Conductive polymer composition and conductive polymer film

Abstract

To provide a conductive polymer composition that is used to produce a transparent electrode having excellent total light transmittance, the conductive polymer composition having excellent storage stability.SOLUTION: A conductive polymer composition comprises a specific polythiophene compound (A) of 0.01-10 wt.%, a water-dispersible metal (B) of 0.01-0.5 wt.% and water.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a conductive polymer composition and a conductive polymer film. [Background technology]

[0002] Conductive polymer materials have been developed in which π-conjugated polymers, such as polyacetylene, polythiophene, polyaniline, and polypyrrole, are doped with electron-accepting compounds as dopants, and their applications are being investigated, for example, as antistatic agents, solid electrolytes for capacitors, conductive paints, electromagnetic wave shields, electrochromic elements, electrode materials, thermoelectric conversion materials, transparent conductive films, chemical sensors, and actuators. Among these, polythiophene-based conductive polymer materials are practically useful in terms of chemical stability (see, for example, Patent Documents 1 and 2).

[0003] Examples of polythiophene-based conductive polymer materials include a PEDOT:PSS aqueous dispersion solution obtained by polymerizing 3,4-ethylenedioxythiophene (EDOT) in an aqueous solution of polystyrene sulfonic acid (PSS), which serves as a dopant, and so-called self-doped conductive polymers that have substituents (sulfo groups, sulfonate groups, etc.) that combine water solubility and doping properties in the polymer main chain, either directly or via a spacer; for example, sulfonated polyaniline, PEDOT-S, etc. are known (see, for example, Non-Patent Documents 1 and 2).

[0004] As an application of these conductive polymers, development into transparent electrodes is being considered (see, for example, Patent Document 3). [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2011-152667 [Patent Document 2] Japanese Patent Application Laid-Open No. 2008-235645 [Patent Document 3] Japanese Patent Application Laid-Open No. 2009-205924 [Non-patent literature]

[0006] [Non-Patent Document 1] Journal of American Chemical Society,112,2801-2803(1990) [Non-patent document 2] Advanced Materials,Vol.23(38)4403-4408(2011) Summary of the Invention [Problem to be solved by the invention]

[0007] Conventionally known transparent electrodes made of a mixture of a conductive polymer and a microstructured metal have had a problem in that they have low total light transmittance.

[0008] Furthermore, it has been found that conventionally known mixtures of conductive polymers and microstructured metals developed for transparent electrodes have problems with operability and storage stability because they tend to form aggregates.

[0009] The present invention has been made in view of the above-mentioned background art, and an object of the present invention is to provide a conductive polymer composition having excellent storage stability for producing a transparent electrode having excellent total light transmittance. [Means for solving the problem]

[0010] As a result of extensive investigations aimed at solving the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by a conductive polymer composition comprising a polythiophene (A) containing at least one structural unit selected from the group consisting of a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2), 0.01 to 0.5 wt % of a water-dispersible metal (B), and water, and have thus completed the present invention.

[0011] That is, the present invention relates to the following conductive polymer composition and conductive polymer film. The conductive polymer film obtained from this composition can be used, for example, as a transparent electrode or a transparent conductive film. [1] A conductive polymer composition comprising 0.01 to 10% by weight of a polythiophene (A) containing at least one structural unit selected from the group consisting of a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2), 0.01 to 0.5% by weight of a water-dispersible metal (B), and water:

[0012] [ka]

[0013] [In the above general formulas (1) and (2), R 2 represents a hydrogen atom, a methyl group, an ethyl group, a linear or branched alkyl group having 3 to 6 carbon atoms, or a fluorine atom, m represents an integer of 1 to 10, and n represents 0 or 1. [2] The conductive polymer composition according to [1], wherein the water-dispersible metal (B) is at least one selected from the group consisting of silver nanoparticles, silver nanoplates, silver nanowires, copper nanoparticles, copper nanoplates, and copper nanowires. [3] The conductive polymer composition according to [1] or [2], wherein the water-dispersible metal (B) is silver nanowires. [4] The conductive polymer composition according to any one of [1] to [3], further comprising a surfactant in addition to the polythiophene (A), the water-dispersible metal (B), and water. [5] The conductive polymer composition according to any one of [1] to [3], further comprising an alcohol in addition to the polythiophene (A), the water-dispersible metal (B), and water. [6] The conductive polymer composition according to any one of [1] to [3], further comprising, in addition to the polythiophene (A), the water-dispersible metal (B), and water, a compound (C) capable of forming an ion pair with a sulfonic acid group of the polythiophene (A). [7] The conductive polymer composition according to any one of [1] to [6], wherein the concentration of water in the conductive polymer composition is in the range of 80 to 99.5% by weight. [8] The conductive polymer composition according to any one of [1] to [7], which has a pH at room temperature in the range of 1.0 to 10.0. [9] A method for producing a film, comprising applying the conductive polymer composition according to any one of [1] to [8] to a support and then drying it.

[10] A film comprising a polythiophene (A) containing at least one structural unit selected from the group consisting of a structural unit represented by the following general formula (1') and a structural unit represented by the following general formula (2'), and a water-dispersible metal (B):

[0014] [ka]

[0015] [In the above general formulas (1') and (2'), R 2 represents a hydrogen atom, a methyl group, an ethyl group, a linear or branched alkyl group having 3 to 6 carbon atoms, or a fluorine atom, m represents an integer of 1 to 10, and n represents 0 or 1. M represents a hydrogen ion, an alkali metal ion, an ammonium ion, an organic ammonium ion, or a quaternary ammonium ion.] [Effects of the Invention]

[0016] The present invention can provide a conductive polymer composition for producing a transparent electrode having excellent total light transmittance, and has the effect that a transparent electrode produced using the conductive polymer composition has a significantly superior total light transmittance compared to that of conventional techniques.

[0017] Furthermore, the conductive polymer composition of the present invention does not cause aggregation and has excellent storage stability, which is a significant advantage that it is extremely preferable for industrial use. DETAILED DESCRIPTION OF THE INVENTION

[0018] The present invention will be described in detail below.

