Conductive polymer composition and conductive polymer film

Abstract

To provide a composition that contains a resin excellent in solubility or dispersibility in organic solvent and organic solvent-soluble with polythiophene having high conductivity, and an organic solvent.SOLUTION: A conductive polymer composition comprising a polythiophene derivative (A) containing the following monomer unit, an amine compound (B), a binder resin (C), and an organic solvent (D) is used.SELECTED DRAWING: None

Description

[Technical Field]

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

[0002] In recent years, conductive polymer materials have been developed in which π-conjugated polymers, such as polyacetylene, polythiophene, polyaniline, and polypyrrole, are doped with electron-accepting compounds as dopants. Applications of such conductive polymer materials have been considered for applications such as antistatic agents, solid electrolytes for electrolytic capacitors, conductive paints, electrochromic devices, electrode materials, thermoelectric conversion materials, transparent conductive films, chemical sensors, and actuators. Some of these applications require high compatibility with resins, while others are sensitive to water. In these application fields, conductive polymer compositions using organic solvents as solvents are in demand.

[0003] Known conductive polymers that dissolve in organic solvents include, for example, polyaniline-type conductive polymers and polythiophene-type conductive polymers (for example, Patent Document 1). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 2019-210356 Summary of the Invention [Problem to be solved by the invention]

[0005] No consideration has been given to compatibility with resins for the organic solvent-type conductive polymer composition disclosed in Patent Document 1. An object of the present invention is to provide a conductive polymer composition that has excellent compatibility with resins. [Means for solving the problem]

[0006] As a result of extensive investigations, the present inventors have found that the above-mentioned problems can be solved by a conductive polymer composition comprising a polythiophene (A) containing at least one structural unit selected from the group consisting of a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2), an amine compound (B), a binder resin (C), and an organic solvent (D), and have thus completed the present invention.

[0007] That is, the present invention relates to the following conductive polymer composition and a method for producing a conductive polymer film using the same. The conductive polymer film obtained from the conductive polymer composition of the present invention can be used, for example, as an antistatic film. [1] A conductive polymer composition comprising: a polythiophene (A) containing at least one structural unit selected from the group consisting of a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2); an amine compound (B); a binder resin (C); and an organic solvent (D).

[0008] [ka]

[0009] {In the above general formulas (1) and (2), R 1 represents a hydrogen atom, a methyl group, an ethyl group, an alkyl group having 3 to 6 carbon atoms, or a fluorine atom. m represents an integer of 1 to 6, and n represents 0 or 1.} [2] The conductive polymer composition according to [1], wherein m represents 2 or 3. [3] The conductive polymer composition according to [1], wherein n represents 1. [4] The amine compound (B) is a compound represented by the formula [NH(R 2 )(R 3 a secondary amine compound represented by [N(R 2 )(R 3 )2], and R 2 represents an alkyl group having 6 to 20 carbon atoms or an alkyl group having a substituent and a total of 6 to 20 carbon atoms. 3are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkyl group having a substituent and a total of 1 to 20 carbon atoms. [5] The conductive polymer composition according to any one of [1] to [3], wherein the amine compound (B) is di-n-octylamine, diisooctylamine, tri-n-octylamine, triisooctylamine, di-n-hexylamine, tri-n-hexylamine, N-methyl-N,N-di-n-octylamine, N-methyl-N,N-diisooctylamine, or N-methyl-N,N-di-n-hexylamine. [6] The conductive polymer composition according to any one of [1] to [5], wherein the binder resin (C) is at least one selected from the group consisting of vinylpyrrolidone resins, urethane resins, acrylic resins, and epoxy resins. [7] The conductive polymer composition according to [1], wherein the content of the binder resin (C) is 10 to 1,500 parts by weight per part by weight of the polythiophene (A). [8] The conductive polymer composition according to any one of [1] to [7], wherein the organic solvent (D) is an alcohol solvent, an aromatic hydrocarbon solvent, a ketone solvent, an ether solvent, a glycol ester solvent, a glycol ether solvent, a halogenated solvent, an amide solvent, a sulfur-containing solvent, or a mixture thereof. [9] The conductive polymer composition according to any one of [1] to [7], wherein the organic solvent (D) is one or more organic solvents selected from the group consisting of 1-butanol, methyl isobutyl ketone, methyl ethyl ketone, and propylene glycol monomethyl ether.

[10] The conductive polymer composition according to [1], wherein the content of the organic solvent (D) is 10 to 3,000 parts by weight per part by weight of the polythiophene (A).

[11] A method for producing a conductive polymer film, comprising applying the conductive polymer composition according to any one of [1] to

[10] to a substrate and then drying the composition to obtain a conductive polymer film. [Effects of the Invention]

[0010] According to one aspect of the present invention, it is possible to provide an organic solvent-type conductive polymer composition that has superior compatibility with resins compared to previously reported compositions. DETAILED DESCRIPTION OF THE INVENTION

[0011] The present invention will be described in detail below. In this specification, unless otherwise specified, the expression "A to B" representing a range of numerical values ​​means "A or more and B or less."

