbenzenesulfonic acid Salts, alkylnaphthalene sulfonates, alkyl diphenyl ether disulfonates, alkylphenoxy polyoxyethylene propyl sulfonates, polyoxyethylene alkyl sulfophenyl ether salts, N-methyl-N-oleyl taurine sodium salt, N-alkyl sulfosuccinic acid monoamide Disodium salt, petroleum sulfonate, sulfated beef tallow oil, fatty acid alkyl ester sulfate ester salt, alkyl sulfate ester salt, polyoxyethylene alkyl ester Tellurium sulfate, fatty acid monoglyceride sulfate, polyoxyethylene alkylphenyl ether sulfate, polyoxyethylene styrylphenyl ether sulfate, alkyl phosphate, polyoxyethylene alkyl ether phosphate, polyoxyethylene Preferred examples include alkyl phenyl ether phosphate esters, saponified saponified styrene / maleic anhydride copolymers, partially saponified olefin / maleic anhydride copolymers, or naphthalene sulfonate formalin condensates. .

  Examples of the nonionic surfactant include, for example, polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene polystyryl phenyl ethers, polyoxyethylene alkyl amines, polyoxyethylene polyoxy Propylene alkyl ethers, glycerin fatty acid esters, sorbitan fatty acid esters, pentaerythritol fatty acid esters, propylene glycol mono fatty acid esters, sucrose fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, Polyethylene glycol fatty acid esters, polyglycerin fatty acid esters, polyoxyethylene hydrogenated castor oil, polyoxyethylene glycerin fat Esters, fatty acid diethanolamides, N, N-bis-2-hydroxyalkylamines, polyoxyethylene alkylamines, triethanolamine fatty acid esters, trialkylamine oxides, alkylalkanolamides, polyethylene glycol, or polyethylene glycol and polypropylene A copolymer with glycol is preferred.

  Of the above surfactants, the term “polyoxyethylene” can be read as “polyoxyalkylene” such as polyoxymethylene, polyoxypropylene, polyoxybutylene, etc. These surfactants can also be used.

  Preferred examples of the amphoteric surfactant include carboxybetaines, aminocarboxylic acids, sulfobetaines, aminosulfuric acid esters, imidazolines, and hydrolyzed collagens.

  Among these surfactants, more preferable as an additive is at least one selected from the group consisting of linear alkylbenzene sulfonates, branched alkylbenzene sulfonates, and dodecylbenzenesulfonic acid, and particularly preferably. Dodecylbenzenesulfonic acid.

  Content of the said surfactant in the conductive polymer film of this invention is 1-50 mass%, More preferably, it is 5-30 mass%, More preferably, it is 5-15 mass%. When the content of the surfactant is less than 1% by mass, the ability of the conductive polymer film to retain water molecules decreases, and the elastic modulus change of the film when an external stimulus is applied may not be obtained. is there. When content of the said surfactant exceeds 50 mass%, the film obtained may become a gel form and the electroconductivity of a film may fall.

  The thickness of the conductive polymer film of the present invention is preferably 1 to 50 μm, more preferably 10 to 40 μm. When the thickness is less than 1 μm, the film strength may be weakened. When the thickness exceeds 50 μm, it takes extra time for water molecules in the deep part of the film to desorb. May be slow.

  In addition, the conductive polymer film of the present invention can contain additional components such as inorganic particles such as pigments and colorants as long as the properties are not impaired.

  The second of the present invention is a method for producing a conductive polymer film.

  The method for producing a conductive polymer film according to the present invention includes a first step of adding a conductive polymer and an additive to a solvent, stirring and mixing to obtain a mixture, and a mixture obtained in the first step as a solution. It includes a second step of forming a film by a casting method and drying the film so that the additive having a function of retaining water molecules is 50 to 1% by mass to obtain a conductive polymer film.

  Hereinafter, the first step and the second step will be described.

[First step]
The first step is a step of adding a conductive polymer and an additive to a solvent, stirring and mixing to obtain a mixture.

  Since the conductive polymer and the additive are as described above, description thereof is omitted here.

  The solvent is not particularly limited as long as it dissolves the conductive polymer and the additive. However, it is preferable to select a solvent having a boiling point lower than that of the additive from the viewpoint of removing only the solvent in the second step described later and facilitating control of the amount of the additive in the conductive polymer. .

