Conductive polymer compositions, conductive polymer films, and their applications

Abstract

A conductive polymer composition that provides a conductive polymer film that contains a polythiophene-based conductive polymer material and a dispersible metal, while stably maintaining a low surface resistance value. [Solution] A conductive polymer composition characterized by containing 0.01 to 10% by mass of polythiophene (A) having 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), 0.01 to 1.0% by mass of a dispersible metal (B), and 0.01 to 10% by mass of polyvinyl acetal resin (C). JPEG2026090023000017.jpg39141 [In the above general formula (1), M + R represents a hydrogen ion, an alkali metal ion, a conjugate acid of an amine compound, or a quaternary ammonium cation. In the general formulas (1) and (2) above, R represents an organic group with a total of 1 to 14 carbon atoms having at least one substituent selected from the group consisting of a sulfonic acid group and a phosphonic acid group.

Description

[Technical Field]

[0001] This invention relates to conductive polymer compositions, conductive polymer films, and their applications. [Background technology]

[0002] Conductive polymer materials have been developed by doping π-conjugated polymers, such as polyacetylene, polythiophene, polyaniline, or polypyrrole, with electron-accepting compounds as dopants. These conductive polymer materials are being considered for applications such as antistatic agents, solid electrolytes in capacitors, conductive paints, radio wave shielding materials, electrochromic elements, electrode materials, thermoelectric conversion materials, transparent conductive films, chemical sensors, and actuators. Among these, polythiophene-based conductive polymer materials are particularly useful in practical applications due to their chemical stability.

[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) as a dopant, and so-called self-doped conductive polymers that have substituents (sulfo groups, sulfonate groups, etc.) in the polymer main chain, either directly or via spacers, that provide both water solubility and doping effects.

[0004] Polymer films formed by creating a mixture of such self-doped polythiophene-based conductive polymers and dispersible metals exhibit excellent conductivity and transmittance, and their application to transparent electrodes and the like is being investigated (see, for example, Patent Documents 1 to 3). [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2021-042150 [Patent Document 2] Japanese Patent Publication No. 2023-005813

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0006] As described above, a polymer film formed by forming a mixture of a conventionally known polythiophene-based conductive polymer material and a dispersible metal has excellent conductivity and transmittance. However, in such a polymer film, the dispersible metal in the polymer film may be oxidized and deteriorated by oxygen in the atmosphere, resulting in an excessive increase in the surface resistance value, and there is room for improvement from this perspective.

[0007] Also, conventionally, as a technique capable of reducing the oxidative deterioration of the dispersible metal in the conductive polymer composition, the technique of Patent Document 3 was known, but such a technique had a problem that it could not be applied to an organic solvent-dispersible metal.

[0008] One aspect of the present invention can provide a conductive polymer film that can stably maintain a low surface resistance value while containing a polythiophene-based conductive polymer material and a dispersible metal, and aims to provide a conductive polymer composition capable of containing an organic solvent-dispersible metal.

Means for Solving the Problems

[0009] In order to solve the above problems, a conductive polymer composition according to one aspect of the present invention contains 0.01 to 10% by mass of polythiophene (A) having 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 1.0% by mass of a dispersible metal (B), and 0.01 to 10% by mass of a polyvinyl acetal resin (C).

[0010]

Chemical Formula

[0011] [In the above general formula (1), M+ R represents a hydrogen ion, an alkali metal ion, a conjugate acid of an amine compound, or a quaternary ammonium cation. In the general formulas (1) and (2) above, R represents an organic group with a total of 1 to 14 carbon atoms having at least one substituent selected from the group consisting of a sulfonic acid group and a phosphonic acid group. [Effects of the Invention]

[0012] According to one aspect of the present invention, it is possible to realize a conductive polymer composition, etc., that can provide a conductive polymer film that stably maintains a low surface resistance value while containing a polythiophene-based conductive polymer material and a dispersible metal. [Modes for carrying out the invention]

[0013] An aspect of the present invention will be described in detail below. Unless otherwise specified in this specification, "A to B" representing a numerical range means "greater than or equal to A and less than or equal to B".

[0014] [Conductive polymer composition] A conductive polymer composition according to one aspect of the present invention contains 0.01 to 10% by mass of polythiophene (A) having 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 1.0% by mass of a dispersible metal (B), and 0.01 to 10% by mass of polyvinyl acetal resin (C).

[0015] [ka]

[0016] [In the above general formula (1), M + R represents a hydrogen ion, an alkali metal ion, a conjugate acid of an amine compound, or a quaternary ammonium cation. In the general formulas (1) and (2) above, R represents an organic group with a total of 1 to 14 carbon atoms having at least one substituent selected from the group consisting of a sulfonic acid group and a phosphonic acid group. Hereinafter, a conductive polymer composition according to one aspect of the present invention may be referred to as "this composition." This composition provides a conductive polymer film that contains a polythiophene-based conductive polymer material and a dispersible metal, while stably maintaining a low surface resistance value.

[0017] (Polythiophene (A)) This composition contains polythiophene (A) having at least one structural unit selected from the group consisting of the structural unit represented by general formula (1) and the structural unit represented by general formula (2). In this specification, "polythiophene (A) having at least one structural unit selected from the group consisting of the structural unit represented by general formula (1) and the structural unit represented by general formula (2)" may be referred to as "polythiophene (A)". Polythiophene (A) is a so-called self-doped conductive polymer.

[0018] R in general formulas (1) and (2) - This represents a state in which the sulfonic acid group or phosphonic acid group contained in R is ionized, and for general formula (1), M is used as its countercation. + This represents a state in which cations are ionically bonded.

[0019] In the general formula (1), M + This represents a hydrogen ion, an alkali metal ion, a conjugate acid of an amine compound, or a quaternary ammonium cation.

[0020] Preferred alkali metal ions include, for example, Li ions, Na ions, or K ions.