[0019] The conductive polymer composition of the present invention is a conductive polymer composition characterized by containing 0.01 to 10% by weight of polythiophene (A) containing at least one structural unit selected from the group consisting of structural units represented by the following general formula (1) and structural units represented by the following general formula (2), 0.01 to 0.5% by weight of a water-dispersible metal (B), and water:

[0020] [ka]

[0021] [In general formulas (1) and (2), R 2 represents a hydrogen atom, a methyl group, an ethyl group, a linear or branched alkyl group having 3 to 6 carbon atoms, or a fluorine atom, m represents an integer of 1 to 10, and n represents 0 or 1. In the above general formulas (1) and (2), R 2 represents a hydrogen atom, a methyl group, an ethyl group, a linear or branched alkyl group having 3 to 6 carbon atoms, or a fluorine atom.

[0022] The linear or branched alkyl group having 3 to 6 carbon atoms is not particularly limited, but examples thereof include an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a neopentyl group, a tert-pentyl group, a cyclopentyl group, an n-hexyl group, a 2-ethylbutyl group, and a cyclohexyl group.

[0023] The above R 2 In terms of film-forming properties, the group is preferably a hydrogen atom, a methyl group, an ethyl group, or a fluorine atom, and more preferably a hydrogen atom or a methyl group.

[0024] In the above general formulas (1) and (2), m represents an integer of 1 to 10, and from the viewpoint of film-forming properties, it is preferably an integer of 1 to 6, more preferably an integer of 1 to 4, and even more preferably 2 or 3.

[0025] In the above general formulas (1) and (2), n represents 0 or 1, and n is preferably 1 in terms of excellent conductivity.

[0026] The structural unit represented by the general formula (2) represents the doped state of the structural unit represented by the general formula (1).

[0027] Dopants that cause an insulator-metal transition through doping can be divided into acceptors and donors. The former enters the vicinity of the polymer chain of a conductive polymer through doping and removes π electrons from the conjugated system of the main chain. As a result, positive charges (holes) are injected into the main chain, and so they are also called p-type dopants. Conversely, the latter donates electrons to the conjugated system of the main chain, and these electrons move through the conjugated system of the main chain, so they are also called n-type dopants.

[0028] The dopant in the present invention is a sulfo group or sulfonate group covalently bonded within the polymer molecule, and is a p-type dopant. Polymers that exhibit conductivity without the addition of an external dopant are called self-doping polymers.

[0029] The polythiophene (A) of the present invention can be produced by polymerizing a thiophene monomer represented by the following general formula (3) in water or an alcohol solvent in the presence of an oxidizing agent, followed by acid treatment as needed.

[0030] [ka]

[0031] In the above general formula (3), M represents a hydrogen ion or a metal ion. 2represents a hydrogen atom, a methyl group, an ethyl group, a linear or branched alkyl group having 3 to 6 carbon atoms, or a fluorine atom, m represents an integer of 1 to 10, and n represents 0 or 1. The metal ion represented by M in general formula (3) is not particularly limited, but examples thereof include transition metal ions, noble metal ions, non-ferrous metal ions, alkali metal ions (e.g., Li ions, Na ions, and K ions), and alkaline earth metal ions.

[0032] When the polymer obtained by polymerization of the thiophene monomer represented by general formula (3) is a salt of a metal ion (when M is a metal ion), M can be converted to a hydrogen ion by treating the resulting polymer with an acid. That is, even when M in general formula (3) is a metal ion, it is possible to produce a polythiophene (A) containing at least one structural unit selected from the group consisting of structural units represented by general formula (1) and structural units represented by general formula (2). Furthermore, by mixing the polythiophene (A) with an alkali metal compound or an amine compound, it is possible to produce a polythiophene containing at least one structural unit selected from the group consisting of structural units represented by general formula (1') and structural units represented by general formula (2').

[0033] The thiophene monomer represented by the general formula (3) is not particularly limited, but specific examples thereof include 6-(2,3-dihydro-thieno[3,4-b][1,4]dioxin-2-yl)hexane-1-sulfonic acid, sodium 6-(2,3-dihydro-thieno[3,4-b][1,4]dioxin-2-yl)hexane-1-sulfonate, lithium 6-(2,3-dihydro-thieno[3,4-b][1,4]dioxin-2-yl)hexane-1-sulfonate, and 6-(2,3-dihydro-thieno[3,4-b][1,4]dioxin-2-yl)hexane-1-sulfonate. ) hexane-1-sulfonic acid potassium, 8-(2,3-dihydro-thieno[3,4-b][1,4]dioxin-2-yl)octane-1-sulfonic acid, 8-(2,3-dihydro-thieno[3,4-b][1,4]dioxin-2-yl)octane-1-sulfonic acid sodium salt, 8-(2,3-dihydro-thieno[3,4-b][1,4]dioxin-2-yl)octane-1-sulfonic acid potassium salt, 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-propanesulfonic acid sodium salt, 3-[(2 ,3-Dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-propanesulfonate potassium, 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-methyl-1-propanesulfonate sodium, 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-ethyl-1-propanesulfonate sodium, 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-propyl-1- Sodium propanesulfonate, sodium 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-butyl-1-propanesulfonate, sodium 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-pentyl-1-propanesulfonate, sodium 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-hexyl-1-propanesulfonate, sodium 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-hexyl-1-propanesulfonate, sodium 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-isopropyl-1-propanesulfonate, sodium 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-isobutyl-1-propanesulfonate, sodium 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-isopentyl-1-propanesulfonate, sodium 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]- Sodium 1-fluoro-1-propanesulfonate, potassium 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-methyl-1-propanesulfonate, 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-methyl-1-propanesulfonic acid, ammonium 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-methyl-1-propanesulfonate, Triethylammonium Hydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-methyl-1-propanesulfonate, Sodium 4-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-butanesulfonate, Potassium 4-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-butanesulfonate, 4-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]- Examples include sodium 1-methyl-1-butanesulfonate, potassium 4-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-methyl-1-butanesulfonate, sodium 4-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-fluoro-1-butanesulfonate, and potassium 4-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-fluoro-1-butanesulfonate.

[0034] In the present invention, the conductivity of the polythiophene (A) is not particularly limited, but it is preferable that the conductivity (electrical conductivity) in the film state is 10 S / cm or more.