  Examples of such solvents are water, n-pentane, iso-pentane, n-hexane, iso-hexane, n-heptane, iso-heptane, 2,2,4-trimethylpentane, n-octane, iso- Aliphatic hydrocarbon solvents such as octane; benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propyl benzene, iso-propyl benzene, diethylbenzene, iso-butyl benzene, triethylbenzene, di-iso-propyl benzene , N-amylnaphthalene, trimethylbenzene and other aromatic hydrocarbon solvents; methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, sec-butanol, tert-butanol, n-penta , Iso-pentanol, 2-methylbutanol, sec-pentanol, tert-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol , Heptanol-3, n-octanol, 2-ethylhexanol, sec-octanol, n-nonyl alcohol, 2,6-dimethylheptanol-4, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetra Decyl alcohol, sec-heptadecyl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, phenylmethylcarbinol, diacetone alcohol Monoalcohol solvents such as coal and cresol; ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, pentanediol-2,4, 2-methylpentanediol-2,4, hexanediol-2,5 , Heptanediol-2,4,2-ethylhexanediol-1,3, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerin and other polyhydric alcohol solvents; acetone, methyl ethyl ketone, methyl-n-propyl Ketone, methyl-n-butyl ketone, diethyl ketone, methyl-iso-butyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone, methyl-n-hexyl ketone, di-iso-butyl ketone, trimethylnonanone, Ketone solvents such as cyclohexanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, diacetone alcohol, acetophenone, fenchon; ethyl ether, iso-propyl ether, n-butyl ether, n-hexyl ether, 2-ethylhexyl Ether, ethylene oxide, 1,2-propylene oxide, dioxolane, 4-methyldioxolane, dioxane, dimethyldioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono -N-hexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl Ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol di-n-butyl ether, diethylene glycol mono-n-hexyl ether, ethoxytriglycol, tetraethylene glycol di -N-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, te Ether solvents such as lahydrofuran and 2-methyltetrahydrofuran; diethyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, iso-propyl acetate, n-butyl acetate, iso-butyl acetate, Sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate, Methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, acetic acid Ethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, diethylene ether Glycol acetate, methoxytriglycol acetate, ethyl propionate, n-butyl propionate, iso-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-lactate Ester solvents such as amyl, diethyl malonate, dimethyl phthalate, diethyl phthalate; N-methylformamide, N, N-dimethylformamide, N, N- Nitrogen-containing solvents such as diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpropionamide, N-methylpyrrolidone; dimethyl sulfide, diethyl sulfide, thiophene, tetrahydrothiophene, dimethyl sulfoxide, sulfolane, Examples thereof include sulfur-containing solvents such as 1,3-propane sultone, and these can be used alone or in admixture of two or more.

  In addition, when the conductive polymer is in a solution form, a mixture may be obtained by adding an additive to the conductive polymer solution and stirring and mixing.

  The temperature at the time of stirring is preferably 10 to 30 ° C., and the stirring time is preferably 5 to 15 minutes.

  From the viewpoint of the balance between the amount of additive remaining in the conductive polymer film of the present invention and the conductivity, the content of the conductive polymer in the mixture obtained in this step is preferably 5 to 40% by mass. More preferably, it is 5-30 mass%.

  Further, from the viewpoint of the balance between the amount of additive remaining in the conductive polymer film of the present invention and the conductivity, the content of the additive in the mixture obtained in this step is preferably 95 to 60% by mass. More preferably, it is 95-70 mass%.

[Second step]
In the second step, the mixture obtained in the first step is formed into a film by a solution casting method, and the film is dried so that the additive having a function of retaining water molecules is 50 to 1% by mass, This is a step of obtaining a conductive polymer film.

  The base material and container to which the mixture is cast are not particularly limited, and examples thereof include glass or Teflon petri dishes, glass substrates, silicon wafers, metal plates, and the like.

  The apparatus used when drying the solvent in the mixture is not particularly limited, and examples thereof include an oven, a hot plate, and a dryer.

  The temperature at which the solvent is dried can be appropriately determined depending on the type of conductive polymer, the type of solvent, the type of additive, and the amount of the additive to be left, but in general, the lower limit of 60 ° C. A range obtained by thermogravimetric analysis (TG) and having an initial temperature of weight reduction of the solvent as an upper limit is preferable. For example, when poly (3,4-ethylenedioxythiophene) (hereinafter also referred to as PEDOT) / polystyrene sulfonic acid (hereinafter also referred to as PSS) is used as the conductive polymer and water is used as the solvent, the solvent is dried. The temperature range is preferably 70 to 120 ° C.

  The time for drying the solvent can be appropriately determined depending on the type of conductive polymer, the type of solvent, the type of additive, and the amount of additive to be left. For example, when PEDOT / PSS is used as the conductive polymer and water is used as the solvent, the time for drying the solvent is preferably 0.5 to 15 hours, more preferably 3 to 12 hours.

  The conductive polymer film of the present invention can be used for various applications, but is preferably used as a vehicle component, and can be applied as, for example, a sound absorbing material or an actuator.

  Applications other than vehicle parts include capacitors, batteries, various sensors, light emitting elements, and the like.