[0021] The conjugate acid of an amine compound is a hydron (H) in the amine compound. + This indicates a species formed by the addition of ) to a cation. The amine compound may be any amine compound that reacts with a sulfonic acid group or a phosphonic acid group to form a conjugate acid, and has sp3 hybrid orbitals N(R 1 )3 is an amine compound represented by [NH(R 1 )3]+ It is represented by [...], pyridine compounds having sp2 hybrid orbitals, or imidazole compounds, etc.

[0022] Substituent R 1 Each independently represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an alkyl group having 1 to 18 carbon atoms with a substituent.

[0023] The alkyl group having 1 to 18 carbon atoms is not particularly limited, and examples include a methyl group, an ethyl group, 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, a cyclohexyl group, an octyl group, a 2-ethylhexyl group, a nonyl group, a decyl group, a dodecyl group, a tetradecyl group, a hexadecyl group, or an octadecyl group.

[0024] Examples of the alkyl group having 1 to 18 carbon atoms with a substituent include an alkyl group having a halogen atom, an alkyl group having 1 to 18 carbon atoms, an amino group, or a hydroxy group, and specifically, a trifluoromethyl group, a 2-hydroxyethyl group, etc. are exemplified.

[0025] Among these, as the substituent R 1 Each independently, a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a hexyl group, an octyl group, a 2-ethylhexyl group, or a 2-hydroxyethyl group is preferable.

[0026] N(R 1Examples of amine compounds represented by )3 include ammonia, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, n-propylamine, isopropylamine, n-butylamine, tert-butylamine, dibutylamine, tributylamine, hexylamine, dihexylamine, trihexylamine, octylamine, dioctylamine, trioctylamine, ethanolamine compounds (e.g., aminoethanol, dimethylaminoethanol, methylaminoethanol, diethanolamine, N-methyldiethanolamine, triethanolamine), 3-amino-1,2-propanediol, 3-methylamino-1,2-propanediol, 3-dimethylamino-1,2-propanediol, N-isopropyl-N,N-dimethylamine, or N-ethyl-N,N-dimethylamine.

[0027] N(R 1 Examples of compounds other than the amine compounds represented in )3 include imidazole compounds (e.g., imidazole, N-methylimidazole, 1,2-dimethylimidazole), pyridine, picoline, or lutidine.

[0028] The total number of carbon atoms in the conjugate acid of the amine compound is not particularly limited, but may be 1 to 30. From the viewpoint of solubility, it is preferable that the total number of carbon atoms be 4 to 30, more preferably 5 to 30, more preferably 5 to 25, more preferably 12 to 24, and more preferably 18 to 24.

[0029] Examples of quaternary ammonium cations include tetramethylammonium cation, tetraethylammonium cation, tetran-propylammonium cation, tetran-butylammonium cation, or tetran-hexylammonium cation. From the viewpoint of availability, tetramethylammonium cation or tetraethylammonium cation are preferred.

[0030] The total number of carbon atoms in a quaternary ammonium cation is not particularly limited, but for example, it may be 4 to 30, preferably 5 to 30, and more preferably 8 to 16.

[0031] In the general formulas (1) and (2) above, R represents an organic group having a total of 1 to 14 carbon atoms and having at least one substituent selected from the group consisting of a sulfonic acid group and a phosphonic acid group.

[0032] Organic groups with a total of 1 to 14 carbon atoms can also be rephrased as hydrocarbon groups with a total of 1 to 14 carbon atoms that may have substituents, and are not particularly limited, but examples include methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, tetradecyl group, propyloxymethyl group, or butyloxymethyl group.

[0033] While polythiophene (A) is not particularly limited, it is more preferable to use polythiophene (A2) containing at least two structural units selected from the group consisting of the structural unit represented by the following general formula (3) and the structural unit represented by the following general formula (4), or polythiophene (A3) containing at least two structural units selected from the group consisting of the structural unit represented by the following general formula (5) and the structural unit represented by the following general formula (6). Furthermore, it is more preferable for polythiophene (A3) to be polythiophene (A3') containing at least two structural units selected from the group consisting of the structural unit represented by the following general formula (5') and the structural unit represented by the following formula (6').

[0034] [ka]

[0035] [In the above general formula (3), M +R represents a hydrogen ion, an alkali metal ion, a conjugate acid of an amine compound, or a quaternary ammonium cation. In the general formulas (3) and (4) above, R 2 [where m represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, or a halogen atom. m represents an integer from 1 to 6, and n represents 0 or 1.]

[0036] [ka]

[0037] [In the above general formula (5), M + R represents a hydrogen ion, an alkali metal ion, a conjugate acid of an amine compound, or a quaternary ammonium cation. In the general formulas (5) and (6) above, R 3 Each instance of R independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, or a halogen atom. 4 'p' represents a hydrogen atom, or a linear or branched alkyl group having 1 to 6 carbon atoms. 'p' represents 0 or 1, 'q' represents an integer from 0 to 6, and 'r' represents 0 or 1.

[0038] [ka]

[0039] [In the above general formula (5'), M + This represents a hydrogen ion, an alkali metal ion, a conjugate acid of an amine compound, or a quaternary ammonium cation. In the above general formulas (3), (5), and (5'), M + The definition and preferred range of M in general formula (1) + This is the same as the definition and preferred range.

[0040] In the above general formulas (3) and (4), R 2 , and R in the above general formulas (5) and (6) 3 This represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, or a halogen atom.

[0041] Examples of linear or branched alkyl groups having 1 to 6 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, cyclopentyl group, n-hexyl group, 2-ethylbutyl group, or cyclohexyl group.

[0042] Examples of halogen atoms include fluorine atoms, chlorine atoms, or bromine atoms.

[0043] R 2 and R 3 Regarding this, in terms of solubility, it is preferable that it be a hydrogen atom, a methyl group, an ethyl group, or a fluorine atom. 2 Regarding this, in terms of solubility, it is more preferable to have a hydrogen atom or a methyl group, and more preferably a methyl group. 3 Regarding this, in terms of solubility, it is more preferable to have a hydrogen atom or a methyl group, and more preferably a hydrogen atom.