[0035] The polythiophene (A) used in the present invention may be synthesized based on publicly known information.

[0036] The conductive polymer composition of the present invention is characterized in that the concentration of the polythiophene (A) containing at least one structural unit selected from the group consisting of the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2) is in the range of 0.01 to 10% by weight. From the viewpoint of excellent conductivity and operability, the concentration of the polythiophene (A) in the conductive polymer composition of the present invention is preferably in the range of 0.05 to 7% by weight, more preferably in the range of 0.1 to 5% by weight.

[0037] The conductive polymer composition of the present invention is characterized by containing a water-dispersible metal (B) at a concentration of 0.01 to 0.5% by weight, which makes it possible to obtain a coating film with high conductivity.

[0038] The water-dispersible metal (B) is not particularly limited, but specific examples include water-dispersible silver particles or water-dispersible copper particles. The shape of these water-dispersible metals is not particularly limited, and shapes such as fillers, rods, tubes, and particles can be used. From the viewpoint of compatibility and dispersibility, metal particles having a nano-level structure are preferred.

[0039] The water-dispersible metal (B) is preferably at least one selected from the group consisting of silver nanoparticles, silver nanoplates, silver nanowires, copper nanoparticles, copper nanoplates, and copper nanowires, in terms of excellent total light transmittance, and more preferably silver nanowires in terms of storage stability.

[0040] The conductive polymer composition of the present invention is characterized by containing 0.01 to 0.5% by weight of the water-dispersible metal (B), and this content refers to the content of the water-dispersible metal (B) itself.

[0041] The content of the water-dispersible metal (B) is preferably 0.1 to 0.5% by weight, more preferably 0.15 to 0.5% by weight, in that it has high compatibility with the conductive polymer and can maintain high conductivity.

[0042] The conductive polymer composition of the present invention may further contain a compound (C) capable of forming an ion pair with the sulfonic acid group of the polythiophene (A) in order to achieve excellent conductivity and coatability. The compound (C) capable of forming an ion pair with the sulfonic acid group is not particularly limited, and examples thereof include alkali metal compounds, ammonia, organic amine compounds, and quaternary ammonium salts. These compounds react with the sulfonic acid group of the polythiophene (A) to form alkali metal ion salts, ammonium ion salts, organic ammonium ion salts, and quaternary ammonium ion salts of the polythiophene (A), respectively.

[0043] The alkali metal compound is not particularly limited, but examples thereof include alkali metal salt compounds (e.g., lithium chloride, potassium chloride, sodium chloride, rubidium chloride, cesium chloride, lithium bromide, potassium bromide, sodium bromide, rubidium bromide, cesium bromide, etc.) and alkali metal hydroxides (e.g., lithium hydroxide, potassium hydroxide, sodium hydroxide, rubidium hydroxide, cesium hydroxide, etc.).

[0044] The alkali metal ion salt of the lithiophene (A) can be prepared by incorporating the alkali metal compound into the conductive polymer composition of the present invention. The alkali metal ion is not particularly limited, but examples thereof include lithium ion, potassium ion, sodium ion, rubidium ion, and cesium ion.

[0045] The organic amine compound is not particularly limited, and examples thereof include primary, secondary, or tertiary amine compounds having a total carbon number of 1 to 30. More specific examples thereof include methylamine, dimethylamine, trimethylamine, ethylamine, triethylamine, normal-propylamine, isopropylamine, normal-butylamine, hexylamine, aminoethanol, dimethylaminoethanol, methylaminoethanol, diethanolamine, N-methyldiethanolamine, triethanolamine, 3-amino-1,2-propanediol, 3-methylamino-1,2-propanediol, 3-dimethylamino-1,2-propanediol, 1,4-butanediamine, triisobutylamine, triisopentylamine, triisooctylamine, imidazole, N-methylimidazole, 1,2-dimethylimidazole, pyridine, picoline, and lutidine.

[0046] By incorporating the organic amine compound into the conductive polymer composition of the present invention, the organic amine compound reacts with the polythiophene (A) to form an organic ammonium ion, thereby preparing an organic ammonium ion salt of the polythiophene (A). The organic ammonium ion is not particularly limited, but examples thereof include primary, secondary, and tertiary ammonium ions having a total carbon number of 1 to 30. More specifically, examples thereof include methylammonium, dimethylammonium, trimethylammonium, ethylammonium, triethylammonium, n-propylammonium, isopropylammonium, n-butylammonium, hexylammonium, 2-hydroxyethylammonium, N,N-dimethyl-N-(2-hydroxyethyl)ammonium, N-methyl-N-(2-hydroxyethyl)ammonium, and di(2-hydroxyethyl)ammonium. ammonium, N-methyl-N,N-di(2-hydroxyethyl)ammonium, N,N,N-tri(2-hydroxyethyl)ammonium, 2,3-dihydroxypropylammonium, N-methyl-N-(2,3-dihydroxypropyl)ammonium, N,N-dimethyl-N-(2,3-dihydroxypropyl)ammonium, 1,4-butanediammonium, triisobutylammonium, triisopentylammonium, triisooctylammonium, imidazole cation, N-methylimidazole cation, 1,2-dimethylimidazole cation, pyridinium ion, picolinium ion, or lutidinium ion.

[0047] The quaternary ammonium compound is not particularly limited, but examples thereof include tetramethylammonium chloride, tetraethylammonium chloride, tetra-normal-propylammonium chloride, tetra-normal-butylammonium chloride, and tetra-normal-hexylammonium chloride.

[0048] By incorporating the quaternary ammonium compound into the conductive polymer composition of the present invention, the quaternary ammonium compound reacts with the polythiophene (A) to form a quaternary ammonium ion, thereby preparing a quaternary ammonium ion salt of the polythiophene (A). The quaternary ammonium ion is not particularly limited, but examples thereof include tetramethylammonium ion, tetraethylammonium ion, tetra-n-propylammonium ion, tetra-n-butylammonium ion, and tetra-n-hexylammonium ion.

[0049] In the conductive polymer composition of the present invention, the content of the compound (C) is preferably 0.001 to 20% by weight, more preferably 0.01 to 15% by weight, and even more preferably 0.1 to 10% by weight, in terms of excellent surface resistivity (low resistance).