  The present invention will be described in further detail using the following examples and comparative examples. However, the technical scope of the present invention is not limited only to the following examples. In order to calculate the amount of additive remaining in the conductive polymer films prepared in the following Examples and Comparative Examples, the dry mass of the film consisting only of the conductive polymer was calculated in advance by the following method. did.

<Calculation of dry mass of film consisting only of conductive polymer>
19g of PEDOT / PSS (refer to the following chemical formula (1)) 1.3 mass% aqueous solution (Baytron, Baytron (registered trademark) PAG) 19g was placed in a Teflon petri dish, and an oven (Fisher Scientific, model: Model 280A) was placed. And dried at a temperature of 70 ° C. for 12 hours to obtain a film. This film is referred to as “film A”.

  The film A was allowed to stand for 1.5 hours in a constant temperature and humidity chamber (model number: SE43CRA, manufactured by Kato Co., Ltd.) maintained at a temperature of 25 ° C. and a humidity of 30%, and the mass of the film after being left was measured.

  Separately, the film A was allowed to stand for 1.5 hours in a constant temperature and humidity chamber (manufactured by Kato Corporation, model number: SE43CRA) maintained at a temperature of 25 ° C. and a humidity of 70%, and the mass of the film after being left was measured.

  The film mass after being left in an environment of 30% humidity and the film mass after being left in an environment of 70% humidity were plotted on a graph. The obtained straight line was extrapolated, and the mass at 0% humidity was defined as the dry mass of the conductive polymer film obtained when 19 g of a 1.3 mass% aqueous solution of PEDOT / PSS was collected.

Example 1
<Preparation of conductive polymer film>
A conductive polymer PEDOT / PSS 1.3 mass% aqueous solution (manufactured by Baytron, Baytron (registered trademark) PAG) 19 g and an additive ethylene glycol (hereinafter also referred to as EG) 1.0 g In a Teflon petri dish, the mixture was stirred with a magnetic stirrer for 10 minutes. Thereafter, the stirred mixture was dried at 70 ° C. for 12 hours using an oven (Fisher Scientific, model number: Model 280A) to obtain 0.3039 g of a conductive polymer film. Since the dry mass of the conductive polymer film calculated separately was 0.247 g, the mass of EG in the conductive polymer film obtained in this example was calculated to be 0.0569 g.

(Example 2)
A conductive polymer film 0.3973 g was obtained in the same manner as in Example 1 except that the PEDOT / PSS aqueous solution was 18 g and the EG was 2.0 g. Since the dry mass of the conductive polymer film calculated separately was 0.234 g, the mass of EG in the conductive polymer film obtained in this example was 0.1633 g.

(Comparative Example 1)
A conductive polymer film (2.226 g) was obtained in the same manner as in Example 1 except that the PEDOT / PSS aqueous solution was 16 g and the EG was 4.0 g. Since the dry mass of the conductive polymer film calculated separately was 0.208 g, the mass of EG in the conductive polymer film obtained in this comparative example was calculated to be 2.018 g.

(Example 3)
In the same manner as in Example 1, except that the PEDOT / PSS aqueous solution was 18 g, the EG was 2.0 g, the oven drying temperature was 100 ° C., and the oven drying time was 5 hours. 2602 g was obtained. Since the dry mass of the conductive polymer film calculated separately was 0.234 g, the mass of EG in the conductive polymer film obtained in this example was calculated to be 0.0262 g.

Example 4
A conductive polymer film 0.304 g was obtained in the same manner as in Example 3 except that the PEDOT / PSS aqueous solution was 16 g and the EG was 4.0 g. Since the dry mass of the conductive polymer film calculated separately was 0.208 g, the mass of EG in the conductive polymer film obtained in this example was calculated to be 0.096 g.

(Comparative Example 2)
A conductive polymer film 0.7184 g was obtained in the same manner as in Example 3 except that the PEDOT / PSS aqueous solution was 14 g and the EG was 6.0 g. Since the dry mass of the conductive polymer film calculated separately was 0.182 g, the mass of EG in the conductive polymer film obtained in this comparative example was calculated to be 0.5364 g.

(Comparative Example 3)
In the same manner as in Example 1 except that the PEDOT / PSS aqueous solution was 18 g, the EG was 2.0 g, the oven drying temperature was 150 ° C., and the oven drying time was 2 hours. 2328 g was obtained. Since the dry weight of the conductive polymer film calculated separately was 0.234 g, it was found that EG was not contained in the conductive polymer film obtained in this comparative example.

(Example 5)
A conductive polymer film 0.2263 g was obtained in the same manner as in Comparative Example 3 except that the PEDOT / PSS aqueous solution was 16 g and the EG was 4.0 g. Since the dry mass of the conductive polymer film calculated separately was 0.208 g, the mass of EG in the conductive polymer film obtained in this example was calculated to be 0.0183 g.