[0044] In the above general formulas (5) and (6), R 4 This represents a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms.

[0045] Examples of linear or branched alkyl groups having 1 to 6 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, cyclopentyl group, n-hexyl group, 2-ethylbutyl group, or cyclohexyl group.

[0046] R 4 Regarding this, in terms of solubility, it is preferably a hydrogen atom, a methyl group, or an ethyl group, and more preferably a hydrogen atom.

[0047] In the general formulas (3) and (4) above, m represents an integer from 1 to 6, preferably an integer from 1 to 4, and more preferably 2 or 3.

[0048] In the general formulas (3) and (4) above, n is 0 or 1, preferably 1. In the general formulas (5) and (6) above, p represents 0 or 1, preferably 0. In the general formulas (5) and (6) above, q represents an integer from 0 to 6, preferably 0. In the general formulas (5) and (6) above, r represents 0 or 1, preferably 0.

[0049] The structural units represented by general formulas (2), (4), (6) and (6') represent the self-doping state of the structural units represented by general formulas (1), (3), (5), and (5'), respectively. This doping state is manifested by the sulfonic acid group or phosphonic acid group in the structural units represented by general formulas (1), (3), (5), and (5') acting as a p-type dopant. Polymers that exhibit conductivity without the addition of external dopants in this manner are called self-doped polymers.

[0050] (Method for producing polythiophene (A)) Polythiophene (A) can be produced by polymerizing a thiophene monomer represented by the following general formula (7) in water or an alcohol solvent in the presence of an oxidizing agent, and then, if necessary, by acid treatment.

[0051] [ka]

[0052] [M in the above general formula (7) + This represents a hydrogen ion or a metal ion. Polythiophene (A2) can be produced by polymerizing a thiophene monomer represented by the following general formula (8) in water or an alcohol solvent in the presence of an oxidizing agent, and then, if necessary, by acid treatment.

[0053] [ka]

[0054] [In the above general formula (8), M + R represents a hydrogen ion or a metal ion. 2 Regarding R in the above general formula (1), 2 This is synonymous. m represents an integer from 1 to 6, and n represents 0 or 1. Polythiophene (A3) can be produced by polymerizing a thiophene monomer represented by the following general formula (9) in water or an alcohol solvent in the presence of an oxidizing agent, and then, if necessary, by acid treatment.

[0055] [ka]

[0056] [In the above general formula (9), M + R represents a hydrogen ion or a metal ion. 3 Each instance of R independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, or a halogen atom. 4 'p' represents a hydrogen atom, or a linear or branched alkyl group having 1 to 6 carbon atoms. 'p' represents 0 or 1, 'q' represents an integer from 0 to 6, and 'r' represents 0 or 1. Polythiophene (A3') can be produced by polymerizing a thiophene monomer represented by the following general formula (9') in water or an alcohol solvent in the presence of an oxidizing agent, and then, if necessary, by acid treatment.

[0057] [ka]

[0058] [In the above general formula (9'), M + This represents a hydrogen ion or a metal ion. In the above general formulas (7), (8), (9), and (9'), M +The metal ions represented by are not particularly limited, but examples include transition metal ions, noble metal ions, non-ferrous metal ions, alkali metal ions (e.g., Li ions, Na ions, or K ions), or alkaline earth metal ions.

[0059] When the polymer obtained after polymerization of the thiophene monomer represented by the general formulas (7), (8), (9), and (9') is a salt of a metal ion, the obtained metal salt polymer can be treated with acid to M + It can be converted into hydrogen ions.

[0060] The thiophene monomer represented by the general formula (8) is not particularly limited, but specifically includes 6-(2,3-dihydro-thieno[3,4-b][1,4]dioxin-2-yl)hexane-1-sulfonic acid, 6-(2,3-dihydro-thieno[3,4-b][1,4]dioxin-2-yl)hexane-1-sulfonate 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 ) Potassium hexane-1-sulfonate, 8-(2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)octan-1-sulfonic acid, 8-(2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)octan-1-sulfonate sodium, 8-(2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)octan-1-sulfonate potassium, 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-propanesulfonate sodium, 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, 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-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]- 1-Fluoro-1-propanesulfonate sodium, 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-methyl-1-propanesulfonate potassium, 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-methyl-1-propanesulfonic acid, 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-methyl-1-propanesulfonate ammonium, 3-[(2,3-di Hydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-methyl-1-propanesulfonate triethylammonium, 4-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-butanesulfonate 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]- 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, potassium 4-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-fluoro-1-butanesulfonate, or potassium 4-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-fluoro-1-butanesulfonate, etc.

[0061] In one embodiment of the present invention, the conductivity of polythiophene (A) is not particularly limited, but it is preferable that the conductivity (electrical conductivity) in the film state be 10 S / cm or more, in order to provide a conductive polymer film with excellent conductivity.

[0062] Furthermore, for polythiophene (A) according to one aspect of the present invention, it is also possible to use one synthesized based on prior art.

[0063] This composition is characterized in that, based on the total amount of the composition as 100% by mass, the content of polythiophene (A) is 0.01 to 10% by mass. The content of polythiophene (A) in this composition is not particularly limited as long as it is within the above range, but in terms of excellent conductivity and handling properties, it is preferably 0.1 to 5% by mass, preferably 0.1 to 3% by mass, and more preferably 0.1 to 1% by mass.

[0064] (Dispersible metal (B)) This composition contains a dispersible metal (B). In this specification, a dispersible metal means a metal that is dispersed in an aqueous solvent or an organic solvent, or a metal that can be dispersed in such a solvent.

[0065] The dispersible metal (B) in this composition is not particularly limited, and any known dispersible metal can be used. Specifically, examples include dispersible silver or dispersible copper. There are no particular restrictions on the shape of these dispersible metals, and they can be used in the form of particles, fillers, plates, rods, pyramids, cubes, tubes, wires, fibers, or other shapes.