[0050] The conductive polymer composition of the present invention preferably has a pH in the range of 1.0 to 10.0, more preferably 1.5 to 8.0, and even more preferably 1.5 to 7.5, in terms of excellent surface resistance (low resistance). The pH can be controlled by the type and content of the compound (C) described above.

[0051] When the conductive polymer composition of the present invention contains the compound (C), the polythiophene (A) containing at least one structural unit selected from the group consisting of structural units represented by the general formula (1) and structural units represented by the general formula (2) can be described as a polythiophene (A) containing at least one structural unit selected from the group consisting of structural units represented by the following general formula (1') and structural units represented by the general formula (2'):

[0052] [ka]

[0053] [In the above general formula (1') and general formula (2'), R2 The definitions and preferred ranges of m and n are as defined in the R 2 The definitions and preferred ranges of m and n are the same as those of n. M represents a hydrogen ion, an alkali metal ion, an ammonium ion, an organic ammonium ion, or a quaternary ammonium ion. The alkali metal ion, ammonium ion, organic ammonium ion, and quaternary ammonium ion in M ​​are as described above. In addition, in the polythiophene (A) containing at least one structural unit selected from the group consisting of the structural unit represented by the general formula (1') and the structural unit represented by the general formula (2'), M does not need to be a single unit, and multiple types of M can coexist.

[0054] The conductive polymer composition of the present invention may contain additives (D) other than those mentioned above.

[0055] The additives (D) other than those mentioned above are not particularly limited, but examples thereof include binders, surfactants, organic solvents, etc. The additives (D) may be used alone or in combination of two or more.

[0056] The binder is not particularly limited, but is preferably, for example, a water-soluble resin, and more specific examples include polyvinyl alcohol, polyvinylpyrrolidone, cellulose, a water-soluble polyester resin compound, a water-soluble polyurethane resin compound, or a mixture of a polyhydric alcohol and an organic acid having two or more carboxyl groups.

[0057] Examples of the water-soluble polyester resin compound include polyethylene terephthalate, polytrimethylene terephthalate, etc. The water-soluble polyester resin compound may be a self-emulsifying type or a reinforced emulsifying type, but is preferably a self-emulsifying water-soluble polyester resin compound from the viewpoint of water resistance and solvent resistance.

[0058] Examples of the water-soluble polyester resin compound include those manufactured by Toyobo Co., Ltd. under the trade name Vylonal (registered trademark), those manufactured by Takamatsu Oil & Fat Co., Ltd. under the trade name PES RESIN, those manufactured by Goo Chemical Co., Ltd. under the trade name PLASCOAT (registered trademark), those manufactured by Toagosei Co., Ltd. under the trade name ARON MELT (registered trademark), those manufactured by Takamatsu Oil & Fat Co., Ltd. under the trade name PES RESIN A, and those manufactured by DIC Corporation under the trade name WATERZOL (registered trademark).

[0059] The water-soluble polyester resin compounds may be used alone or in combination of two or more.

[0060] The water-soluble polyurethane resin compound is mainly used in industrial applications as a urethane resin emulsion, and may be a self-emulsifying type or a reinforced emulsifying type. However, from the viewpoint of water resistance and solvent resistance, a self-emulsifying water-soluble polyurethane resin compound is preferable. Examples of the self-emulsifying type include an anionic type, a cationic type, and a nonionic type, and any of these may be used. Furthermore, the water-soluble polyurethane resin compound is not particularly limited, but examples thereof include a polyether type, a polyester type, and a polycarbonate type.

[0061] Examples of water-soluble polyurethane resin compounds that can be easily obtained commercially include those manufactured by Sanyo Chemical Industries, Ltd. under the trade names U-coat (registered trademark), Permarin (registered trademark), and Euplen (registered trademark), those manufactured by Kusumoto Chemicals Co., Ltd. under the trade name NeoRez, those manufactured by ADEKA Corporation under the trade name Adeka Bontiter (registered trademark), those manufactured by Meisei Chemical Industry Co., Ltd. under the trade name Pascol (registered trademark), and those manufactured by DIC Corporation under the trade name Hydran (registered trademark).

[0062] The water-soluble polyurethane resin compounds can be used alone or in combination of two or more.

[0063] The polyhydric alcohol is not particularly limited, but examples thereof include erythritol and pentaerythritol.

[0064] The organic acid having two or more carboxyl groups is not particularly limited, but examples thereof include adipic acid and phthalic acid.

[0065] The surfactant is not particularly limited, but examples thereof include anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, fluorine-based surfactants, and silicone-based surfactants, and more preferably at least one selected from the group consisting of nonionic surfactants and amphoteric surfactants.

[0066] The anionic surfactant is not particularly limited, but examples thereof include sodium lauryl alcohol sulfate and sodium dodecylbenzenesulfonate.

[0067] The cationic surfactant is not particularly limited, and commercially available products can be used, or commonly known products can be separately produced and used.

[0068] The nonionic surfactant is not particularly limited, but examples thereof include polyethylene glycol surfactants, acetylene glycol surfactants, polyhydric alcohol surfactants, and polymeric nonionic surfactants.

[0069] The polyethylene glycol surfactant is not particularly limited, but examples thereof include higher alcohol ethylene oxide adducts, alkylphenol ethylene oxide adducts, fatty acid ethylene oxide adducts, polyhydric alcohol fatty acid ester ethylene oxide adducts, higher alkylamine ethylene oxide adducts, ethylene oxide adducts of fats and oils, and polypropylene glycol ethylene oxide adducts.

[0070] The acetylene glycol surfactant is not particularly limited, but examples thereof include 2,4,7,9-tetramethyl-5-decyne-4,7-diol, Surfynol (manufactured by Air Products Co., Ltd., registered trademark), and Olfine (manufactured by Nissin Chemical Industry Co., Ltd., registered trademark).

[0071] The polyhydric alcohol surfactant is not particularly limited, but examples thereof include fatty acid esters of glycerol, fatty acid esters of pentaerythritol, fatty acid esters of sorbitol and sorbitan, fatty acid esters of sucrose, alkyl ethers of higher alcohols, and fatty acid amides of alkanolamines.

