Conductive polymer solution, conductive polymer film, and coated article

Abstract

To provide: a conductive polymer solution capable of forming a conductive coating film excellent in hardness; a conductive polymer film increased in hardness and conductivity; and an article coated therewith.SOLUTION: The conductive polymer solution contains: 0.1-5 wt.% of a polythiophene (A) that can be produced by polymerizing thiophene monomers represented by the general formula (3) in the figure in water or an alcohol solvent in the presence of an oxidant; and 0.1-7 wt.% of a silane compound (B) represented by general formula Si(-OR3)(-R4)(-R5)(-R6).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention aims to provide a film having both excellent conductivity and hardness, and relates to a novel conductive composition solution characterized by containing a specific self-doped conductive polymer having high conductivity and a specific silicate. The present invention also relates to a film obtained by drying the solution, and to an article coated with the film. [Background technology]

[0002] Conductive polymer materials have been developed in which π-conjugated polymers, such as polyacetylene, polythiophene, polyaniline, or 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, actuators, etc. Among these conductive polymer materials, polythiophene-based conductive polymer materials are practically useful in terms of chemical stability.

[0003] Examples of polythiophene-based conductive polymer materials include PEDOT / PSS aqueous dispersions 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 provide both water solubility and doping properties in the polymer main chain, either directly or via a spacer; for example, sulfonated polyaniline and PEDOT-S are known (see, for example, Patent Documents 1, 2, and 3). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2015-63652 [Patent Document 2] Japanese Patent Application Laid-Open No. 2015-147834 [Patent Document 3] Japanese Patent Application Publication No. 2018-90755 Summary of the Invention [Problem to be solved by the invention]

[0005] Conductive polymers are not only used as antistatic agents and solid electrolytes in solid electrolytic capacitors, but in recent years they have also been used on the outermost surfaces of devices and films as antistatic films, low-resistance films, and other transparent conductive films, and are therefore required to have high hardness properties in addition to conductivity and water resistance.

[0006] The present invention has been made in view of the above-mentioned background art, and its object is to provide a conductive polymer film that has both conductivity (appropriate surface resistance value) and high hardness suitable for an antistatic film. [Means for solving the problem]

[0007] As a result of extensive research into solving the above problems, the present inventors have found that the above problems can be solved by using the conductive polymer solution of the present invention, which is characterized by containing a specific self-doped conductive polymer and a specific silane compound, and have thus completed the present invention.

[0008] That is, the present invention relates to a conductive polymer solution composition, a conductive polymer film, and an article coated therewith, as shown below.

[0009] [1] A conductive polymer solution containing 0.1 to 5 wt % of a polythiophene (A) containing at least two or more structural units of at least one kind 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 containing 0.1 to 7 wt % of a silane compound (B) represented by the following general formula (4):

[0010] [ka]

[0011] In general formula (1), M represents a hydrogen ion, an alkali metal ion, an ammonium ion, an organic ammonium ion, or a quaternary ammonium cation. 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.

[0012] [ka]

[0013] [In general formula (4), R 3 represents a methyl group, an ethyl group, or a linear or branched alkyl group having 3 to 8 carbon atoms. 4 , R 5 , and R 6 each independently represents a methyl group, an ethyl group, a linear or branched alkyl group having 3 to 8 carbon atoms, a methoxy group, an ethoxy group, or a linear or branched alkoxy group having 3 to 8 carbon atoms. [2] The conductive polymer solution according to [1], wherein the silane compound (B) is tetramethoxysilane, tetraethoxysilane, methyltriethoxysilane, methyltrimethoxysilane, dimethyldiethoxysilane, or dimethyldimethoxysilane.

[0014] [3] The conductive polymer solution according to [1] or [2], wherein the content of the silane compound (B) is 0.5 to 10 parts by weight per 1 part by weight of the polythiophene (A).

[0015] [4] The conductive polymer solution according to any one of [1] to [3], further comprising, in addition to the polythiophene (A) and the silane compound (B), 0.1 to 7 wt % of a silane compound (B2) having an epoxy group and / or an amino group.

[0016] [5] The conductive polymer solution according to [4], wherein the silane compound (B2) having an epoxy group and / or an amino group is 3-glycidyloxypropyltrimethoxysilane or 3-glycidyloxypropyltriethoxysilane.

[0017] [6] The conductive polymer solution according to any one of [1] to [5], further comprising a silicone compound (E), wherein the content of the silicone compound (E) is 0.001 to 5% by weight relative to the total amount of the conductive polymer solution.

[0018] [7] The conductive polymer solution according to any one of [1] to [6], further comprising water, wherein the content of the water is 50 to 99.9% by weight relative to the total amount of the conductive polymer solution.

[0019] [8] A method for producing a film, comprising applying the conductive polymer solution according to any one of [1] to [7] to a support and then drying the applied conductive polymer solution.

[0020] [9] A film comprising a polythiophene (A) containing at least two or more structural units 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 silane compound (B) represented by the following general formula (4):

[0021] [ka]

[0022] In general formula (1), M represents a hydrogen ion, an alkali metal ion, an ammonium ion, an organic ammonium ion, or a quaternary ammonium cation. In general formulas (1) and (2), R 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.

[0023] [ka]

[0024] [In general formula (4), R 3 represents a methyl group, an ethyl group, or a linear or branched alkyl group having 3 to 8 carbon atoms. 4 , R 5 , and R 6 each independently represents a methyl group, an ethyl group, a linear or branched alkyl group having 3 to 8 carbon atoms, a methoxy group, an ethoxy group, or a linear or branched alkoxy group having 3 to 8 carbon atoms.

[10] The film according to [9], wherein the content of the silane compound (B) is 0.5 to 10 parts by weight per 1 part by weight of the content of the polythiophene (A).

[0025]

[11] The film according to [9] or

[10] , further comprising a silane compound (B2) having an epoxy group and / or an amino group as a constituent component, wherein the content of the silane compound (B2) having an epoxy group and / or an amino group is 0.1 to 10 parts by weight per part by weight of the content of the polythiophene (A).

[0026]

[12] The film according to any one of [9] to

[11] , further comprising a silicone compound (E) as a constituent component, wherein the content of the silicone compound (E) is 0.01 to 10 parts by weight per 1 part by weight of the content of the polythiophene (A).