[0066] In this composition, the dispersible metal (B) is preferably at least one dispersible metal selected from the group consisting of silver nanoparticles, silver nanoplates, silver nanowires, copper nanoparticles, copper nanoplates, and copper nanowires, in terms of excellent conductivity, and more preferably dispersible silver nanowires from the viewpoint of storage stability. These dispersible metals can be dispersed in both aqueous and organic solvents.

[0067] The preferred size of the dispersible metal (B) described above varies depending on its shape. For example, for nanoparticles, the particle diameter is preferably 1 to 1000 nm. For nanowires, the length is preferably 1 to 50 μm. For nanofibers, the diameter is preferably 1 to 100 nm and the length is preferably 100 times the diameter or more. For nanorods, the diameter is preferably 1 to 100 nm and the length is preferably 20 to 100 times the diameter. For nanocubes, the length of each side is preferably 1 to 200 nm. For nanoplates, the thickness is preferably 1 to 100 nm and the width is preferably 2 to 20 times the thickness.

[0068] The method for incorporating the dispersible metal (B) into this composition is not particularly limited, but examples include incorporating a paste of the dispersible metal (B), or incorporating a dispersion (dispersion liquid) of the dispersible metal (B).

[0069] This composition is characterized by having a dispersible metal (B) content of 0.01 to 1.0% by mass, based on 100% by mass of the total composition. This content refers to the content of the dispersible metal (B) itself. That is, when this composition is manufactured using a dispersion of dispersible metal (B), components such as solvents contained in the dispersion are not taken into account in the dispersible metal (B) content.

[0070] The content of the dispersible metal (B) in this composition is not particularly limited as long as it is within the above range, but it is preferably 0.1 to 0.8% by mass, preferably 0.1 to 0.5% by mass, and more preferably 0.1 to 0.3% by mass, in that it has high compatibility and can maintain high conductivity.

[0071] Furthermore, the content of the dispersible metal (B) in this composition is not particularly limited as long as it satisfies the above range, but in terms of the resulting polymer film exhibiting excellent durability, it is preferably 0.01 to 100 parts by mass, preferably 0.05 to 20 parts by mass, and more preferably 0.1 to 10 parts by mass per 1 part by mass of polythiophene (A).

[0072] (Polyvinyl acetal resin (C)) This composition contains polyvinyl acetal resin (C). In this specification, polyvinyl acetal resin refers to a resin having a structural unit having a hydroxyl group represented by the following formula (a-1), a structural unit having an acetyl group represented by the following formula (a-2), and a structural unit having an acetal group represented by the following general formula (a-3).

[0073] [ka]

[0074] [In the above general formula (a-3), R 1a This represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. In polyvinyl acetal resin (C), R in the general formula (a-3) 1a While not particularly limited as long as it is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, it is preferably an alkyl group having 1 to 20 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms, i.e., a methyl group, an ethyl group, an n-propyl group, or an isopropyl group.

[0075] The content of the structural unit having a hydroxyl group represented by formula (a-1) in the polyvinyl acetal resin (C) is not particularly limited, but is preferably 10 to 50 mol%, more preferably 15 to 40 mol%, and even more preferably 20 to 30 mol%, based on 100 mol% of the total amount of prestructural units in the polyvinyl acetal resin (C).

[0076] The content of the structural unit having an acetyl group represented by formula (a-2) in the polyvinyl acetal resin (C) is not particularly limited, but is preferably 1 to 20 mol%, more preferably 1 to 17 mol%, and even more preferably 1 to 15 mol%, based on 100 mol% of the total amount of prestructural units in the polyvinyl acetal resin (C).

[0077] The content of structural units having an acetal group represented by the general formula (a-3) in the polyvinyl acetal resin (C) is not particularly limited, but is preferably 50 to 85 mol%, more preferably 60 to 80 mol%, and even more preferably 65 to 75 mol%, based on 100 mol% of the total amount of pre-structural units in the polyvinyl acetal resin (C).

[0078] The content of each structural unit in polyvinyl acetal resin (C) can be measured, for example, by NMR (nuclear magnetic resonance) spectroscopy.

[0079] The polyvinyl acetal resin (C) may contain structural units other than those represented by formula (a-1) or (a-2), or the general formula (a-3). Examples of such other structural units include ethylene structural units, or structural units having functional groups such as carboxyl groups, sulfonic acid groups, alkylene oxide groups, and amide groups. The polyvinyl acetal resin (C) may contain one or more such other structural units.

[0080] As the polyvinyl acetal resin (C), commercially available polyvinyl acetal resins can also be used. Examples of such commercially available polyvinyl acetal resins include the S-LEC® B series and S-LEC® K series manufactured by Sekisui Chemical Co., Ltd.

[0081] Furthermore, as the polyvinyl acetal resin (C), a polyvinyl acetal resin produced by a known method can also be used. For example, a polyvinyl acetal resin can be produced by reacting a polyvinyl alcohol resin with an aldehyde to acetalize it.

[0082] This composition is characterized in that, with the total amount of the composition being 100% by mass, the content of polyvinyl acetal resin (C) is 0.01 to 10% by mass. By including polyvinyl acetal resin (C) within the above range, the polyvinyl acetal resin (C) functions as a binder, reducing the permeation of oxygen into the composition, thereby reducing the oxidation of the dispersible metal (B) in the composition. As a result, the polymer film formed by creating a film of this composition can stably maintain a low surface resistance value.

[0083] The content of polyvinyl acetal resin (C) in this composition is not particularly limited as long as it is within the above range, but it is preferably 0.05 to 5% by mass, preferably 0.1 to 1% by mass, and more preferably 0.2 to 0.5% by mass, in order to exhibit excellent durability properties.

[0084] Furthermore, the content of polyvinyl acetal resin (C) in this composition is not particularly limited as long as it satisfies the above range, but it is preferably 0.01 to 100 parts by mass, preferably 0.05 to 20 parts by mass, and more preferably 0.1 to 10 parts by mass, per 1 part by mass of polythiophene (A).