(Example 6)
A conductive polymer film 0.2585 g was obtained in the same manner as in Comparative Example 3 except that the PEDOT / PSS aqueous solution was 14 g and the EG was 6.0 g. Since the dry mass of the conductive polymer film calculated separately was 0.182 g, the mass of EG in the conductive polymer film obtained in this example was calculated to be 0.0765 g.

(Comparative Example 4)
A conductive polymer film 0.4522 g was obtained in the same manner as in Comparative Example 3, except that the PEDOT / PSS aqueous solution was 12 g and the EG was 8.0 g. Since the dry mass of the conductive polymer film calculated separately was 0.156 g, the mass of EG in the conductive polymer film obtained in this example was calculated to be 0.2962 g.

(Comparative Example 5)
In the same manner as in Example 1, except that the PEDOT / PSS aqueous solution was 16 g, the EG was 4.0 g, the oven drying temperature was 210 ° C., and the oven drying time was 30 minutes. 2069 g was obtained. Since the dry weight of the conductive polymer film calculated separately was 0.208 g, it was found that EG was not contained in the conductive polymer film obtained in this comparative example.

(Comparative Example 6)
A conductive polymer film 0.182 g was obtained in the same manner as in Comparative Example 5 except that the PEDOT / PSS aqueous solution was 14 g and the EG was 6.0 g. Since the dry weight of the conductive polymer film calculated separately was 0.182 g, it was found that EG was not contained in the conductive polymer film obtained in this comparative example.

(Comparative Example 7)
A conductive polymer film 0.156 g was obtained in the same manner as in Comparative Example 5 except that the PEDOT / PSS aqueous solution was 12 g and the EG was 8.0 g. Since the dry weight of the conductive polymer film calculated separately was 0.156 g, it was found that EG was not contained in the conductive polymer film obtained in this comparative example.

(Comparative Example 8)
A conductive polymer film 0.130 g was obtained in the same manner as in Comparative Example 5 except that the PEDOT / PSS aqueous solution was 10 g and the EG was 10 g. Since the dry weight of the conductive polymer film calculated separately was 0.130 g, it was found that EG was not contained in the conductive polymer film obtained in this comparative example.

(Example 7)
A conductive polymer PEDOT / PSS 1.3 mass% aqueous solution (manufactured by Baytron, Baytron (registered trademark) PAG) and 18 g of additive, N, N′-dimethylformamide (hereinafter also referred to as DMF) 2.0 g was taken in a Teflon petri dish and stirred with a magnetic stirrer for 10 minutes. Then, the stirred mixture was dried at 70 ° C. for 12 hours using an oven (Fisher Scientific, model number: Model 280A) to obtain 0.2864 g of a conductive polymer film. Since the dry mass of the conductive polymer film calculated separately was 0.234 g, the mass of DMF in the conductive polymer film obtained in this example was calculated to be 0.0524 g.

(Example 8)
A conductive polymer film 0.2967 g was obtained in the same manner as in Example 7 except that the PEDOT / PSS aqueous solution was 16 g and DMF was 4.0 g. Since the dry mass of the conductive polymer film calculated separately was 0.208 g, the mass of DMF in the conductive polymer film obtained in this example was calculated to be 0.0887 g.

Example 9
A conductive polymer film 0.6791 g was obtained in the same manner as in Example 7 except that the PEDOT / PSS aqueous solution was 14 g and the DMF was 6.0 g. Since the dry mass of the conductive polymer film calculated separately was 0.182 g, the mass of DMF in the conductive polymer film obtained in this example was calculated to be 0.4971 g.

(Comparative Example 9)
In the same manner as in Example 7 except that 19 g of the PEDOT / PSS aqueous solution, 1.0 g of DMF, the drying temperature of the oven was 150 ° C., and the drying time in the oven was 2 hours, the conductive polymer film 0. 2469 g was obtained. Since the dry weight of the conductive polymer film calculated separately was 0.247 g, it was found that the conductive polymer film obtained in this comparative example did not contain DMF.

(Example 10)
A conductive polymer film 0.2368 g was obtained in the same manner as in Comparative Example 9 except that the PEDOT / PSS aqueous solution was 18 g and the DMF was 2.0 g. Since the dry mass of the conductive polymer film calculated separately was 0.234 g, the mass of DMF in the conductive polymer film obtained in this example was calculated to be 0.0028 g.

Example 11
A conductive polymer film 0.2139 g was obtained in the same manner as in Comparative Example 9 except that the PEDOT / PSS aqueous solution was 16 g and the DMF was 4.0 g. Since the dry mass of the conductive polymer film calculated separately was 0.208 g, the mass of DMF in the conductive polymer film obtained in this example was calculated to be 0.0059 g.