[0027]

[13] A coated article in which at least a portion of a substrate is covered with the film according to any one of [9] to

[12] . [Effects of the Invention]

[0028] The conductive polymer film prepared from the novel conductive polymer solution of the present invention exhibits the effect of achieving both highly desirable conductivity (moderate surface resistivity) and high hardness for an antistatic film. Therefore, the antistatic film prepared from the conductive polymer solution of the present invention is expected to be used as a conductive protective film with high physical durability. DETAILED DESCRIPTION OF THE INVENTION

[0029] The present invention is described in detail below. The present invention relates to a conductive polymer solution containing 0.1 to 5 wt % of a polythiophene (A) containing at least two or more structural units of at least one kind 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 containing 0.1 to 7 wt % of a silane compound (B) represented by the following general formula (4):

[0030] [ka]

[0031] In general formula (1), M represents a hydrogen ion, an alkali metal ion, an ammonium ion, an organic ammonium ion, or a quaternary ammonium cation. 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.

[0032] [ka]

[0033] [In general formula (4), R 3represents a methyl group, an ethyl group, or a linear or branched alkyl group having 3 to 8 carbon atoms. 4 , R 5 , and R 6 each independently represents a methyl group, an ethyl group, a linear or branched alkyl group having 3 to 8 carbon atoms, a methoxy group, an ethoxy group, or a linear or branched alkoxy group having 3 to 8 carbon atoms. In the above general formula (1), M represents a hydrogen ion, an alkali metal ion, an ammonium ion, an organic ammonium ion, or a quaternary ammonium cation.

[0034] The polythiophene (A) will be described below.

[0035] As the alkali metal ion, for example, Li ion, Na ion, and K ion are preferable.

[0036] The organic ammonium ion is not particularly limited, and examples thereof include primary, secondary, or tertiary organic ammonium ions having a total carbon number of 1 to 30. More specific examples thereof include methylammonium ion, dimethylammonium ion, trimethylammonium ion, ethylammonium ion, triethylammonium ion, normal-propylammonium ion, isopropylammonium ion, normal-butylammonium ion, hexylammonium ion, 2-hydroxyethylammonium ion, N,N-dimethyl-N-(2-hydroxyethyl)ammonium ion, N-methyl-N-(2-hydroxyethyl)ammonium ion, di(2-hydroxyethyl)ammonium ion, N-methyl-N,N Examples of the ammonium ion include N,N,N-di(2-hydroxyethyl)ammonium ion, N,N,N-tri(2-hydroxyethyl)ammonium ion, 2,3-dihydroxypropylammonium ion, N-methyl-N-(2,3-dihydroxypropyl)ammonium ion, N,N-dimethyl-N-(2,3-dihydroxypropyl)ammonium ion, triisobutylammonium ion, triisopentylammonium ion, triisooctylammonium ion, imidazolium ion, N-methylimidazolium ion, 1,2-dimethylimidazolium ion, pyridinium ion, methylpyridinium ion, imidazolium ion, 1-methylimidazolium ion, 2-methylimidazolium ion, picolinium ion, and lutidinium ion.

[0037] The quaternary ammonium cation is not particularly limited, but examples thereof include tetramethylammonium cation, tetraethylammonium cation, tetra-n-propylammonium cation, tetra-n-butylammonium cation, tetra-n-hexylammonium cation, etc. Among these, from the viewpoint of availability, the tetramethylammonium cation or tetraethylammonium cation is preferred.

[0038] From the viewpoint of the coatability of the conductive polymer solution, M is selected from the group consisting of hydrogen ions, alkali metal ions (e.g., Li ions, Na ions, and K ions), tetramethylammonium cations, tetraethylammonium cations, ammonium ions, trimethylammonium ions, triethylammonium ions, 2-hydroxyethylammonium ions, N-methyl-N-(2-hydroxyethyl)ammonium ions, 2,3-dihydroxypropylammonium ions, N-methyl-N-(2,3-dihydroxypropyl)ammonium ions, di(2-hydroxyethyl)ammonium ions, N,N,N-tri(2-hydroxyethyl)ammonium ions, pyridinium ions, methylpyridinium ions, and imidazolium ions. , 1-methylimidazolium ion, and 2-methylimidazolium ion, and more preferably at least one ion selected from the group consisting of hydrogen ion, Li ion, Na ion, K ion, tetramethylammonium cation, tetraethylammonium cation, ammonium ion, trimethylammonium ion, triethylammonium ion, 2-hydroxyethylammonium ion, di(2-hydroxyethyl)ammonium ion, N,N,N-tri(2-hydroxyethyl)ammonium ion, pyridinium ion, imidazolium ion, 1-methylimidazolium ion, and 2-methylimidazolium ion.

[0039] 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.

[0040] 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.

[0041] 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.

[0042] 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.

[0043] In the above general formulas (1) and (2), n is 0 or 1, but is preferably 1 from the viewpoint of film-forming properties.

[0044] The structural unit represented by the general formula (2) represents the doped state of the structural unit represented by the general formula (1).

[0045] 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.

[0046] 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. Such a polymer that exhibits conductivity without the addition of an external dopant is called a self-doped conductive polymer.

[0047] The polythiophene (A) containing at least two or more structural units of at least one kind selected from the group consisting of structural units represented by the above general formula (1) and structural units represented by the general formula (2) (provided that M is not a hydrogen ion) can be produced by mixing and reacting a polythiophene (A') containing at least two or more structural units of at least one kind 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') with at least one compound selected from the group consisting of alkali metal compounds, ammonia, organic amine compounds, and quaternary ammonium salts.

[0048] [ka]

[0049] [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. In the above general formulas (1') and (2'), R 2 The definition and preferred range of m or n are as follows: 2 , m, or n.

[0050] The alkali metal compound is not particularly limited, but examples thereof include alkali metal halide 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.).

[0051] The organic amine compound is not particularly limited, and examples thereof include primary, secondary, or tertiary organic 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, triisobutylamine, triisopentylamine, triisooctylamine, imidazole, N-methylimidazole, 1,2-dimethylimidazole, pyridine, methylpyridine, imidazole, 1-methylimidazole, 2-methylimidazole, picoline, and lutidine.

[0052] The quaternary ammonium compound is not particularly limited, and examples thereof include tetramethylammonium chloride, tetraethylammonium chloride, tetra-normal-propylammonium chloride, tetra-normal-butylammonium chloride, tetra-normal-hexylammonium chloride, tetramethylammonium bromide, tetraethylammonium bromide, tetra-normal-propylammonium bromide, tetra-normal-butylammonium bromide, tetra-normal-hexylammonium bromide, tetramethylammonium iodide, tetraethylammonium iodide, tetra-normal-propylammonium iodide, tetra-normal-butylammonium iodide, tetra-normal-hexylammonium iodide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-normal-propylammonium hydroxide, tetra-normal-butylammonium hydroxide, and tetra-normal-hexylammonium hydroxide.