[0012] An object of one embodiment of the present invention is to provide an organic solvent-based conductive polymer composition that has excellent compatibility with resins, and to provide a conductive polymer film using the same. Furthermore, the conductive polymer film produced using one embodiment of the present invention has the effect of having a surface resistivity that is significantly superior to that of conventional techniques.

[0013] As described above, the conductive polymer composition of the present embodiment includes a polythiophene (A) containing at least one structural unit selected from the group consisting of a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2), an amine compound (B), a binder resin (C), and an organic solvent (D).

[0014] [ka]

[0015] {In the above general formulas (1) and (2), R 1 represents a hydrogen atom, a methyl group, an ethyl group, an alkyl group having 3 to 6 carbon atoms, or a fluorine atom. m represents an integer of 1 to 6, and n represents 0 or 1.} The 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.

[0016] Substituent R 1 In terms of excellent film-forming properties, is preferably a hydrogen atom, a methyl group, an ethyl group, or a fluorine atom, and more preferably a methyl group.

[0017] M 1 represents a hydrogen ion.

[0018] m represents an integer of 1 to 6, preferably 1, 2, 3, or 4, and more preferably 2 or 3.

[0019] n represents 0 or 1, and is preferably 1. When n is 0, the CH2s on both sides of the oxygen atom are bonded by a single bond.

[0020] The structural unit represented by the general formula (2) represents the doped state of the structural unit represented by the general formula (1).

[0021] 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.

[0022] The dopant in this embodiment is a sulfo group or sulfonate group covalently bonded within the polymer molecule, and is a p-type dopant. Polymers that exhibit conductivity without the addition of an external dopant are called self-doping polymers.

[0023] The polythiophene represented by the above formula (1) or (2) is not particularly limited, but specific examples thereof include 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-methyl-1-propanesulfonic acid polymer, 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-ethyl-1-propanesulfonic acid polymer, 3- [(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-propyl-1-propanesulfonic acid polymer, 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-butyl-1-propanesulfonic acid polymer, 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-pentyl- 1-Propanesulfonic acid polymer, 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-hexyl-1-propanesulfonic acid polymer, 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-isopropyl-1-propanesulfonic acid polymer, 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-isopropyl-1-propanesulfonic acid polymer, [(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-isobutyl-1-propanesulfonic acid polymer, 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-isopentyl-1-propanesulfonic acid polymer, 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-fluoro-1-propanesulfonic acid polymer, and the like.

[0024] The conductivity of the polythiophene (A) is not particularly limited, but is preferably 10 S / cm or more in terms of conductivity (electrical conductivity) in a film state.

[0025] The polythiophene (A) may be synthesized based on publicly known information.

[0026] The amine compound (B) is not particularly limited, but may be, for example, [NH(R 2 )(R 3 a secondary amine compound represented by [N(R 2 )(R 3 )2] is preferably a tertiary amine compound represented by the formula (I). 2 represents an alkyl group having 6 to 20 carbon atoms or an alkyl group having a substituent and a total of 6 to 20 carbon atoms. 3 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkyl group having a substituent and a total of 1 to 20 carbon atoms.

[0027] The alkyl group having 6 to 20 carbon atoms is not particularly limited, but examples thereof include an n-hexyl group, an n-octyl group, a methylhexyl group, an ethylhexyl group, an n-nonyl group, an n-decyl group, an ethyloctyl group, a butylhexyl group, an n-undecyl group, an n-dodecyl group, an n-hexadecyl group, an n-heptadecyl group, an octylnonyl group, an n-octadecyl group, an n-nonadecyl group, an n-icosyl group, and an octyldodecane group.

[0028] The alkyl group having a total of 6 to 20 carbon atoms and having a substituent is not particularly limited, but examples thereof include alkyl groups having 6 to 20 carbon atoms and having a halogen atom, an amino group, or a hydroxy group, and specific examples thereof include an 8-hydroxyoctyl group and a 9-aminononyl group.

[0029] Among these, the substituent R 2 From the viewpoint of availability, the alkyl group is preferably an alkyl group having 6 to 12 carbon atoms, and specific examples thereof are preferably an n-hexyl group, an isohexyl group, an n-heptyl group, a methylhexyl group, an n-octyl group, an isooctyl group, a methylheptyl group, an ethylhexyl group, an n-nonyl group, an n-decyl group, or an n-dodecyl group; more preferably an alkyl group having 6 to 8 carbon atoms, and specific examples thereof are more preferably an n-hexyl group, an n-octyl group, or an isooctyl group; more preferably an alkyl group having 6 carbon atoms, and specific examples thereof are more preferably an n-hexyl group.