[0072] The amphoteric surfactant is not particularly limited, but examples thereof include betaine-type amphoteric surfactants, such as alkyl dimethyl betaine, lauryl dimethyl betaine, stearyl dimethyl betaine, and lauryl dihydroxyethyl betaine.

[0073] The fluorine-based surfactant is not particularly limited as long as it has a perfluoroalkyl group, and examples thereof include PLASCOAT (registered trademark) RY-2, perfluoroalkane, perfluoroalkylcarboxylic acid, perfluoroalkylsulfonic acid, and perfluoroalkylethylene oxide adducts.

[0074] The silicone surfactant is not particularly limited, but examples thereof include polyether-modified polydimethylsiloxane, polyetherester-modified polydimethylsiloxane, hydroxyl group-containing polyether-modified polydimethylsiloxane, acrylic group-containing polyether-modified polydimethylsiloxane, acrylic group-containing polyester-modified polydimethylsiloxane, perfluoropolyether-modified polydimethylsiloxane, perfluoropolyester-modified polydimethylsiloxane, and silicone-modified acrylic compounds.

[0075] In addition, fluorine-based surfactants and silicone-based surfactants are effective as leveling agents to improve the flatness of the coating film.

[0076] The organic solvent is not particularly limited, but examples thereof include alcohols, and more specific examples thereof include methanol, ethanol, propanol, butanol, methoxyethanol, ethoxyethanol, butoxyethanol, and ethylene glycol.

[0077] In the conductive polymer composition of the present invention, the content of the additives (D) is each independently 0.001 to 20% by weight, but from the viewpoint of excellent operability, it is preferably each independently 0.01 to 15% by weight, and more preferably each independently 0.1 to 10% by weight.

[0078] To reiterate, the conductive polymer composition of the present invention is characterized by containing 0.01 to 10 wt % of polythiophene (A) including at least one structural unit selected from the group consisting of structural units represented by the following general formula (1) and structural units represented by the following general formula (2), 0.01 to 0.5 wt % of water-dispersible metal (B), and water.

[0079] The water is constituted by the water accompanying the aqueous solution of polythiophene (A) or the aqueous dispersion of water-dispersible metal (B), but the conductive polymer composition of the present invention may also be constituted by additional water. The water to be added is not particularly limited, and examples thereof include purified water, distilled water, ion-exchanged water, and pure water. It is preferable to use water of as high purity as possible.

[0080] The concentration (content) of water in the conductive polymer composition of the present invention is not particularly limited, but in terms of excellent workability, it is preferably in the range of 80 to 99.5 wt %, and more preferably 85 to 99.5 wt %.

[0081] The method for preparing the conductive polymer composition of the present invention is not particularly limited, but examples include a method of mixing an aqueous solution or solid of the polythiophene (A), an aqueous dispersion of the water-dispersible metal (B), and water. At this time, the compound (C) and / or the additive (D) can be added and mixed as needed. While it is preferable to add each material to water and mix them, the order in which the materials are added and mixed is not particularly limited, and the conductive polymer composition of the present invention can be prepared by mixing these materials in any order.

[0082] The temperature at which the mixture is mixed is not particularly limited, but may be, for example, from room temperature to heated, preferably from 0°C to 100°C.

[0083] The atmosphere in which the mixture is mixed is not particularly limited, but may be air or an inert gas.

[0084] Furthermore, when mixing, in addition to a general mixing and dissolving operation using a stirrer tip, stirring blades, etc., ultrasonic irradiation or homogenization treatment (for example, using a mechanical homogenizer, ultrasonic homogenizer, high-pressure homogenizer, etc.) may be performed. When homogenization treatment is performed, it is preferable to perform it at a low temperature to prevent thermal degradation of the polymer.

[0085] The viscosity (20° C.) of the conductive polymer composition of the present invention is preferably 200 mPa·s or less, more preferably 100 mPa·s or less, and even more preferably 50 mPa·s or less.

[0086] The concentration of each component in the conductive polymer composition of the present invention may be adjusted by the compounding ratio, or may be adjusted by concentrating or diluting after compounding. The concentration method may be a method of distilling off the solvent under reduced pressure or a method using an ultrafiltration membrane.

[0087] In the conductive polymer composition of the present invention, the concentration of all components other than water is preferably in the range of 0.5 to 20% by weight, more preferably in the range of 0.5 to 15% by weight.

[0088] The method for forming a conductive polymer film from the conductive polymer composition of the present invention is not particularly limited, but an example thereof is a method in which the conductive polymer composition of the present invention is applied to a support and then dried.

[0089] The support is not particularly limited as long as it can be coated with the conductive polymer composition of the present invention, and examples thereof include polymer substrates and inorganic substrates. Examples of polymer substrates include thermoplastic resins, nonwoven fabrics, paper, and resist film substrates. Examples of thermoplastic resins include polyethylene, polypropylene, polyethylene terephthalate, polyacrylate, and polycarbonate. Examples of nonwoven fabrics include natural fibers and synthetic fibers. Examples of paper include those containing common cellulose as a main component. Examples of inorganic substrates include glass, glass fiber, ceramics, aluminum oxide, and tantalum oxide.

[0090] Examples of methods for applying the conductive polymer composition include casting, dipping, bar coating, dispenser coating, roll coating, gravure coating, flexographic printing, screen printing, and offset printing.

[0091] The drying temperature for the coating film is not particularly limited as long as it is a temperature at which a uniform conductive polymer film can be obtained and is equal to or lower than the heat resistance temperature of the substrate, but is preferably in the range of room temperature to 300°C, more preferably in the range of room temperature to 250°C, and even more preferably in the range of room temperature to 200°C.

[0092] The drying atmosphere may be air, an inert gas, a vacuum, or a reduced pressure, but from the viewpoint of preventing deterioration of the polymer film, an inert gas such as nitrogen or argon is preferred.

[0093] The thickness of the resulting conductive polymer film is not particularly limited, but is preferably 10 -3 ~10 2 The range of 10 μm is preferable. -3 ~10 -1 μm.

[0094] The conductive polymer film obtained from the conductive polymer composition of the present invention has excellent conductivity.

[0095] The conductive polymer film is used, for example, as an electrode material, a transparent conductive film, and also as an electromagnetic wave shield.