[0053] The polythiophene (A) may be a commercially available product or may be synthesized based on publicly known information. The synthesis method is not particularly limited, but for example, the polythiophene (A) can be produced by polymerizing a thiophene monomer represented by the following general formula (3) in the presence of an oxidizing agent in water or an alcohol solvent, and then optionally treating with an acid to produce the polythiophene (A').

[0054] [ka]

[0055] [In the above general formula (3), R 2 , m, n, and M are R in the above general formulas (1) and (2). 2 , m, n, and M have the same definitions.] Regarding the polymer obtained after polymerization of the thiophene monomer represented by general formula (3) (wherein M is not a hydrogen ion), M can be converted to a hydrogen ion by acid treatment. The polymerization method and the method for converting M to a hydrogen ion are not particularly limited, and any method described in a known document can be selected and used. By the conversion to a hydrogen ion, a polythiophene (A') containing 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') can be produced.

[0056] The thiophene monomer represented by the general formula (3) is not particularly limited, but specific examples thereof include 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-propanesulfonate, sodium 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-methyl-1-propanesulfonate, Sodium thieno[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-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 pansulfonate, 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-isobutyl-1-propanesulfonate 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-propanesulfonate, 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-methyl-1-propanesulfonic acid, 3-[(2,Ammonium 3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-methyl-1-propanesulfonate, Triethylammonium 3-[(2,3-dihydrothieno[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, 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-methyl-1-butanesulfonate, sodium 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-methyl-1-butanesulfonate, sodium 4-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-fluoro-1-butanesulfonate , 4-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-fluoro-1-butanesulfonic acid potassium salt, 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-sulfonic acid sodium salt, 6-(2,3-dihydro-thieno[3,4-b][1,4]dioxin-2-yl)hexane-1-sulfonic acid lithium salt Examples include thieno[3,4-b][1,4]dioxin-2-yl)hexane-1-sulfonic acid potassium salt, 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, and 8-(2,3-dihydro-thieno[3,4-b][1,4]dioxin-2-yl)octane-1-sulfonic acid potassium salt.

[0057] 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.

[0058] The content of the polythiophene (A) in the conductive polymer solution of the present invention is characterized by being 0.1 to 5% by weight based on the entire conductive polymer solution, but from the viewpoint of achieving both high conductivity and high hardness, the content is preferably 0.1 to 4% by weight, more preferably 0.1 to 3% by weight, even more preferably 0.2 to 3% by weight, and still more preferably 0.2 to 2% by weight.

[0059] The silane compound (B) will be described below.

[0060] The conductive polymer solution of the present invention is a polymer represented by the following general formula (4):

[0061] [ka]

[0062] [In general formula (4), R 3 represents a methyl group, an ethyl group, or a linear or branched alkyl group having 3 to 8 carbon atoms. 4 , R 5 , and R 6 each independently represents a methyl group, an ethyl group, a linear or branched alkyl group having 3 to 8 carbon atoms, a methoxy group, an ethoxy group, or a linear or branched alkoxy group having 3 to 8 carbon atoms. The conductive polymer solution is characterized in that it contains a silane compound (B) represented by the following formula: and the content of the silane compound (B) is 0.1 to 7% by weight of the entire conductive polymer solution.

[0063] The linear or branched alkyl group having 3 to 8 carbon atoms is not particularly limited, but examples thereof include a propyl group, an i-propyl group, a cyclopropyl group, a butyl group, an i-butyl group, a sec-butyl group, a tert-butyl group, a hexyl group, a cyclohexyl group, an octyl group, and a 2-ethylhexyl group.

[0064] The linear or branched alkoxy group having 3 to 8 carbon atoms is not particularly limited, but examples thereof include a propoxy group, an i-propoxy group, a cyclopropyloxy group, a butoxy group, an i-butoxy group, a sec-butoxy group, a tert-butoxy group, a hexyloxy group, a cyclohexyloxy group, an octyloxy group, and a 2-ethylhexyloxy group.

[0065] The silane compound (B) represented by the general formula (4) is not particularly limited, but specific examples include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, tetrahexyloxysilane, tetraoctyloxysilane, tetra(2-ethylhexyloxy)silane, methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, ethyltrimethoxysilane, diethyldimethoxysilane, triethylmethoxysilane, propyltrimethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, t-butyltrimethoxysilane, and t-butyltriethoxysilane.

[0066] The silane compound (B) used in the present invention may be used alone or in combination of two or more. Note that, as the silane compound (B), a commercially available product may be used as is, or a product produced by a generally known method may be used.

[0067] As the silane compound (B) represented by the above general formula (4), tetramethoxysilane, tetraethoxysilane, methyltriethoxysilane, methyltrimethoxysilane, dimethyldiethoxysilane, or dimethyldimethoxysilane is preferred, and tetraethoxysilane is more preferred, in terms of excellent film hardness.

[0068] The content of the silane compound (B) in the conductive polymer solution of the present invention is 0.1 to 7% by weight based on the total weight of the conductive polymer solution, but from the viewpoint of achieving an excellent balance between high conductivity and high hardness, the content is more preferably 0.2 to 5% by weight, and even more preferably 0.5 to 4% by weight.

[0069] In the conductive polymer solution of the present invention, the content of the silane compound (B) is preferably 0.5 to 10 parts by weight relative to 1 part by weight of the polythiophene (A), more preferably 1 to 9 parts by weight relative to 1 part by weight of the polythiophene (A), and more preferably 2 to 8 parts by weight relative to 1 part by weight of the polythiophene (A), in terms of achieving both excellent film hardness and conductivity.

[0070] The conductive polymer solution of the present invention may further contain, in addition to the polythiophene (A) and the silane compound (B), a silane compound (B2) having an epoxy group and / or an amino group, and the content of the silane compound (B2) having an epoxy group and / or an amino group is preferably 0.1 to 7% by weight of the entire conductive polymer solution.

[0071] The silane compound (B2) is not particularly limited, but examples thereof include aminopropyltrimethoxysilane, epoxypropyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, propyltriethoxysilane, aminopropyltriethoxysilane, epoxypropyltriethoxysilane, and 3-glycidyloxypropyltriethoxysilane. Of these, 3-glycidyloxypropyltrimethoxysilane and 3-glycidyloxypropyltriethoxysilane are preferred because they are excellent in both film hardness and conductivity. Note that, as for the silane compound (B2), commercially available products can be used as they are, or those produced by a commonly known method can also be used.

[0072] The content of the silane compound (B2) in the conductive polymer solution of the present invention is more preferably 0.1 to 5 wt %, more preferably 0.1 to 2 wt %, and even more preferably 0.1 to 1 wt %, based on the total weight of the conductive polymer solution.