Example 12
A conductive polymer film 0.1901 g was obtained in the same manner as in Comparative Example 9 except that the PEDOT / PSS aqueous solution was 14 g and the DMF was 6.0 g. Since the dry mass of the conductive polymer film calculated separately was 0.182 g, the mass of DMF in the conductive polymer film obtained in this example was calculated to be 0.0081 g.

(Comparative Example 10)
A conductive polymer PEDOT / PSS 1.3 mass% aqueous solution (manufactured by Baytron, Baytron (registered trademark) PAG) 18 g and an additive methanol (hereinafter also referred to as MeOH) 2.0 g, It took in the Teflon petri dish and stirred for 10 minutes with the magnetic stirrer. Thereafter, the stirred mixture was dried at 70 ° C. for 12 hours using an oven (Fisher Scientific, model number: Model 280A) to obtain 0.234 g of a conductive polymer film. Since the dry weight of the conductive polymer film calculated separately was 0.234 g, it was found that MeOH was not contained in the conductive polymer film obtained in this comparative example.

(Comparative Example 11)
A conductive polymer film 0.182 g was obtained in the same manner as in Comparative Example 10, except that the PEDOT / PSS aqueous solution was 14 g and MeOH was 6.0 g. Since the dry weight of the conductive polymer film calculated separately was 0.182 g, it was found that MeOH was not contained in the conductive polymer film obtained in this comparative example.

(Example 13)
PEDOT / PSS as a conductive polymer 1.3% by mass aqueous solution (manufactured by Baytron, Baytron (registered trademark) PAG) 18 g and 1-pentanol 2.0 g as an additive were taken in a Teflon petri dish. The mixture was stirred with a magnetic stirrer for 10 minutes. Then, the stirred mixture was dried at 70 ° C. for 12 hours using an oven (Fisher Scientific, model number: Model 280A) to obtain 0.2746 g of a conductive polymer film. Since the dry mass of the conductive polymer film calculated separately was 0.234 g, the mass of 1-pentanol in the conductive polymer film obtained in this example was calculated to be 0.0406 g.

(Example 14)
A conductive polymer film 0.2818 g was obtained in the same manner as in Example 13 except that the PEDOT / PSS aqueous solution was 16 g and 1-pentanol was 4.0 g. Since the dry mass of the conductive polymer film calculated separately was 0.208 g, the mass of 1-pentanol in the conductive polymer film obtained in this example was calculated to be 0.0738 g.

(Example 15)
Conductive polymer as in Example 13, except that 16 g of PEDOT / PSS aqueous solution, 4.0 g of 1-pentanol, oven drying temperature of 100 ° C., and oven drying time of 6 hours were used. 0.2562 g of film was obtained. Since the dry mass of the conductive polymer film calculated separately was 0.208 g, the mass of 1-pentanol in the conductive polymer film obtained in this example was calculated to be 0.0482 g.

(Example 16)
A conductive polymer film 0.2964 g was obtained in the same manner as in Example 15 except that the PEDOT / PSS aqueous solution was 14 g and 1-pentanol was 6.0 g. Since the dry mass of the conductive polymer film calculated separately was 0.182 g, the mass of 1-pentanol in the conductive polymer film obtained in this example was calculated to be 0.1144 g.

(Comparative Example 12)
A conductive polymer film 0.234 g was obtained in the same manner as in Example 13 except that the oven drying temperature was 150 ° C. and the oven drying time was 2 hours. Since the dry weight of the conductive polymer film calculated separately was 0.234 g, it was found that the conductive polymer film obtained in this comparative example did not contain 1-pentanol. .

(Example 17)
Take a Teflon petri dish with 18 g of a 1.3% by weight aqueous solution of PEDOT / PSS, which is a conductive polymer (manufactured by Baytron, Baytron (registered trademark) PAG) and 2.0 g of 1-butanol as an additive, The mixture was stirred for 10 minutes with a magnetic stirrer. Thereafter, the stirred mixture was dried at 70 ° C. for 12 hours using an oven (Fisher Scientific, model number: Model 280A) to obtain 0.2501 g of a conductive polymer film. Since the dry mass of the conductive polymer film calculated separately was 0.234 g, the mass of 1-butanol in the conductive polymer film obtained in this example was calculated to be 0.0161 g.

(Example 18)
A conductive polymer film 0.2372 g was obtained in the same manner as in Example 17 except that the PEDOT / PSS aqueous solution was 16 g and 1-butanol was 4.0 g. Since the dry mass of the conductive polymer film calculated separately was 0.208 g, the mass of 1-butanol in the conductive polymer film obtained in this example was calculated to be 0.0292 g.

Example 19
A conductive polymer film 0.2382 g was obtained in the same manner as in Example 17 except that the PEDOT / PSS aqueous solution was 14 g and 1-butanol was 6.0 g. Since the dry mass of the conductive polymer film calculated separately was 0.182 g, the mass of 1-butanol in the conductive polymer film obtained in this example was calculated to be 0.0562 g.