[0096] The conductive polymer film is characterized by containing a polythiophene (A) containing at least one structural unit selected from the group consisting of a structural unit represented by the general formula (1') and a structural unit represented by the general formula (2'), and a water-dispersible metal (B). [Example]

[0097] Examples of the present invention are given below.

[0098] The analytical instruments and measurement methods used in the present examples are listed below.

[0099] [GC measurement] Apparatus: Shimadzu GC-2014.

[0100] [NMR measurement] Device: Gemini-200, manufactured by VARIAN.

[0101] [Surface resistivity measurement] Apparatus: Mitsubishi Chemical Loresta GP MCP-T600.

[0102] [Film thickness measurement] Device: DEKTAK XT manufactured by BRUKER.

[0103] [Viscosity measurement] Equipment: Complete viscometer / BROOKFIELD VISCOMETER DV-1 Prime.

[0104] [Total light transmittance] Equipment: Haze Meter NDH 4000, manufactured by Nippon Denshoku Industries Co., Ltd.

[0105] [Color b*] Equipment: Konica Minolta CM-700d spectrophotometer.

[0106] [Conductivity measurement of self-doped conductive polymers] 0.5 ml of a composition containing a self-doping conductive polymer was applied to a 25 mm square non-alkali glass plate, dried overnight at room temperature, and then heated at 150°C for 30 minutes to obtain a conductive polymer film. The film thickness and surface resistance were calculated using the following formula.

[0107] Conductivity [S / cm]=10 4 / (Surface resistivity [Ω / □]×film thickness [μm]).

[0108] Synthesis Example 1 (Synthesis of sodium 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-methyl-1-propanesulfonate)

[0109] [ka]

[0110] Under a nitrogen atmosphere, a 100 mL eggplant-shaped flask was charged with 0.437 g (10.9 mmol) of 60% sodium hydride and 37 mL of toluene, followed by the addition of 1.52 g (8.84 mL) of (2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methanol. The mixture was then heated to reflux with stirring and stirred at this reflux temperature for 1 hour. Subsequently, a mixture of 1.21 g (8.89 mmol) of 2,4-butanesultone and 10 mL of toluene was added dropwise while continuing reflux, followed by further stirring at reflux for 2 hours. After cooling, the resulting reaction mixture was added dropwise to 160 mL of acetone for reprecipitation. The resulting powder was filtered and vacuum dried to obtain 1.82 g of a pale yellow powder in 62% yield. NMR measurement confirmed that this was sodium 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-methyl-1-propanesulfonate represented by the above formula (6).

[0111] Synthesis Example 2: Synthesis of polythiophene (A) [polymer containing structural units represented by the following formulas (7) and (8)].

[0112] [ka]

[0113] [ka]

[0114] A 500 mL separable flask was charged with 10 g (30 mmol) of sodium 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-methyl-1-propanesulfonate (synthesized according to Synthesis Example 1) and 150 g of water. After dissolution, 2.94 g (18.1 mmol) of anhydrous iron(III) chloride was added at room temperature and stirred for 20 minutes. A mixed solution consisting of 14.5 g (60.4 mmol) of sodium persulfate and 100 g of water was then added dropwise. The addition rate was adjusted so that the reaction solution temperature did not exceed 30°C. After stirring at room temperature for 3 hours, the reaction solution was added dropwise to 800 g of acetone to precipitate a black Na-type polymer. The polymer was filtered and dried under vacuum to obtain 18.0 g of crude polymer of sodium 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-methyl-1-propanesulfonate.

[0115] Next, 14.5 g of this crude polymer was added to water to prepare a 2 wt% solids solution. 700 g of this solution was passed through a column packed with 200 mL of cation exchange resin Lewatit MonoPlus S100 (H-type) (space velocity = 1.1), yielding 738 g of an H-type polymer solution. This polymer solution was then purified by cross-flow ultrafiltration (filter = Vivaflow 200, molecular weight cutoff = 5,000, permeability = 5), yielding 698 g of a deep ultramarine-colored solution of a polymer (hereinafter referred to as A-1) containing structural units represented by formulas (7) and (8). The amount of polymer (solid content) contained in the polythiophene solution was 0.74 wt%. Furthermore, ICP-MS analysis revealed that the polythiophene solution contained 44 ppm of iron ions and 12 ppm of sodium ions, based on the solid content.

[0116] Synthesis example 3. The polythiophene aqueous solution obtained by the method of Synthesis Example 2 was desolvated to prepare 301.13 g of an aqueous solution containing 1.31 wt% of polythiophene (A-1), to which 2.19 g of a 50% aqueous solution of monoethanolamine (corresponding to the above-mentioned compound (C)) was added and mixed thoroughly with stirring. The pH of the resulting aqueous solution of polythiophene (hereinafter referred to as A-2) was 5.3.

[0117] Synthesis example 4. The polythiophene aqueous solution obtained by the method of Synthesis Example 2 was desolvated to prepare 300.25 g of an aqueous solution containing 1.31 wt% of polythiophene (A-1), to which 2.28 g of a 50% aqueous monoethanolamine solution (corresponding to the above-mentioned compound (C)) was added and mixed thoroughly with stirring. The pH of the resulting aqueous solution of polythiophene (hereinafter referred to as A-3) was 6.8.

[0118] Example 1 The polythiophene aqueous solution obtained in Synthesis Example 2 was desolvated to prepare 1.92 g of an aqueous solution containing 1.3 wt% polythiophene (A-1). To this solution, 5.00 g of a silver nanowire dispersion (aqueous dispersion with a solids concentration of 0.5 wt%) as an aqueous dispersion of water-dispersible metal (B), 0.04 g of GOO Chemical's PLASCOAT® RZ-105 (aqueous solution with a solids concentration of 25 wt%, surfactant), 0.75 g of ethanol, and 2.29 g of water were added and thoroughly stirred to obtain a conductive polymer composition with a solids concentration of 0.60%. 0.5 g of this conductive polymer composition was cast onto a glass surface that had been UV-ozone treated. A coating film was formed using a bar coater and heated in an oven (120 °C) for 5 minutes to obtain a conductive polymer film. The evaluation results of the resulting conductive film are shown in Table 1.