[0073] In the conductive polymer solution of the present invention, the content of the silane compound (B2) is preferably 0.1 to 10 parts by weight relative to 1 part by weight of the polythiophene (A), more preferably 0.2 to 7 parts by weight relative to 1 part by weight of the polythiophene (A), and more preferably 0.3 to 5 parts by weight relative to 1 part by weight of the polythiophene (A), in terms of achieving both excellent film hardness and electrical conductivity.

[0074] The conductive polymer solution of the present invention may further contain another compound in addition to the polythiophene (A) and silane compound (B) (which may further contain a silane compound (B2)). The other compound is not particularly limited, but examples thereof include at least one surfactant (C) selected from the group consisting of nonionic surfactants and amphoteric surfactants, an alcohol (D), and / or a silicone compound (E) (these do not include the polythiophene (A), the silane compound (B), and the silane compound (B2)).

[0075] When the conductive polymer solution of the present invention contains at least one surfactant (C) selected from the group consisting of the nonionic surfactants and amphoteric surfactants, the content thereof is preferably 0.001 to 10% by weight, more preferably 0.1 to 5% by weight, based on the total weight of the conductive polymer solution. By adding the surfactant (C), improvements in the operability and film-forming properties of the conductive polymer solution are expected.

[0076] From the viewpoint of film-forming properties, the surfactant (C) is preferably at least one surfactant (C) selected from the group consisting of polyethylene glycol surfactants, acetylene glycol surfactants, polyhydric alcohol surfactants, betaine amphoteric surfactants, fluorine-based surfactants, polymeric nonionic surfactants, and silicone surfactants.

[0077] 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.

[0078] The acetylene glycol surfactant is not particularly limited, but examples thereof include 2,4,7,9-tetramethyl-5-decyne-4,7-diol, Surfynol (registered trademark, manufactured by Air Products Co., Ltd.), and Olfine (registered trademark, manufactured by Nissin Chemical Industry Co., Ltd.).

[0079] 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.

[0080] The betaine type amphoteric surfactant is not particularly limited, but examples thereof include alkyl dimethyl betaine, lauryl dimethyl betaine, stearyl dimethyl betaine, and lauryl dihydroxyethyl betaine.

[0081] The fluorine-based surfactant is not particularly limited as long as it has a perfluoroalkyl group, and examples thereof include perfluoroalkanes, perfluoroalkylcarboxylic acids, perfluoroalkylsulfonic acids, and perfluoroalkylethylene oxide adducts.

[0082] The polymeric nonionic surfactant is not particularly limited, but examples thereof include polyvinylpyrrolidone and polyvinylpyrrolidone copolymers. The average molecular weight of the polyvinylpyrrolidone used in the present invention is 1,000 to 2,000,000, preferably 10,000 to 1,500,000. The polyvinylpyrrolidone copolymer is not particularly limited, but is preferably one having both a hydrophilic portion and a hydrophobic portion in the polymer chain, such as a [vinylpyrrolidone-vinyl acetate] block copolymer, a [vinylpyrrolidone-methyl methacrylate] copolymer, a [vinylpyrrolidone-normal butyl methacrylate] copolymer, or a [vinylpyrrolidone-acrylamide] copolymer.

[0083] 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.

[0084] The above-mentioned fluorine-based surfactants and silicone-based surfactants are effective as leveling agents to improve the flatness (smoothness) of the coating film.

[0085] In the present invention, the surfactant (C) preferably has a water solubility of 0.01% by weight or more at 80°C, more preferably 0.01% by weight or more at 30°C, and even more preferably 0.01% by weight or more at 10°C, and is preferably a surfactant having a Griffin HLB (Hydrophile-Lipophile Balance) in the range of 7 to 20.

[0086] The Griffin HLB (Hydrophile-Lipophile Balance) is a value that indicates the hydrophilicity of a surfactant. The higher the value, the greater the hydrophilicity, and is expressed by the following formula:

[0087] Griffin HLB of nonionic surfactants = (molecular weight of hydrophilic group portion) / (molecular weight of surfactant) × 100 / 5 =(Hydrophilic group weight) / (Hydrophobic group weight + Hydrophilic group weight)×100 / 5 = (wt % of hydrophilic groups) / 5 In the present invention, the surfactant (C) is more preferably an acetylene glycol type surfactant or a polymer type surfactant.

[0088] The surfactant (C) may be added to the conductive polymer solution in the form of a solid, or may be added as a solution prepared in advance. In this case, the surfactant (C) may be added to the conductive polymer solution alone, or two or more kinds may be mixed and added.

[0089] When the conductive polymer solution of the present invention contains the surfactant (C), the conductive polymer solution preferably has a polythiophene (A) concentration of 0.1 to 5 wt %, a silane compound (B) concentration of 0.1 to 7 wt %, and a surfactant (C) concentration of 0.001 to 10 wt %.

[0090] As described above, the conductive polymer solution of the present invention may further contain an alcohol (D). By including the alcohol (D), it is expected that the oxidation resistance and light degradation resistance of the conductive polymer film will be improved.

[0091] The alcohol (D) is not particularly limited, but examples thereof include at least one alcohol (D) selected from the group consisting of monohydric alcohols, dihydric alcohols, trihydric alcohols, and sugar alcohols.

[0092] The monohydric alcohol is not particularly limited, but examples thereof include methanol, ethanol, 1-propanol, isopropanol, butanol, methyl cellosolve, ethyl cellosolve, propyl cellosolve, butyl cellosolve, 1-methoxy-2-propanol, and 1-ethoxy-2-propanol. From the viewpoint of operability, ethanol or 1-methoxy-2-propanol is preferred. The dihydric alcohol is not particularly limited, but ethylene glycol is preferred from the viewpoint of availability. The trihydric alcohol is not particularly limited, but glycerol is preferred. The sugar alcohol is not particularly limited, but erythritol, sorbitol, mannitol, xylitol, arabitol, and the like are preferred. Sorbitol is more preferred.

[0093] When the conductive polymer solution of the present invention contains the alcohol (D), the content thereof is preferably 0.001 to 80% by weight, more preferably 0.01 to 70% by weight, and still more preferably 0.01 to 60% by weight.

[0094] As described above, the conductive polymer solution of the present invention may further contain a silicone compound (E) (excluding the silicone surfactant). By including the silicone compound (E), it is expected that the friction of the coating film will be reduced and the durability will be improved.

[0095] The silicone compound (E) is not particularly limited, but examples thereof include silicone resin, silicone oligomer, spherical silica particles, silicone oil, and silicone powder. From the viewpoint of solution stability, however, silicone oligomer or silicone oil is preferred, and silicone oligomer of dimethylpolysiloxane or silicone oil of dimethylpolysiloxane is more preferred.