[0085] (Silent solvent (D)) In addition to the above components, this composition preferably contains an organic solvent (D). In other words, this composition preferably uses an organic solvent as its solvent. The inclusion of an organic solvent (D) in this composition may improve its handling properties.

[0086] Conventionally, polyvinyl alcohol has been known as a component that can reduce the oxidative degradation of dispersible metals in conductive polymer compositions, as described in Patent Document 3. However, since polyvinyl alcohol does not dissolve in organic solvents, it cannot be applied to conductive polymer compositions containing organic solvents, meaning that organic solvent-dispersible metals cannot be used as dispersible metals. On the other hand, the polyvinyl acetal resin (C) contained in this composition dissolves in organic solvents. Therefore, this composition can provide a conductive polymer film that can stably maintain a low surface resistance value even when it contains an organic solvent (D). Accordingly, this composition can contain organic solvent-dispersible metals as dispersible metal (B).

[0087] The organic solvent (D) that this composition may contain is not particularly limited, but examples include alcohol solvents (e.g., methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butanol, 1-butanol, isobutanol, tertiary butanol, or ethylene glycol), aromatic hydrocarbon solvents (benzene, toluene, or xylene, etc.), ketone solvents (acetone, methyl ethyl ketone, methyl propyl ketone, methyl isobutyl ketone, or diacetone alcohol, etc.), ether solvents (methyl cellosolve, ethyl cellosolve, butyl cellosolve, or 1,4-dioxane, etc.), glycol ester solvents (ethylene glycol monoethyl ether acetate, propyl Examples of organic solvents (D) include ethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, or diethylene glycol monobutyl ether acetate, etc.; glycol ether solvents (methyl carbitol, ethyl carbitol, butyl carbitol, ethylene glycol monomethyl ether, or propylene glycol monomethyl ether, etc.); halogen solvents (chloroform, dichloromethane, 1,2-dichloroethane, or chlorobenzene, etc.); amide solvents (N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, dimethylimidazolidinone, or hexamethylphosphate triamide, etc.); or sulfur-containing solvents (dimethyl sulfoxide, or sulfolane, etc.). These organic solvents may be used individually as the organic solvent (D), or two or more organic solvents may be used in combination.

[0088] Among the organic solvents mentioned above, as the organic solvent (D), one or more selected from the group consisting of ethanol, isopropyl alcohol, 1-butanol, methyl isobutyl ketone, methyl ethyl ketone, N-methyl-2-pyrrolidone, and propylene glycol monomethyl ether are preferred, with ethanol being more preferred, due to their high dispersibility of the dispersible metal (B) (especially silver nanowires).

[0089] If the composition contains an organic solvent (D), its content is not particularly limited, but is preferably in the range of 79 to 99.7% by mass, and more preferably 85 to 99.5% by mass, based on 100% by mass of the total amount of the composition. Furthermore, regarding this content, if each component that the composition may contain, for example, a dispersible metal (B), is in the form of an organic solvent dispersion, the organic solvent contained in such dispersion is also taken into account as part of the content of organic solvent (D) in the composition.

[0090] Furthermore, the content of organic solvent (D) in this composition is not particularly limited, but is preferably 10 to 3,000 parts by mass, more preferably 50 to 2,000 parts by mass, and even more preferably 100 to 1,500 parts by mass, per 1 part by mass of polythiophene (A).

[0091] (water) This composition may also contain water in addition to the above components. In other words, this composition may be a composition using water as the solvent, or a composition using a mixed solvent of organic solvent (D) and water as the solvent.

[0092] The water that this composition may contain is not particularly limited, but examples include distilled water, ion-exchanged water, RO water, or ultrapure water.

[0093] If the composition contains water, the amount is not particularly limited, but is preferably in the range of 50 to 99.7% by mass, more preferably 60 to 99.5% by mass, and may also be 70 to 95% by mass, or 79 to 90% by mass, based on 100% by mass of the total amount of the composition. Furthermore, regarding the amount, if each component that the composition may contain, for example, dispersible metal (B), is in the form of an aqueous dispersion, the water contained in such dispersion is also taken into account as part of the water content of the composition.

[0094] (Other ingredients) This composition may further contain a dispersant, an inorganic filler, a carbon material, a binder, a viscosity modifier, a pH adjuster, an antioxidant, an antifoaming agent, a thickening agent, an anti-precipitation agent, or an antibacterial agent. Any of these components can be commercially available.

[0095] • Dispersant While not particularly limited, examples of dispersants include compounds whose main chain consists of polyester, polyacrylic, polyurethane, polyamine, or polycaprolactone-based materials, and whose side chains have polar groups such as amino groups, carboxyl groups, sulfone groups, or hydroxyl groups.

[0096] Examples of polyester-based dispersants that can be used include Disparon® KS873N, Disparon DA703-50, or Disparon DA7400 (manufactured by Kusumoto Chemical Co., Ltd.).

[0097] Examples of polyacrylic dispersants include Disperbyk(registered trademark)-2000, 2001, 2008, 2009, 2010, 2020, 2020N, ​​2022, 2025, 2050, 2070, 2095, 2150, 2151, 2155, 2163, 2164, BYKJET-9130, 9131, 9132, 9133, 9151 (manufactured by Bic Chemie), Efka(registered trademark) PX4310, PX4320, PX4330, PA4401, 4402, PA4403, 4570, 7411, 7477, PX4700, PX4701 (manufactured by BASF), and TERPLUS(registered trademark). D-1200, D-1410, D-1420, MD-1000 (manufactured by Otsuka Chemical Co., Ltd.), Floren DOPA-15BHFS, 17HF, 22, G-700, 900, NC-500, or GW-1500 (manufactured by Kyoeisha Chemical Co., Ltd.) may be used.

[0098] As a polyamine-based dispersant, for example, Disparon® 1860 (manufactured by Kusumoto Chemical Co., Ltd.) can be used.