[0119] Example 2. In Example 1, 1.46 g of an aqueous solution containing 1.3 wt % of polythiophene (A-1) was prepared, and to this was added 6.20 g of a silver nanowire dispersion (aqueous dispersion with a solids concentration of 0.5 wt %) as the aqueous dispersion of the water-dispersible metal (B), and 1.55 g of water. Except for this, a conductive polymer composition and a conductive polymer film were obtained and evaluated in accordance with the method of Example 1. The results are shown in Table 1.

[0120] Example 3. In Example 1, 0.92 g of an aqueous solution containing 1.3 wt % of polythiophene (A-1) was prepared, and to this was added 7.60 g of a silver nanowire dispersion (aqueous dispersion with a solids concentration of 0.5 wt %) as the aqueous dispersion of the water-dispersible metal (B), and 0.69 g of water. Except for this, a conductive polymer composition and a conductive polymer film were obtained and evaluated in accordance with the method of Example 1. The results are shown in Table 1.

[0121] Comparative Example 1 The polythiophene aqueous solution obtained in Synthesis Example 2 was desolvated to prepare 3.85 g of an aqueous solution containing 1.3 wt% polythiophene (A-1). To this solution, 0.04 g of RZ-105 (aqueous solution with a solids concentration of 25 wt%, surfactant) as additive (D), 0.75 g of ethanol, and 5.36 g of water were added and mixed thoroughly, resulting in a conductive polymer composition with a solids concentration of 0.60%. 0.5 g of this conductive polymer composition was cast onto a glass surface that had been UV-ozone treated, and a coating film was formed using a bar coater. The coating film was then heated in an oven (120°C) for 5 minutes to obtain a conductive polymer film. The evaluation results of the resulting conductive film are shown in Table 1.

[0122] Comparative Example 2 2.08 g of PEDOT:PSS (aqueous dispersion with a solids concentration of 1.2 wt%) was mixed with 5.00 g of silver nanowire dispersion (aqueous dispersion with a solids concentration of 0.5 wt%), 0.04 g of RZ-105 (aqueous solution with a solids concentration of 25 wt%), 0.75 g of ethanol, and 2.13 g of water, and the mixture was stirred thoroughly to obtain a conductive polymer composition with a solids concentration of 0.60%. 0.5 g of this conductive polymer composition was cast onto a glass substrate that had been UV-ozone treated. A coating film was then formed using a bar coater and heated in an oven (120 °C) for 5 minutes to obtain a conductive polymer film. The evaluation results of the resulting conductive film are shown in Table 1.

[0123] [Table 1]

[0124] Example 4 A conductive polymer composition and a conductive polymer film were obtained and evaluated in the same manner as in Example 1, except that 1.92 g of an aqueous solution containing 1.3 wt % of polythiophene (A) obtained by removing the solvent from the aqueous polythiophene solution obtained in Synthesis Example 2 was used instead of 1.92 g of an aqueous solution of polythiophene (A-2) obtained in Synthesis Example 3. The results are shown in Table 2.

[0125] Example 5 A conductive polymer composition and a conductive polymer film were obtained and evaluated in accordance with the method of Example 2, except that 1.46 g of an aqueous solution containing 1.3 wt % of polythiophene (A) obtained by removing the solvent from the aqueous polythiophene solution obtained in Synthesis Example 2 was used instead of 1.46 g of an aqueous solution of polythiophene (A-2) obtained in Synthesis Example 3. The results are shown in Table 2.

[0126] Example 6 A conductive polymer composition and a conductive polymer film were obtained and evaluated in accordance with the method of Example 3, except that in Example 3, 0.92 g of an aqueous solution of polythiophene (A-2) obtained in Synthesis Example 3 was used instead of 0.92 g of an aqueous solution containing 1.3 wt % of polythiophene (A) obtained by removing the solvent from the aqueous polythiophene solution obtained in Synthesis Example 2. The results are shown in Table 2.

[0127] Example 7 In Example 1, instead of using 1.92 g of an aqueous solution containing 1.3 wt% polythiophene (A) obtained by desolvating the polythiophene aqueous solution obtained in Synthesis Example 2, 3.84 g of an aqueous solution of polythiophene (A-2) obtained in Synthesis Example 3 was used, and the amount of water added was changed from 2.29 g to 0.37 g. A conductive polymer composition and a conductive polymer film were obtained and evaluated in accordance with the method of Example 1. That is, the solid content (wt%) of the total composition of polythiophene (A-2) was adjusted to 0.50 wt%. The results are shown in Table 2.

[0128] Example 8 7.68 g of the aqueous solution of polythiophene (A-2) obtained in Synthesis Example 3 was used, and 3.47 g of water was evaporated under reduced pressure. Then, 5.00 g of a silver nanowire dispersion (aqueous dispersion with a solids concentration of 0.5 wt%) as an aqueous dispersion of water-dispersible metal (B), 0.04 g of GOO Chemical's PLASCOAT® RZ-105 (aqueous solution with a solids concentration of 25 wt%, surfactant) as an additive (D), and 0.75 g of ethanol were added and thoroughly stirred to obtain a conductive polymer composition with a solids concentration of 0.60%. That is, the solids content (wt%) of the polythiophene (A-2) in the total composition was adjusted to 1.00 wt%. A conductive polymer film was obtained and evaluated in the same manner as in Example 1. The results are shown in Table 2.

[0129] Example 9 In Example 1, instead of using 1.92 g of an aqueous solution containing 1.3 wt % polythiophene (A) obtained by removing the solvent from the polythiophene aqueous solution obtained in Synthesis Example 2, 1.92 g of an aqueous solution of polythiophene (A-2) obtained in Synthesis Example 3 was used, and the amount of PLASCOAT (registered trademark) RZ-105 (aqueous solution with a solids concentration of 25 wt %, surfactant) added by GOO Chemical Co., Ltd. was changed from 0.04 g to 0.08 g, and the amount of water added was also changed from 2.29 g to 2.25 g. A conductive polymer composition and a conductive polymer film were obtained and evaluated in accordance with the method of Example 1. The results are shown in Table 2.