[0096] When the conductive polymer solution of the present invention contains the silicone compound (E), the content thereof is preferably 0.001 to 5% by weight, more preferably 0.01 to 3% by weight, based on the total weight of the conductive polymer solution.

[0097] In the conductive polymer solution of the present invention, the content of the silicone compound (E) is preferably 0.01 to 10 parts by weight relative to 1 part by weight of the polythiophene (A), more preferably 0.05 to 7 parts by weight relative to 1 part by weight of the polythiophene (A), and more preferably 0.1 to 5 parts by weight relative to 1 part by weight of the polythiophene (A), in terms of reducing the frictional force on the film surface.

[0098] The conductive polymer solution of the present invention is a solution composition and may contain any liquid component within the range specified by the present invention (excluding the above-mentioned silane compound (B), silane compound (B2), surfactant (C), alcohol (D), and silicone compound (E)). The optional liquid component is preferably a liquid component other than the above-mentioned components, such as water, ethyl acetate, and dimethylformamide. Of these, water is preferred as the liquid component. When the conductive polymer solution of the present invention contains water, it becomes a conductive polymer aqueous solution.

[0099] When the conductive polymer solution of the present invention contains the liquid component (e.g., water), the content thereof is preferably 50 to 99.9 wt % relative to the entire conductive polymer solution, more preferably 60 to 99.5 wt %, more preferably 70 to 99.2 wt %, and even more preferably 80 to 99 wt %.

[0100] The method for preparing the conductive polymer solution of the present invention is not particularly limited, and examples thereof include a method of mixing a solution or solid of the polythiophene (A) of the present invention with a silane compound (B), and, if necessary, a silane compound (B2), a surfactant (C), an alcohol (D), a silicone compound (E), a liquid component (e.g., water), and / or other additives. The conductive polymer solution of the present invention can be prepared by mixing the above components in any amount within the range of the present invention in any order.

[0101] The temperature at which the mixture is mixed is not particularly limited, but may be, for example, room temperature or heated, preferably 0°C or higher and 100°C or lower.

[0102] The atmosphere in which the mixture is mixed is not particularly limited, but may be air or an inert gas.

[0103] When mixing the conductive polymer solution of the present invention, ultrasonic irradiation or homogenization treatment (for example, using a mechanical homogenizer, ultrasonic homogenizer, high-pressure homogenizer, etc.) may be performed in addition to a general mixing and dissolving operation using a stirrer tip, stirring blades, etc. When homogenization treatment is performed, it is preferable to perform it at a low temperature in order to prevent thermal degradation of the polymer.

[0104] The concentration of the conductive polymer solution of the present invention may be adjusted by the compounding ratio, or may be adjusted by concentrating the solution after compounding. The concentration method may be a method of distilling off the solvent under reduced pressure or a method using an ultrafiltration membrane.

[0105] The particle size of the polythiophene (A) of the present invention is not particularly limited, but the smaller the particle size, the better the solubility, which is also desirable from the viewpoint of conductivity and uniform film formation during film formation. For example, if the particle size (D50) of the polythiophene (A) is 0.02 μm or less, the solubility will be better.

[0106] The viscosity (20°C) of the conductive polymer solution of the present invention is not particularly limited, but is preferably, for example, 200 mPa·s or less, more preferably 100 mPa·s or less, and even more preferably 50 mPa·s or less.

[0107] The method for forming a conductive polymer film from the conductive polymer solution of the present invention is not particularly limited, but may include, for example, a method in which the conductive polymer solution is applied to a support and then dried. By carrying out this method, a conductive polymer film can be easily obtained on the support (hereinafter, the support and the conductive polymer film will be collectively referred to as a "coated article").

[0108] The support is not particularly limited as long as it can be coated with the conductive polymer solution of the present invention, and examples thereof include polymer substrates and inorganic substrates. Examples of the polymer substrate include thermoplastic resins, nonwoven fabrics, paper, and resist film substrates. Examples of the thermoplastic resin include polyethylene, polypropylene, polyethylene terephthalate, polyacrylate, and polycarbonate. The nonwoven fabric may be made of, for example, natural fibers, synthetic fibers, or glass fibers. The paper may be one primarily composed of common cellulose. Examples of the inorganic substrate include glass, ceramics, aluminum oxide, and tantalum oxide.

[0109] The film is characterized by containing a polythiophene (A) containing at least two or more structural units selected from the group consisting of a structural unit represented by the general formula (1) above and a structural unit represented by the general formula (2) above, and a silane compound (B) represented by the general formula (4) above.

[0110] In addition, the content of the silane compound (B) in the film is not particularly limited, but in order to achieve both excellent hardness and excellent conductivity, it is preferably 0.5 to 10 parts by weight per 1 part by weight of the polythiophene (A), more preferably 1 to 9 parts by weight per 1 part by weight of the polythiophene (A), and more preferably 2 to 8 parts by weight per 1 part by weight of the polythiophene (A).

[0111] Furthermore, when the film of the present invention contains a silane compound (B2) having an epoxy group and / or an amino group, the content of the silane compound (B2) having an epoxy group and / or an amino group is not particularly limited, but in terms of achieving an excellent balance between film hardness and electrical conductivity, the content is preferably 0.1 to 10 parts by weight per part by weight of the polythiophene (A), more preferably 0.2 to 7 parts by weight per part by weight of the polythiophene (A), and more preferably 0.3 to 5 parts by weight per part by weight of the polythiophene (A).

[0112] Furthermore, when the film of the present invention contains a silicone compound (E), the content of the silicone compound (E) is not particularly limited, but from the viewpoint of reducing the frictional force on the film surface, it is preferably 0.01 to 10 parts by weight per 1 part by weight of the polythiophene (A), more preferably 0.05 to 7 parts by weight per 1 part by weight of the polythiophene (A), and more preferably 0.1 to 5 parts by weight per 1 part by weight of the polythiophene (A).

[0113] The support is not particularly limited as long as it can be coated with the conductive polymer solution of the present invention, and examples thereof include polymer substrates and inorganic substrates. Examples of the polymer substrate include thermoplastic resins, nonwoven fabrics, paper, and resist film substrates. Examples of the thermoplastic resin include polyethylene, polypropylene, polyethylene terephthalate, polyacrylate, and polycarbonate. The nonwoven fabric may be made of, for example, natural fibers, synthetic fibers, or glass fibers. The paper may be one primarily composed of common cellulose. Examples of the inorganic substrate include glass, metal oxides such as ITO, ceramics, aluminum oxide, and tantalum oxide.