[0099] Examples of polycaprolactone-based dispersants include Azisper® PB821, PB822, PB881 (manufactured by Ajinomoto Fine Techno Co., Ltd.), Hinoact® KF-1000, KF-1500, KF-1700, T-6000, T-7000, T-8000, T-8000E, T-9050 (manufactured by Kawaken Fine Chemical Co., Ltd.), S olsperse® 20000, 24000, 32000, 32500, 32550, 32600, 33000, 33500, 34000, 35200, 36000, 37500, 39000, 71000, 76400, 76500, 86000, 88000, J180, J200 (manufactured by Lubrizol), or TEGO® Dispers 652, 655, 685, 688, 690 (manufactured by Evonik Japan) may be used.

[0100] Other commercially available dispersants include, for example, Esream® AD-3172M, 374M, 508E, 221P, 221J, DP-2, DJ-2, Marialim® AKM-0531, AFB-1521, AAB-0851, SC-0505K, SC-1015F, or SC-0708A (manufactured by NOF Corporation).

[0101] • Binders other than polyvinyl acetal resin (C) Binders other than polyvinyl acetal resin (C) are substances that bind polythiophene (A) and dispersible metals (B), etc., and examples include polymer compounds such as resins other than polyvinyl acetal resin (C). Polyvinyl acetal resin (C) also has the effects described above and can function as a binder.

[0102] Specifically, examples of binders other than polyvinyl acetal resin (C) include fluororesins, polyolefins, conjugated diene polymers, acrylic resins, polyvinyl alcohol resins, cellulose resins, and latex resins.

[0103] Examples of fluororesins include polyvinylidene fluoride, polytetrafluoroethylene, ethylene-tetrafluoroethylene copolymer, and vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene copolymer.

[0104] Examples of polyolefins include polyethylene, polypropylene, and modified versions thereof.

[0105] Examples of conjugated diene polymers include styrene-butadiene copolymers, acrylonitrile-butadiene copolymers, and acrylonitrile-butadiene-styrene copolymers, as well as their hydrides.

[0106] Examples of acrylic resins include methacrylic acid ester copolymers, acrylic acid ester copolymers, methacrylic acid ester-acrylic acid ester copolymers, styrene-acrylic acid ester copolymers, and acrylonitrile-acrylic acid ester copolymers.

[0107] Examples of polyvinyl alcohol-based resins include polyvinyl alcohol and polyvinyl acetate.

[0108] Examples of cellulose-based resins include ethylcellulose, methylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, and carboxymethylcellulose.

[0109] Examples of latexes include copolymers of unsaturated carboxylic acid monomers with other monomers copolymerizable thereto. Examples of unsaturated carboxylic acid monomers include (meth)acrylic acid, and examples of other monomers include styrene. Such copolymers can be produced, for example, by known emulsion polymerization. Specific examples include styrene-butadiene latex, acrylic latex, acrylonitrile-butadiene latex, fluorine latex, and silicone latex.

[0110] • Inorganic filler Examples of inorganic fillers include silica, silica-alumina, glass, calcium carbonate, calcium hydroxide, talc, alumina, titania, zirconia, boehmite, antimony oxide, chromium oxide, nickel oxide, copper oxide, tin oxide, titanium oxide, zirconium oxide, indium oxide, zinc oxide, magnesium hydroxide, aluminum hydroxide, hydrotalcite, mica, silver particles, copper particles, gold particles, and aluminum particles.

[0111] • Carbon materials Examples of carbon materials include carbon nanotubes, carbon black, graphite, and vapor-grown carbon fibers.

[0112] (Method for producing this composition) The method for producing this composition is not particularly limited, but for example, it involves mixing the above-mentioned polythiophene (A), a dispersible metal (B), a polyvinyl acetal resin (C), and, if necessary, a solvent (preferably an organic solvent (D)) and other components. It is preferable, however, that each material be added and dissolved in the solvent before mixing. Furthermore, the order in which the materials are added and mixed is not particularly limited, and this composition can be produced by mixing these materials in any order.

[0113] In the method for producing this composition, the temperature at which each material is mixed is not particularly limited, but can be, for example, at room temperature (15-25°C) or under heating. 0°C to 100°C is preferred. Furthermore, the atmosphere during mixing is not particularly limited and can be air or an inert gas.

[0114] In the method for producing this composition, when mixing each material, in addition to general mixing and dissolution operations using a stirrer tip or stirring blade, ultrasonic irradiation and homogenization (for example, using a mechanical homogenizer, ultrasonic homogenizer, or high-pressure homogenizer) may be performed. When homogenizing, it is preferable to perform the process at a low temperature to prevent thermal degradation of the polymer.

[0115] The concentration of each component in this composition may be adjusted by the mixing ratio, or by concentration or dilution after mixing. The method of concentration is not particularly limited and may include removing the solvent under reduced pressure or using an ultrafiltration membrane.

[0116] [Conductive polymer film] A conductive polymer film according to one aspect of the present invention comprises a polythiophene (A) having 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), a dispersible metal (B), and a polyvinyl acetal resin (C).

[0117] [ka]

[0118] [In the above general formula (1), M + R represents a hydrogen ion, an alkali metal ion, a conjugate acid of an amine compound, or a quaternary ammonium cation. In the above general formulas (1) and (2), R represents an organic group with a total of 1 to 14 carbon atoms having at least one substituent selected from the group consisting of a sulfonic acid group and a phosphonic acid group. Hereinafter, a conductive polymer film according to one aspect of the present invention may be referred to as "the polymer film." Because the polymer film has the above-described structure, it can stably maintain a low surface resistance value while containing a polythiophene-based conductive polymer material and a dispersible metal.

[0119] This polymer film may contain polythiophene (A), a dispersible metal (B), and polyvinyl acetal resin (C), as well as other components (solvents and other components) that may be included in this composition.