(Comparative Example 13)
A conductive polymer film 0.234 g was obtained in the same manner as in Example 17 except that the oven drying temperature was 150 ° C. and the oven drying time was 2 hours. Since the dry weight of the conductive polymer film calculated separately was 0.234 g, it was found that the conductive polymer film obtained in this comparative example did not contain 1-butanol.

(Example 20)
A conductive polymer PEDOT / PSS 1.3 mass% aqueous solution (manufactured by Baytron, Baytron (registered trademark) PAG) 18 g and an additive N-methyl-2-pyrrolidone (hereinafter also referred to as NMP) 2.0 g was taken in a Teflon petri dish and stirred with a magnetic stirrer for 10 minutes. Thereafter, the stirred mixture was dried at 70 ° C. for 12 hours using an oven (Fisher Scientific, model number: Model 280A) to obtain 0.283 g of a conductive polymer film. Since the dry mass of the conductive polymer film calculated separately was 0.234 g, the mass of NMP in the conductive polymer film obtained in this example was calculated to be 0.049 g.

(Example 21)
A conductive polymer film 0.307 g was obtained in the same manner as in Example 20 except that the PEDOT / PSS aqueous solution was 16 g and NMP was 4.0 g. Since the dry mass of the conductive polymer film calculated separately was 0.208 g, the mass of NMP in the conductive polymer film obtained in this example was calculated to be 0.099 g.

(Example 22)
A conductive polymer PEDOT / PSS 1.3 mass% aqueous solution (manufactured by Baytron, Baytron (registered trademark) PAG) 18 g and an additive methyl ethyl ketone (hereinafter also referred to as MEK) 2.0 g, It took in the Teflon petri dish and stirred for 10 minutes with the magnetic stirrer. Then, the stirred mixture was dried at 70 ° C. for 12 hours using an oven (Fisher Scientific, model number: Model 280A) to obtain 0.242 g of a conductive polymer film. Since the dry mass of the conductive polymer film calculated separately was 0.234 g, the mass of MEK in the conductive polymer film obtained in this example was calculated to be 0.008 g.

(Example 23)
A conductive polymer film 0.229 g was obtained in the same manner as in Example 22 except that the PEDOT / PSS aqueous solution was 16 g and the MEK was 4.0 g. Since the dry mass of the conductive polymer film calculated separately was 0.208 g, the mass of MEK in the conductive polymer film obtained in this example was calculated to be 0.021 g.

(Example 24)
19.5 g of PEDOT / PSS 1.3% by mass aqueous solution (manufactured by Baytron, Baytron (registered trademark) PAG), which is a conductive polymer, and polyethylene glycol (hereinafter also referred to as PEG) having a molecular weight of 200 as an additive 0.5 g was taken in a Teflon petri dish and stirred with a magnetic stirrer for 10 minutes. Thereafter, the stirred mixture was dried at 70 ° C. for 12 hours using an oven (manufactured by Fisher Scientific, model number: Model 280A) to obtain 0.2885 g of a conductive polymer film. Since the dry weight of the conductive polymer film calculated separately was 0.2535 g, the weight of PEG in the conductive polymer film obtained in this example was calculated to be 0.035 g.

(Example 25)
A conductive polymer film 0.313 g was obtained in the same manner as in Example 24 except that the PEDOT / PSS aqueous solution was 19 g and the PEG having a molecular weight of 200 was 1.0 g. Since the dry mass of the conductive polymer film calculated separately was 0.247 g, the mass of PEG in the conductive polymer film obtained in this example was calculated to be 0.066 g.

(Example 26)
Instead of PEG having a molecular weight of 200, 0.3145 g of a conductive polymer film was obtained in the same manner as Example 24, except that 0.5 g of PEG having a molecular weight of 400 was used. Since the dry mass of the conductive polymer film calculated separately was 0.2535 g, the mass of PEG in the conductive polymer film obtained in this example was calculated to be 0.061 g.

(Example 27)
Instead of PEG with a molecular weight of 200, 0.355 g of a conductive polymer film was obtained in the same manner as in Example 25 except that 1.0 g of PEG with a molecular weight of 400 was used. Since the dry mass of the conductive polymer film calculated separately was 0.247 g, the mass of PEG in the conductive polymer film obtained in this example was calculated to be 0.108 g.

(Example 28)
A conductive polymer film 0.3225 g was obtained in the same manner as in Example 24 except that 0.5 g of PEG having a molecular weight of 1000 was used instead of PEG having a molecular weight of 200. Since the dry mass of the conductive polymer film calculated separately was 0.2535 g, the mass of PEG in the conductive polymer film obtained in this example was calculated to be 0.069 g.