[0114] Examples of methods for applying the conductive polymer solution include casting, dipping, bar coating, dispenser, roll coating, gravure coating, flexographic printing, spray coating, spin coating, and inkjet printing. Preferred are bar coating and spin coating.

[0115] In the drying operation, the drying temperature is not particularly limited, but is preferably a temperature at which a uniform conductive polymer film is obtained and the heat resistance temperature of the substrate or lower, more preferably in the range of room temperature to 300°C, more preferably in the range of room temperature to 250°C, and still more preferably in the range of room temperature to 200°C.

[0116] In the above drying operation, the drying atmosphere may be any of air, inert gas, vacuum, and reduced pressure. From the viewpoint of preventing deterioration of the film, an inert gas such as nitrogen or argon is preferred.

[0117] The thickness of the above film is not particularly limited, but is preferably 10 -3 ~10 2 The range of 10 μm is preferred. -3 ~10 -1 The conductivity of this film cannot be uniquely determined because it varies depending on the type and amount of the water-soluble polyester and other additives added, but for example, it is preferably 1.0E+11 Ω / □ or less, and more preferably 1.0E+10 Ω / □ or less.

[0118] The coated article of the present invention refers to the above-mentioned support, at least a part of which is covered with the above-mentioned conductive polymer film, and is used, for example, as an antistatic film, a solid electrolyte for an electrolytic capacitor, or a separator for a capacitor. [Example]

[0119] Examples of the present invention are given below.

[0120] The analytical instruments and measurement methods used in the present examples are listed below. [GC measurement] Equipment: Shimadzu GC-2014 [NMR measurement] Equipment: VARIAN, Gemini-200 [Surface resistance measurement] Equipment: Mitsubishi Chemical Loresta GP MCP-T600 [Film thickness measurement] Device: BRUKER DEKTAK XT [Viscosity measurement] Complete Viscometer / BROOKFIELD VISCOMETER DV-1 Prime [conductivity] Conductivity [S / cm]=10 4 / (surface resistance value [Ω / □] × film thickness [μm]) [Particle size measurement] Equipment: Nikkiso Microtrac Nanotrac UPA-UT151 [Conductivity measurement of self-doped conductive polymers] 0.5 ml of the solution containing the self-doped conductive polymer was applied to a 25 mm square non-alkali glass plate, dried overnight at room temperature, and then heated on a hot plate at 120°C for 20 minutes and then at 160°C for 10 minutes to obtain a conductive polymer film. The film thickness and surface resistance were calculated using the following formula. [Evaluation of coating properties and anti-static properties] A wet film of the conductive polymer solution was created on glass or PET film using a bar coater, and then dried to create a conductive film. If the resulting coating film had no coating unevenness and a stable surface resistance, it was judged to have good coatability, and if the surface resistance of the resulting conductive polymer film was 1.0E+11Ω / □ or less, it was judged to have good antistatic properties. [Transparency evaluation of coating film (transmittance, haze rate)] Equipment: Nippon Denshoku Haze Meter NDH4000 Condition: Substrate blank [Coating film hardness evaluation] The hardness of the coating was evaluated using a pencil hardness tester manufactured by Allgood Co., Ltd., in accordance with JIS standard K5600-5-4. The hardness of the coating was measured by pressing pencils of varying hardness (Mitsubishi Uni Pencils) against the coating surface at a 45° angle. A cart with the pencils attached was run over a distance of at least 7 mm at a speed of 0.5–1 mm / s. This procedure was repeated with different pencil hardnesses until a scratch of 3 mm or more was produced. The hardness of the hardest pencil that did not produce a scratch was recorded as the hardness of the coating. The test was also performed twice and repeated until the results were consistent. [Measurement of frictional force of coating] The frictional force of the coating was measured using an Imada digital force gauge ZTS-50N and a test stand MH-500N series. Using a friction coefficient measurement attachment COF2-2N, a 500g load was applied to the coating, and the frictional force was measured when the coating surface was slid at a speed of 270 mm / min.

[0121] Synthesis example 1. Synthesis of sodium 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-methyl-1-propanesulfonate [compound represented by formula (6)]. 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 reaction mixture was then heated to reflux and stirred at the same temperature for 1 hour. A mixture of 1.21 g (8.89 mmol) of 2,4-butanesultone and 10 ml of toluene was then added dropwise, followed by stirring at the same temperature 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 following formula (6).

[0122] [ka]

[0123] 1 H-NMR(D2O)δ(ppm);6.67(s,2H),4.54-4.60(m,1H),4.45(dd,1H,J=12.0,2.2Hz),4.26(dd,1H,J=12 .0,6.8Hz),3.90-3.81(m,4H),3.10-3.18(m,1H),2.30-2.47(m,1H),1.77-1.92(m,1H),1.45(d,3H) 13 C-NMR(D2O)δ(ppm);14.91,31.22,53.13,66.18,69.18,73.29,73.36,100.81,100.94,140.88,141.06 Synthesis example 2. Synthesis of polythiophene (A) [a polymer containing a structural unit represented by formula (7) or (8)]. 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 while maintaining the reaction solution temperature at 30°C or below. After stirring at room temperature for 3 hours, the reaction solution was added dropwise to 800 g of acetone, precipitating 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.

[0124] Next, 14.5 g of this crude polymer was added to water to prepare a 2 wt% solution. 700 g of the resulting solution was passed through a column packed with 200 ml of cation exchange resin Lewatit MonoPlus S100 (H-type) at a spatial velocity of 1.1, yielding 738 g of H-type polymer solution. This polymer solution was further purified by cross-flow ultrafiltration (filter: Vivaflow 200, molecular weight cutoff: 5,000, permeability: 5) to yield 698 g of a deep ultramarine solution of a polymer containing structural units represented by formula (7) or (8). The polymer solution contained 0.74 wt% of the polymer. It also contained 44 ppm and 12 ppm (relative to the polymer) of iron ions and sodium ions, respectively.

[0125] [ka]

[0126] [ka]

[0127] Example 1 To 8.33 g of a solution containing 1.2 wt % of polythiophene (A) [a polymer containing a structural unit represented by formula (7) or (8)] obtained in Synthesis Example 2, 0.4 g of tetraethoxysilane (TEOS), 0.1 g of 3-glycidyloxypropylmethoxysilane (GPTMS), 8.0 g of ethanol, 2.0 g of 1-methoxy-2-propanol, and 1.17 g of water were added and mixed thoroughly with stirring. 0.20 g of the resulting conductive polymer solution was applied to a 5 cm x 10 cm piece of glass using a printing tester (RK Print Coat Instrument K Controller / Wire Bar wet film thickness 8 μm). The glass was then dried at 120 °C for 10 minutes in a dryer to obtain a conductive film-coated glass. The resulting film exhibited a uniform, spotless appearance, and the surface resistance of the film was consistently 1.4E+8 Ω / □ regardless of the measurement location. The film produced in this example had a pencil hardness of 4H, a frictional force of 1.6 N, and a transmittance of 97.14% (substrate blank). The results are shown in Table 1.