[0120] The specific characteristics of each component contained in this polymer film are the same as those described in the section on [Conductive Polymer Composition], so we will refer to that description and omit further details in this section.

[0121] (Method for manufacturing this polymer film) The polymer film can be produced from a composition comprising polythiophene (A), a dispersible metal (B), and a polyvinyl acetal resin (C), preferably by forming a film of this composition. The method for forming the film of this composition is not particularly limited, but for example, it can be a method of coating the composition onto a support and then drying it. That is, in one embodiment of the present invention, a method for producing a conductive polymer film is provided, characterized by coating the composition onto a support and then drying it.

[0122] Hereinafter, a method for manufacturing a conductive polymer film relating to one aspect of the present invention may be referred to as "the method for manufacturing this polymer film."

[0123] The support used in the method for producing this polymer film is not particularly limited as long as it can be coated with this composition, but examples include polymer substrates and inorganic substrates. Examples of polymer substrates include thermoplastic resins, nonwoven fabrics, paper, or resist film substrates. Examples of thermoplastic resins include polyethylene, polypropylene, polyethylene terephthalate (PET), polyacrylate, or polycarbonate. Examples of nonwoven fabrics include those made of natural fibers or synthetic fibers. Examples of paper include those mainly composed of cellulose. Examples of inorganic substrates include glass, glass fibers, ceramics, aluminum oxide, or tantalum oxide.

[0124] In the method for producing this polymer film, examples of methods for applying the composition include casting, dipping, bar coating, dispenser coating, roll coating, gravure coating, flexographic printing, screen printing, or offset printing.

[0125] In the method for producing this polymer film, the temperature at which the composition coated on the support is dried is not particularly limited as long as it is below the temperature at which a uniform conductive polymer film can be obtained and the heat resistance temperature of the support. However, it 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.

[0126] The atmosphere in which the above drying is performed may be air, an inert gas, a vacuum, or under reduced pressure. From the viewpoint of suppressing the degradation of the resulting conductive polymer film, an inert gas such as nitrogen or argon is preferred.

[0127] The thickness of the resulting conductive polymer film is not particularly limited, but 10 -3 ~10 3 A range of μm is preferred, and more preferably 10 -3 ~10 2 The thickness is μm. In other words, in the method for producing this polymer film, it is preferable to apply the composition such that the thickness of the resulting conductive polymer film falls within the above range.

[0128] This polymer film has excellent conductivity and transmittance, and can stably maintain a low surface resistance. Therefore, this polymer film can be suitably used as an electrode material, a transparent conductive film, a radio wave shielding material, etc., and can be suitably used in various articles incorporating these, such as solid electrolytes for capacitors, transparent electrodes, protective films for polarizing plates, or OCA (optical transparent adhesive) for touch panels. In other words, an article comprising this polymer film is provided in one embodiment of the present invention.

[0129] 〔summary〕 One aspect of the present invention may include the following [1] to [9].

[0130] [1] A conductive polymer composition characterized by containing 0.01 to 10% by mass of polythiophene (A) having 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 1.0% by mass of a dispersible metal (B), and 0.01 to 10% by mass of polyvinyl acetal resin (C).

[0131] [ka]

[0132] [In the above general formula (1), M + R represents a hydrogen ion, an alkali metal ion, a conjugate acid of an amine compound, or a quaternary ammonium cation. In the general formulas (1) and (2) above, R represents an organic group with a total of 1 to 14 carbon atoms having at least one substituent selected from the group consisting of a sulfonic acid group and a phosphonic acid group. [2] The conductive polymer composition according to [1], wherein the dispersible metal (B) is at least one dispersible metal selected from the group consisting of silver nanoparticles, silver nanoplates, silver nanowires, copper nanoparticles, copper nanoplates, and copper nanowires.

[0133] [3] The conductive polymer composition according to [1] or [2], wherein the dispersible metal (B) is silver nanowire.

[0134] [4] The conductive polymer composition according to any one of [1] to [3], wherein the content of polythiophene (A) is 0.1 to 5% by mass.

[0135] [5] The conductive polymer composition according to any one of [1] to [4], wherein the content of the dispersible metal (B) is 0.01 to 100 parts by mass per 1 part by mass of the polythiophene (A).

[0136] [6] The conductive polymer composition according to any one of [1] to [5], further comprising 79 to 99.7% by mass of an organic solvent (D).

[0137] A method for producing a conductive polymer film, characterized by applying a conductive polymer composition described in any of [7], [1] to [6] to a support, and then drying it.

[0138] [8] A conductive polymer film comprising polythiophene (A), a dispersible metal (B), and a polyvinyl acetal resin (C), having 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).

[0139] [ka]

[0140] [In the above general formula (1), M + R represents a hydrogen ion, an alkali metal ion, a conjugate acid of an amine compound, or a quaternary ammonium cation. In the above general formulas (1) and (2), R represents an organic group with a total of 1 to 14 carbon atoms having at least one substituent selected from the group consisting of a sulfonic acid group and a phosphonic acid group. An article comprising the conductive polymer film described in [9][8].

[0141] [Additional Notes] The present invention is not limited to the embodiments described above, and various modifications are possible within the scope of the claims. Embodiments obtained by appropriately combining the technical means disclosed in different embodiments are also included in the technical scope of the present invention. [Examples]

[0142] Examples are shown below, but the present invention is not limited to these examples. The materials and analytical instruments used in these examples are listed below. In addition, the "%" or ratio values ​​indicating the content in the following examples and comparative examples are based on mass unless otherwise specified.