(Example 29)
In the same manner as in Example 25 except that 1.0 g of PEG having a molecular weight of 1000 was used instead of PEG having a molecular weight of 200, 0.408 g of a conductive polymer film was obtained. Since the dry mass of the conductive polymer film calculated separately was 0.247 g, the mass of PEG in the conductive polymer film obtained in this example was calculated to be 0.161 g.

(Example 30)
18 g of a 20% by mass aqueous solution of polypyrrole (hereinafter also referred to as PPy), which is a conductive polymer, having a repeating unit represented by the following chemical formula (2) (manufactured by Sigma-Aldrich Japan, product number 48255-2), EG 2.0 g as an additive was taken in a Teflon petri dish and stirred for 10 minutes with a magnetic stirrer. Thereafter, the stirred mixture was dried at 100 ° C. for 6 hours using an oven (Fisher Scientific, model number: Model 280A) to obtain 1.0404 g of a conductive polymer film. Since the dry mass of the conductive polymer film calculated separately was 0.900 g, the mass of EG in the conductive polymer film obtained in this example was calculated to be 0.1404 g.

(Comparative Example 14)
Conductive polymer film 0.800 g in the same manner as in Example 30 except that 16 g of PPy aqueous solution, 4.0 g of EG, oven drying temperature 210 ° C., and oven drying time 30 minutes. Got. Since the dry mass of the conductive polymer film calculated separately was 0.800 g, it was found that EG was not contained in the conductive polymer film obtained in this comparative example.

(Example 31)
18 g of a 20% by mass aqueous solution of polyaniline (hereinafter also referred to as PAn), which is a conductive polymer, having a repeating unit represented by the following chemical formula (3) (product number 56109-6, manufactured by Sigma-Aldrich Japan), EG 2.0 g as an additive was taken in a Teflon petri dish and stirred for 10 minutes with a magnetic stirrer. Then, the stirred mixture was dried for 6 hours at a temperature of 100 ° C. using an oven (Fisher Scientific, model number: Model 280A) to obtain 4.1002 g of a conductive polymer film. Since the dry mass of the conductive polymer film calculated separately was 3.600 g, the mass of EG in the conductive polymer film obtained in this example was calculated to be 0.5002 g.

(Comparative Example 15)
3.182 g of the conductive polymer film in the same manner as in Example 31 except that 16 g of the aqueous solution of PAn, 4.0 g of EG, the drying temperature of the oven was 210 ° C., and the drying time in the oven was 30 minutes. Got. Since the dry weight of the conductive polymer film calculated separately was 3.182 g, it was found that EG was not contained in the conductive polymer film obtained in this comparative example.

(Example 32)
19.0 g of a 1.3% by mass aqueous solution of PEDOT / PSS, which is a conductive polymer (manufactured by Baytron, Baytron (registered trademark) PAG), and dodecylbenzenesulfonic acid (hereinafter also referred to as DBS) as an additive 1 0.0 g was taken in a Teflon petri dish and stirred with a magnetic stirrer for 10 minutes. Then, the stirred mixture was dried at 70 ° C. for 12 hours using an oven (Fisher Scientific, model number: Model 280A) to obtain 0.2708 g of a conductive polymer film. Since the dry mass of the conductive polymer film calculated separately was 0.247 g, the mass of DBS in the conductive polymer film obtained in this example was calculated to be 0.0238 g.

(Example 33)
A conductive polymer film 0.3043 g was obtained in the same manner as in Example 32 except that the PEDOT / PSS aqueous solution was 18 g and the DBS was 2.0 g. Since the dry mass of the conductive polymer film calculated separately was 0.234 g, the mass of DBS in the conductive polymer film obtained in this example was calculated to be 0.0703 g.

(Example 34)
A conductive polymer film 0.3444 g was obtained in the same manner as in Example 32 except that the PEDOT / PSS aqueous solution was 16 g and the DBS was 4.0 g. Since the dry weight of the conductive polymer film calculated separately was 0.208 g, the weight of DBS in the conductive polymer film obtained in this example was calculated to be 0.1364 g.

  The characteristic evaluation of the conductive polymer film obtained in each of the above Examples and Comparative Examples was performed by the following method.

<Evaluation 1: Film shape>
The case where the obtained film has a self-supporting property was evaluated as ◯, and the case where the obtained film was a gel and did not have a self-supporting property was evaluated as ×.

<Evaluation 2: Measurement of change in elastic modulus of film>
The change in elastic modulus of the film was measured using an apparatus 10 as shown in FIG.