[0128] Subsequently, the obtained conductive film was rubbed 10 times with a cloth moistened with water, ethanol, or isopropanol, but no peeling, dissolution, or adhesion to the cloth was observed, demonstrating good solvent resistance.

[0129] Example 2. To 8.33 g of a solution containing 1.2 wt % of polythiophene (A) [a polymer containing a structural unit represented by formula (7) or (8)] obtained in Synthesis Example 2 [conductivity 119 S / cm], 0.5 g of tetraethoxysilane (TEOS), 0.1 g of 3-glycidyloxypropylmethoxysilane (GPTMS), 8.0 g of ethanol, 2.0 g of 1-methoxy-2-propanol, and 1.07 g of water were added and thoroughly stirred. A conductive polymer film was obtained in accordance with the method of Example 1, and its resistance, pencil hardness, and frictional force were evaluated. The results are shown in Table 1.

[0130] Subsequently, the obtained conductive film was rubbed 10 times with a cloth moistened with water, ethanol, or isopropanol, but no peeling, dissolution, or adhesion to the cloth was observed, demonstrating good solvent resistance.

[0131] Example 3. To 8.33 g of a solution containing 1.2 wt % of polythiophene (A) [a polymer containing a structural unit represented by formula (7) or (8)] obtained in Synthesis Example 2 [conductivity 119 S / cm], 0.6 g of tetraethoxysilane (TEOS), 0.1 g of 3-glycidyloxypropylmethoxysilane (GPTMS), 8.0 g of ethanol, 2.0 g of 1-methoxy-2-propanol, and 0.97 g of water were added and thoroughly stirred. A conductive polymer film was obtained in accordance with the method of Example 1, and the resistance, pencil hardness, and frictional force were evaluated. The results are shown in Table 1.

[0132] Subsequently, the obtained conductive film was rubbed 10 times with a cloth moistened with water, ethanol, or isopropanol, but no peeling, dissolution, or adhesion to the cloth was observed, demonstrating good solvent resistance.

[0133] Example 4. To 8.33 g of a solution containing 1.2 wt % of polythiophene (A) [a polymer containing a structural unit represented by formula (7) or (8)] obtained in Synthesis Example 2 [conductivity 119 S / cm], 0.7 g of tetraethoxysilane (TEOS), 0.1 g of 3-glycidyloxypropylmethoxysilane (GPTMS), 8.0 g of ethanol, 2.0 g of 1-methoxy-2-propanol, and 0.87 g of water were added and thoroughly stirred. A conductive polymer film was obtained in accordance with the method of Example 1, and its resistance, pencil hardness, and frictional force were evaluated. The results are shown in Table 1.

[0134] Subsequently, the obtained conductive film was rubbed 10 times with a cloth moistened with water, ethanol, or isopropanol, but no peeling, dissolution, or adhesion to the cloth was observed, demonstrating good solvent resistance.

[0135] Example 5. To 8.33 g of a solution containing 1.2 wt % of polythiophene (A) [a polymer containing a structural unit represented by formula (7) or (8)] obtained in Synthesis Example 2 [electrical conductivity 119 S / cm], 0.5 g of tetraethoxysilane (TEOS), 8.0 g of ethanol, 2.0 g of 1-methoxy-2-propanol, and 1.17 g of water were added and thoroughly stirred. A conductive polymer film was obtained in accordance with the method of Example 1, and its resistance, pencil hardness, and frictional force were evaluated. The results are shown in Table 2.

[0136] Subsequently, the obtained conductive film was rubbed 10 times with a cloth moistened with water, ethanol, or isopropanol, but no peeling, dissolution, or adhesion to the cloth was observed, demonstrating good solvent resistance.

[0137] Example 6 To 8.33 g of a solution containing 1.2 wt % of the polythiophene (A) obtained in Synthesis Example 2 [a polymer containing a structural unit represented by formula (7) or (8)] [electrical conductivity 119 S / cm], 0.6 g of tetraethoxysilane (TEOS), 0.1 g of 3-glycidyloxypropylmethoxysilane (GPTMS), 0.041 g of a silicone compound (E) surface modifier KP-109 (solid content concentration 48.2 wt %) manufactured by Shin-Etsu Silicones Co., Ltd., 8.0 g of ethanol, 2.0 g of 1-methoxy-2-propanol, and 0.929 g of water were added and thoroughly stirred. A conductive polymer film was obtained in accordance with the method of Example 1, and the resistance, pencil hardness, and frictional force were evaluated. The results are shown in Table 2.

[0138] Subsequently, the obtained conductive film was rubbed 10 times with a cloth moistened with water, ethanol, or isopropanol, but no peeling, dissolution, or adhesion to the cloth was observed, demonstrating good solvent resistance.

[0139] Example 7 To 8.33 g of a solution containing 1.2 wt % of the polythiophene (A) obtained in Synthesis Example 2 [a polymer containing a structural unit represented by formula (7) or (8)] [electrical conductivity 119 S / cm], 0.6 g of tetraethoxysilane (TEOS), 0.1 g of 3-glycidyloxypropylmethoxysilane (GPTMS), 0.207 g of silicone compound (E) surface modifier KP-109 (solid content concentration 48.2 wt %) manufactured by Shin-Etsu Silicones Co., Ltd., 8.0 g of ethanol, 2.0 g of 1-methoxy-2-propanol, and 0.763 g of water were added and thoroughly stirred. A conductive polymer film was obtained in accordance with the method of Example 1, and the resistance, pencil hardness, and frictional force were evaluated. The results are shown in Table 2.

[0140] Subsequently, the obtained conductive film was rubbed 10 times with a cloth moistened with water, ethanol, or isopropanol, but no peeling, dissolution, or adhesion to the cloth was observed, demonstrating good solvent resistance.