[0143] (material) • Polythiophene (A) Polythiophene (poly(3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-methyl-1-propanesulfonic acid) prepared in accordance with Synthesis Example 1 and Synthesis Example 2 of Japanese Patent Publication No. 2019-196443; corresponds to a polymer composed of the structural unit represented by the above general formula (3) and the structural unit represented by the above general formula (4). However, R 2 =methyl group, M + (=Hydrogen ion, m=2, n=1; hereinafter abbreviated as "PT".) ·Dispersible metal (B) Silver nanowire (AgNW) 0.5 wt% ethanol solution (product name T-AG237) / Manufactured by Seikoh PMC Co., Ltd. • Polyvinyl acetal resin (C) S-REC (registered trademark) K series (KS-10) / Manufactured by Sekisui Chemical Co., Ltd. S-REC® B Series (BL-10, BM-2, and BH-A) / Manufactured by Sekisui Chemical Co., Ltd. Polyvinyl butyral resin / Manufactured by Pharmatech Ltd. • Organic solvent (D) Ethanol (EtOH) • Comparative component (used in the comparative example) Epoxy resin: ADEKA Resin EP-3908S / Manufactured by ADEKA Corporation Polycarbodiimide resin: Carbodilite V-02 / Manufactured by Nisshinbo Chemical Co., Ltd. Polyalkylene glycol resin: Esream AD-374M / Manufactured by NOF Corporation Polyvinyl alcohol / Manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. (Measurement of surface resistance) The surface resistance of the conductive polymer films prepared in the examples and comparative examples was measured using a Loresta GP MCP-T600 measuring device manufactured by Mitsubishi Chemical Corporation. This measurement was performed a total of four times, and the average value was taken as the surface resistance value of the conductive polymer film at the time of measurement.

[0144] [Example 1] Preparation of conductive polymer compositions A conductive polymer composition was prepared by adding polythiophene (A), dispersible metal (B), and polyvinyl acetal resin (C) of the type listed in Table 1 to ethanol, which is an organic solvent (D), in the amounts (concentrations) listed in Table 1, and stirring and mixing.

[0145] Preparation of conductive polymer films The conductive polymer composition prepared above was applied to a PET film substrate to a wet film thickness of 52 μm. Next, the applied conductive polymer composition was heated and dried in air at 80°C for 5 minutes to form a conductive polymer film. The surface resistance of the formed conductive polymer film was measured using the method described above at three time points: immediately after film formation (initial), 2 days after film formation, and 12 days after film formation. The results are shown in Table 1.

[0146] [Examples 2-6, Comparative Examples 1-5] Except for changing the composition of the conductive polymer composition as shown in Table 1, the conductive polymer composition and conductive polymer film were prepared using the same procedure as in Example 1, and the surface resistance of the obtained conductive polymer film was measured. The results are shown in Table 1. In Comparative Example 5, the polyvinyl alcohol did not dissolve in the solvent, and therefore the conductive polymer composition and conductive polymer film could not be prepared. Consequently, the surface resistance could not be measured.

[0147] [Table 1]

[0148] In Table 1, the content of each component is expressed as a mass percentage (wt%) relative to the total amount of the conductive polymer composition (100% by mass).

[0149] As shown in Table 1, the conductive polymer films of Examples 1 to 6 all maintained low surface resistance values ​​even 12 days after film formation. On the other hand, the conductive polymer films of Comparative Examples 1 and 4 showed a significant increase in surface resistance values ​​2 to 12 days after film formation and were unable to maintain low surface resistance values. Furthermore, the conductive polymer films of Comparative Examples 2 and 3 already had high surface resistance values ​​immediately after film formation, and in the case of Comparative Example 5, film formation of the conductive polymer film itself was impossible.

[0150] From the above results, it has been shown that a conductive polymer composition according to one aspect of the present invention can provide a conductive polymer film that can stably maintain a low surface resistance value. [Industrial applicability]

[0151] A conductive polymer composition according to one aspect of the present invention can provide a conductive polymer film that can stably maintain a low surface resistance value. Such a conductive polymer film can be suitably used as an electrode material, a transparent conductive film, a radio wave shielding material, and the like. Furthermore, it can be suitably used in various components that incorporate these on a substrate (support), such as solid electrolytes for capacitors, transparent electrodes, protective films for polarizing plates, or OCA (optical transparent adhesive) for touch panels.

Claims

1. A polythiophene (A) having at least one structural unit selected from the group consisting of the structural unit represented by the following general formula (1) and the structural unit represented by the following general formula (2) is present in an amount of 0.01 to 10% by mass. Dispersible metal (B) in an amount of 0.01 to 1.0 mass%, and A conductive polymer composition characterized by containing 0.01 to 10% by mass of polyvinyl acetal resin (C). 【Chemistry 1】 [In the above general formula (1), M ＋ R represents a hydrogen ion, an alkali metal ion, a conjugate acid of an amine compound, or a quaternary ammonium cation. In the general formulas (1) and (2) above, R represents an organic group having 1 to 14 carbon atoms and having at least one substituent selected from the group consisting of a sulfonic acid group and a phosphonic acid group.

2. The conductive polymer composition according to claim 1, wherein the dispersible metal (B) is at least one dispersible metal 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 claim 1, wherein the dispersible metal (B) is silver nanowire.

4. The conductive polymer composition according to claim 1, wherein the content of the polythiophene (A) is 0.1 to 5% by mass.

5. The conductive polymer composition according to claim 1, wherein the content of the dispersible metal (B) is 0.01 to 100 parts by mass per 1 part by mass of the polythiophene (A).

6. Furthermore, the conductive polymer composition according to claim 1, further comprising 79 to 99.7% by mass of an organic solvent (D).

7. A method for producing a conductive polymer film, characterized by applying the conductive polymer composition described in any one of claims 1 to 6 to a support, and then drying it.

8. A polythiophene (A) having 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), Dispersible metals (B), and A conductive polymer film containing polyvinyl acetal resin (C). 【Chemistry 2】 [In the above general formula (1), M ＋ R represents a hydrogen ion, an alkali metal ion, a conjugate acid of an amine compound, or a quaternary ammonium cation. In the above general formulas (1) and (2), R represents an organic group having a total of 1 to 14 carbon atoms and having at least one substituent selected from the group consisting of a sulfonic acid group and a phosphonic acid group.

9. An article comprising a conductive polymer film as described in claim 8.

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