  The conductive polymer film 14 obtained in each example and each comparative example was cut into a strip of 3 mm × 60 mm, and a conductive paste (Dotite D-550, manufactured by Fujikura Kasei Co., Ltd.) was formed on each 10 mm portion from both ends. ) Was applied. Next, 10 mm portions from both ends of the strip-shaped film coated with the conductive paste are fixed to the fixing jig 13 (the conductive wire 15 is directly connected) of the stress evaluation device 12 integrated with the constant temperature and humidity chamber 11. I let you. The fixed film was allowed to stand for 1.5 hours under the conditions of 25 ° C. and a relative humidity of 70% RH, and water was saturated and adsorbed. Thereafter, a stress-strain curve when a voltage of 4 V was applied to the fixed film by a voltage application device 16 and a stress-strain curve when no voltage was applied were measured. The modulus of elasticity was calculated from the slope of the obtained stress-strain curve, and the difference between the modulus of elasticity when a voltage of 4 V was applied and the modulus of elasticity when no voltage was applied was defined as the “elastic modulus change width”.

<Evaluation 3: Measurement of film conductivity>
(Measurement method of conductivity)
The conductivity (σ) was obtained by calculating the reciprocal of the volume resistivity (ρv). The volume resistivity is expressed as a product of the sheet resistance (ρs) and the film thickness (t) (that is, ρv = ρs × t). Therefore, the conductivity (σ) is expressed by the following formula 1. .

  The sheet resistance and film thickness were measured by the following method and substituted into the above Equation 1 to calculate the conductivity.

(Measuring method of sheet resistance)
The sheet resistance (ρs) was measured by mounting a 4-terminal 4-probe PSP probe on a resistivity meter (Dia Instruments, Lorester GP, MC P-T600 type).

(Measuring method of film thickness)
The film thickness (t) was measured using DIGIMATIC MICROMETER (manufactured by Mitutoyo Corporation).

  The obtained results are shown in Tables 1 to 7 below.

  As can be seen from Tables 1 to 7, it has been found that the conductive polymer film of the present invention containing the conductive polymer and the additive exhibits a change in elastic modulus by stimulation of humidity and voltage. In Table 1, when Example 5 which is a conductive polymer film of the present invention is compared with Comparative Example 3 which is a conductive polymer film containing no additive, the conductivity of the film of Example 5 is slightly reduced. However, it was found that a larger elastic modulus change range was exhibited. Moreover, the film of the comparative example 1, the comparative example 2, and the comparative example 4 whose content of an additive is outside the range of the present invention became a gel. Furthermore, when Table 1 and Table 3 were compared, it was found that EG, which is a dihydric alcohol, exhibits a larger elastic modulus change width than 1-pentanol and 1-butanol, which are monohydric alcohols.

  Moreover, when surfactant was used as an additive (Examples 32-34), it turned out that a bigger elastic modulus change range can be expressed with the addition amount smaller than an organic compound.

It is the schematic of the apparatus used when measuring an elasticity modulus.

Explanation of symbols

10 Elastic modulus change measuring device,
11 constant temperature and humidity chamber,
12 Stress evaluation device,
13 Fixing jig,
14 conductive polymer film,
15 conductors,
16 Voltage application device.

Claims (10)

50 to 99% by mass of a conductive polymer,
50 to 1% by mass of an additive having a function of retaining water molecules,
Conductive polymer film containing   The additive is at least one selected from the group consisting of alcohol compounds, phenol compounds, aldehyde compounds, ketone compounds, carboxylic acid compounds, carboxylic acid ester compounds, ether compounds, sulfonic acid compounds, amine compounds, and amide compounds. The conductive polymer film according to claim 1, wherein the conductive polymer film is an organic compound.   The organic compound is at least one organic compound selected from the group consisting of 1-butanol, 1-pentanol, ethylene glycol, polyethylene glycol, methyl ethyl ketone, and N-methyl-2-pyrrolidone. The conductive polymer film according to claim 2.   The conductive polymer film according to claim 3, wherein the content of the organic compound is 5 to 20% by mass.   The conductive polymer film according to claim 1, wherein the additive is a surfactant.   The conductive agent according to claim 5, wherein the surfactant is at least one selected from the group consisting of linear alkylbenzene sulfonates, branched alkylbenzene sulfonates, and dodecylbenzene sulfonic acid. Polymer film.   The conductive polymer film according to claim 5 or 6, wherein a content of the surfactant is 5 to 15% by mass. A first step of adding a conductive polymer and an additive to a solvent, stirring and mixing to obtain a mixture;
The mixture obtained in the first step is formed into a film by a solution casting method, the film is dried so that the additive having a function of retaining water molecules is 50 to 1% by mass, and a conductive polymer film is formed. A second step of obtaining;
A method for producing a conductive polymer film, comprising:   The method for producing a conductive polymer film according to claim 8, wherein a temperature at which the film is dried is 70 to 120 ° C.   The method for producing a conductive polymer film according to claim 8 or 9, wherein the time for drying the film is 0.5 hours to 15 hours.

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