[0141] Example 8 To 8.33 g of a solution containing 1.2 wt % of the polythiophene (A) obtained in Synthesis Example 2 [a polymer containing a structural unit represented by formula (7) or (8)] [electrical conductivity 119 S / cm], 0.6 g of tetraethoxysilane (TEOS), 0.1 g of 3-glycidyloxypropylmethoxysilane (GPTMS), 0.415 g of silicone compound (E) surface modifier KP-109 (solid content concentration 48.2 wt %) manufactured by Shin-Etsu Silicones Co., Ltd., 8.0 g of ethanol, 2.0 g of 1-methoxy-2-propanol, and 0.555 g of water were added and thoroughly stirred. A conductive polymer film was obtained in accordance with the method of Example 1, and its resistance, pencil hardness, and frictional force were evaluated. The results are shown in Table 2.

[0142] Subsequently, the obtained conductive film was rubbed 10 times with a cloth moistened with water, ethanol, or isopropanol, but no peeling, dissolution, or adhesion to the cloth was observed, demonstrating good solvent resistance.

[0143] Comparative Example 1 To 8.33 g of a solution containing 1.2 wt % of polythiophene (A) [a polymer containing a structural unit represented by formula (7) or (8)] obtained in Synthesis Example 2 [conductivity: 119 S / cm], 0.1 g of 3-glycidyloxypropylmethoxysilane (GPTMS), 8.0 g of ethanol, 2.0 g of 1-methoxy-2-propanol, and 1.57 g of water were added and thoroughly stirred. Conductive polymer films were obtained in the same manner as in Example 1, and their resistance, pencil hardness, and frictional force were evaluated. The results are shown in Table 3. The resulting conductive films were subsequently rubbed 10 times with a cloth moistened with water, ethanol, or isopropanol, respectively, without peeling, dissolution, or adhesion to the cloth, demonstrating good solvent resistance.

[0144] Comparative Example 2 To 8.33 g of a solution containing 1.2 wt % of polythiophene (A) [a polymer containing a structural unit represented by formula (7) or (8)] obtained in Synthesis Example 2 [electrical conductivity 119 S / cm], 8.0 g of ethanol, 2.0 g of 1-methoxy-2-propanol, and 1.67 g of water were added and thoroughly stirred and mixed. A coating film was prepared in accordance with Example 1, but coating unevenness occurred. The surface resistance of the prepared film (with unevenness) was 15 Ω / □, and the pencil hardness was B. The results are shown in Table 3.

[0145] Comparative Example 3. A coating film was prepared in the same manner as in Example 2, except that 8.33 g of an aqueous dispersion solution containing 1.2 wt % of PEDOT / PSS was used instead of 8.33 g of a solution containing 1.2 wt % of polythiophene (A) [a polymer containing a structural unit represented by the formula (7) or (8)] [electrical conductivity 119 S / cm] in Example 2. The results are shown in Table 3.

[0146] Subsequently, the resulting conductive film was rubbed with a cloth moistened with water or ethanol, resulting in peeling, dissolution, and adhesion to the cloth. The solvent resistance was poor.

[0147] As is clear from Examples 1 to 8 and Comparative Examples 1 to 3, it was found that by using this conductive polymer solution, it is possible to prepare a coating film that has good coatability and desirable antistatic properties (surface resistance range of approximately 1E+07 to 1E+10 Ω / □), and that combines high transparency with good pencil hardness and solvent resistance. Furthermore, it was found that when the conductive polymer solution of the present invention further contains a silicone compound (E), the frictional force on the film surface is reduced, making it possible to provide a conductive polymer film that is resistant to scratches and the like.

[0148] [Table 1]

[0149] [Table 2]

[0150] [Table 3] [Industrial Applicability]

[0151] The conductive polymer solution of the present invention can form a conductive polymer film having good conductivity (appropriate surface resistance) and hardness as an antistatic film.

Claims

1. A conductive polymer solution containing 0.1 to 5 wt % of polythiophene (A) containing at least two or more structural units 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), and containing 0.1 to 7 wt % of a silane compound (B) which is tetramethoxysilane, tetraethoxysilane, methyltriethoxysilane, methyltrimethoxysilane, dimethyldiethoxysilane, or dimethyldimethoxysilane: 【Chemistry 1】 [In general formula (1), M represents a hydrogen ion, an alkali metal ion, an ammonium ion, an organic ammonium ion, or a quaternary ammonium cation. 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 4 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 solution according to claim 1, wherein the content of the silane compound (B) is 0.5 to 10 parts by weight per 1 part by weight of the polythiophene (A).

3. 3. The conductive polymer solution according to claim 1, further comprising, in addition to the polythiophene (A) and the silane compound (B), 0.1 to 7 wt % of a silane compound (B2) having an epoxy group and / or an amino group.

4. 4. The conductive polymer solution according to claim 3, wherein the silane compound (B2) having an epoxy group and / or an amino group is 3-glycidyloxypropyltrimethoxysilane or 3-glycidyloxypropyltriethoxysilane.

5. 5. The conductive polymer solution according to claim 1, further comprising one or more silicone compounds (E) selected from the group consisting of silicone oligomers and silicone oils, wherein the content of the silicone compounds (E) is 0.001 to 5% by weight with respect to the total amount of the conductive polymer solution.

6. 6. The conductive polymer solution according to claim 1, further comprising water, wherein the content of the water is 50 to 99.9% by weight relative to the total amount of the conductive polymer solution (excluding cases where the total including the content of the water exceeds 100% by weight).

7. A method for producing a film, comprising applying the conductive polymer solution according to any one of claims 1 to 6 to a support and then drying the applied conductive polymer solution.

8. A film comprising: polythiophene (A) containing at least two or more structural units 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); and silane compound (B) which is tetramethoxysilane, tetraethoxysilane, methyltriethoxysilane, methyltrimethoxysilane, dimethyldiethoxysilane, or dimethyldimethoxysilane in an amount of 0.5 to 10 parts by weight per part by weight of the polythiophene (A). 【Chemistry 2】 [In general formula (1), M represents a hydrogen ion, an alkali metal ion, an ammonium ion, an organic ammonium ion, or a quaternary ammonium cation. 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 4 carbon atoms, or a fluorine atom, m represents an integer of 1 to 10, and n represents 0 or 1.

9. 9. The film according to claim 8, further comprising a silane compound (B2) having an epoxy group and / or an amino group as a constituent component, wherein the content of the silane compound (B2) having an epoxy group and / or an amino group is 0.1 to 10 parts by weight per 1 part by weight of the content of the polythiophene (A).

10. 10. The film according to claim 8 or claim 9, further comprising, as a constituent component thereof, one or more silicone compounds (E) selected from the group consisting of silicone oligomers and silicone oils, wherein the content of the silicone compounds (E) is 0.01 to 10 parts by weight per 1 part by weight of the content of the polythiophene (A).

11. A coated article, wherein at least a portion of a substrate is covered with the film according to any one of claims 8 to 10.

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