[0130] [Table 2]

[0131] Example 10 A conductive polymer composition and a conductive polymer film were obtained and evaluated in the same manner as in Example 1, except that 1.92 g of an aqueous solution containing 1.3 wt % of polythiophene (A) obtained by removing the solvent from the aqueous polythiophene solution obtained in Synthesis Example 2 was used instead of 1.92 g of an aqueous solution of polythiophene (A-3) obtained in Synthesis Example 4. The results are shown in Table 3.

[0132] Example 11 A conductive polymer composition and a conductive polymer film were obtained and evaluated in accordance with the method of Example 2, except that 1.92 g of an aqueous solution containing 1.3 wt % of polythiophene (A) obtained by removing the solvent from the aqueous polythiophene solution obtained in Synthesis Example 2 was used instead of 1.92 g of an aqueous solution of polythiophene (A-3) obtained in Synthesis Example 4. The results are shown in Table 3.

[0133] Example 12 A conductive polymer composition and a conductive polymer film were obtained and evaluated in accordance with the method of Example 3, except that in Example 3, 1.92 g of an aqueous solution containing 1.3 wt % of polythiophene (A) obtained by removing the solvent from the aqueous polythiophene solution obtained in Synthesis Example 2 was used instead of 1.92 g of an aqueous solution of polythiophene (A-3) obtained in Synthesis Example 4. The results are shown in Table 3.

[0134] Example 13 In Example 1, instead of using 1.92 g of an aqueous solution containing 1.3 wt% polythiophene (A) obtained by desolvating the polythiophene aqueous solution obtained in Synthesis Example 2, 3.84 g of an aqueous solution of polythiophene (A-3) obtained in Synthesis Example 4 was used, and the amount of water added was changed from 2.29 g to 0.37 g. A conductive polymer composition and a conductive polymer film were obtained and evaluated in accordance with the method of Example 1. That is, the solid content (wt%) of the total composition of polythiophene (A-3) was adjusted to 0.50 wt%. The results are shown in Table 3.

[0135] Example 14 7.68 g of the aqueous solution of polythiophene (A-3) obtained in Synthesis Example 4 was used, and 3.47 g of water was evaporated under reduced pressure. Then, 5.00 g of a silver nanowire dispersion (aqueous dispersion with a solids concentration of 0.5 wt%) as an aqueous dispersion of water-dispersible metal (B), 0.04 g of GOO Chemical's PLASCOAT® RZ-105 (aqueous solution with a solids concentration of 25 wt%, surfactant) as an additive (D), and 0.75 g of ethanol were added and thoroughly stirred to obtain a conductive polymer composition with a solids concentration of 0.60%. That is, the solids content (wt%) of the polythiophene (A-3) in the total composition was adjusted to 1.00 wt%. A conductive polymer film was obtained and evaluated in the same manner as in Example 1. The results are shown in Table 3.

[0136] Example 15 In Example 1, instead of using 1.92 g of an aqueous solution containing 1.3 wt % polythiophene (A) obtained by removing the solvent from the polythiophene aqueous solution obtained in Synthesis Example 2, 1.92 g of an aqueous solution of polythiophene (A-3) obtained in Synthesis Example 4 was used, and the amount of PLASCOAT (registered trademark) RZ-105 (aqueous solution with a solids concentration of 25 wt %, a surfactant) added by GOO Chemical Co., Ltd. was changed from 0.04 g to 0.08 g, and the amount of water added was also changed from 2.29 g to 2.25 g. A conductive polymer composition and a conductive polymer film were obtained and evaluated in accordance with the method of Example 1. The results are shown in Table 3.

[0137] [Table 3] [Industrial Applicability]

[0138] The conductive polymer composition of the present invention forms a good conductive polymer film and has high conductivity, and therefore is expected to be applicable not only to various conductive coating agents (antistatic agents), electrode materials, and transparent conductive films, but also to electromagnetic wave shielding.

Claims

1. A conductive polymer composition comprising 0.01 to 10% by weight of a self-doping water-soluble polythiophene (A) containing at least one structural unit selected from the group consisting of a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2), 0.01 to 0.5% by weight of a water-dispersible metal (B), and water: 【Chemistry 1】 [In the above general formulas (1) and (2), R ２ represents a hydrogen atom, a methyl group, an ethyl group, a linear or branched alkyl group having 3 to 6 carbon atoms, or a fluorine atom, m represents an integer of 1 to 10, and n represents 0 or 1.

2. 2. The conductive polymer composition according to claim 1, wherein the water-dispersible metal (B) is at least one selected from the group consisting of silver nanoparticles, silver nanoplates, silver nanowires, copper nanoparticles, copper nanoplates, and copper nanowires.

3. 3. The conductive polymer composition according to claim 1, wherein the water-dispersible metal (B) is silver nanowires.

4. 4. The conductive polymer composition according to claim 1, further comprising a surfactant in addition to the polythiophene (A), the water-dispersible metal (B), and water.

5. 4. The conductive polymer composition according to claim 1, further comprising an alcohol in addition to the polythiophene (A), the water-dispersible metal (B), and water.

6. 4. The conductive polymer composition according to claim 1, further comprising, in addition to the polythiophene (A), the water-dispersible metal (B), and water, a compound (C) capable of forming an ion pair with a sulfonic acid group of the polythiophene (A).

7. 7. The conductive polymer composition according to claim 1, wherein the concentration of water in the conductive polymer composition is in the range of 80 to 99.5% by weight.

8. 8. The conductive polymer composition according to claim 1, wherein the pH at room temperature is in the range of 1.0 to 10.

0.

9. A method for producing a film, comprising applying the conductive polymer composition according to any one of claims 1 to 8 to a support and then drying the applied conductive polymer composition.

10. A film comprising a self-doped water-soluble polythiophene (A) containing at least one structural unit selected from the group consisting of a structural unit represented by the following general formula (1') and a structural unit represented by the following general formula (2'), and a water-dispersible metal (B). 【Chemistry 2】 [In the above general formulas (1') and (2'), R ２ represents a hydrogen atom, a methyl group, an ethyl group, a linear or branched alkyl group having 3 to 6 carbon atoms, or a fluorine atom, m represents an integer of 1 to 10, and n represents 0 or 1. M represents a hydrogen ion, an alkali metal ion, an ammonium ion, an organic ammonium ion, or a quaternary ammonium ion.

Images