[0030] The alkyl group having 1 to 20 carbon atoms is not particularly limited, and examples thereof 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, an isohexyl group, a 2-ethylbutyl group, a cyclohexyl group, an n-heptyl group, an ethyl methyl ... Examples of the alkyl group include an octyl group, an isohexyl group, a methylhexyl group, an n-octyl group, an isooctyl group, a methylheptyl group, an ethylhexyl group, an n-nonyl group, an n-decyl group, an ethyloctyl group, a butylhexyl group, an n-undecyl group, an n-dodecyl group, an n-hexadecyl group, an n-heptadecyl group, an octylnonyl group, an n-octadecyl group, an n-nonadecyl group, an n-icosyl group, and an octyldodecyl group.

[0031] Examples of the substituted alkyl group having 1 to 20 carbon atoms include an alkyl group having 7 to 20 carbon atoms and having a halogen atom, an amino group, or a hydroxy group, and specific examples include a trifluoromethyl group, a 2-hydroxyethyl group, an 8-hydroxyoctyl group, and a 9-aminononyl group.

[0032] Among these, the substituent R 3are each independently preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and specific examples thereof are preferably 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 n-hexyl group, an isohexyl group, a 2-ethylbutyl group, an n-heptyl group, a methylhexyl group, an n-octyl group, an isooctyl group, a methylheptyl group, an ethylhexyl group, an n-nonyl group, an n-decyl group, or an n-dodecyl group, and More preferably, they are independently a hydrogen atom or an alkyl group having 6 to 12 carbon atoms, and specific examples thereof are more preferably an n-hexyl group, an isohexyl group, an n-octyl group, an isooctyl group, a methylheptyl group, an ethylhexyl group, an n-nonyl group, an n-decyl group, or an n-dodecyl group, and more preferably, they are each independently a hydrogen atom or an alkyl group having 6 to 8 carbon atoms, and specific examples thereof are more preferably an n-hexyl group, an isohexyl group, an n-octyl group, or an isooctyl group.

[0033] The amine compound (B) is not particularly limited, and examples thereof include n-heptylamine, di-n-heptylamine, tri-n-heptylamine, n-octylamine, di-n-octylamine, diisooctylamine, tri-n-octylamine, triisooctylamine, di-n-hexylamine, tri-n-hexylamine, n-nonylamine, di-n-nonylamine, tri-n-nonylamine, Amine, n-decylamine, di-n-decylamine, tri-n-decylamine, n-dodecylamine, di-n-dodecylamine, tri-n-dodecylamine, n-hexadecylamine, di-n-hexadecylamine, tri-n-hexadecylamine, n-octadecylamine, di-n-octadecylamine, tri-n-octadecylamine, n-icosylamine, di-n-icosylamine, tri-n-icosylamine N-methyl-N,N-di-n-octylamine, N-methyl-N,N-diisooctylamine, or N-methyl-N,N-di-n-hexylamine, N,N-dimethyl-n-heptylamine, N,N-dimethyl-n-octylamine, N,N-dimethyl-n-nonylamine, N,N-dimethyl-n-decylamine, N,N-dimethyl-n-dodecylamine, N,N-dimethyl-n-hexadecylamine N,N-dimethyl-n-octadecylamine, N,N-dimethyl-n-icosylamine, N,N-diethyl-n-heptylamine, N,N-diethyl-n-octylamine, N,N-diethyl-n-nonylamine, N,N-diethyl-n-decylamine, N,N-diethyl-n-dodecylamine, N,N-diethyl-n-hexadecylamine, N,N-diethyl-n-octadecylamine, N,N-Diethyl-n-icosylamine, N-Methyl-Nn-hexylamine, N-Methyl-Nn-heptylamine, N-Methyl-Nn-octylamine, N-Methyl-Nn-nonylamine, N-Methyl-Nn-dodecylamine, N-Methyl-Nn-hexadecylamine, N-Methyl-Nn-octadecylamine, N-Ethyl-Nn-hexylamine, N-Ethyl-Nn-heptylamine, N-Ethyl-Nn-octylamine, N-Ethyl-Nn-nonylamine, N-Ethyl-Nn-dodecylamine, N-Ethyl-Nn-hexadecylamine, N-Ethyl-Nn-octadecylamine Examples of the amino acid amine include decylamine, 7-hydroxyheptylamine, 8-hydroxyoctylamine, 9-hydroxynonylamine, 10-hydroxydecylamine, 12-hydroxydodecylamine, 16-hydroxyhexadecylamine, 18-hydroxyoctadecylamine, 20-hydroxyicosylamine, 7-aminoheptylamine, 8-aminooctylamine, 9-aminononylamine, 10-aminodecylamine, 12-aminododecylamine, 16-aminohexadecylamine, 18-aminooctadecylamine, and 20-aminoicosylamine.

[0034] Of these, the amine compound (B) is preferably di-n-octylamine, diisooctylamine, tri-n-octylamine, triisooctylamine, di-n-hexylamine, tri-n-hexylamine, N-methyl-N,N-di-n-octylamine, N-methyl-N,N-diisooctylamine, or N-methyl-N,N-di-n-hexylamine, because of its excellent film-forming properties.

[0035] The binder resin (C) is not particularly limited, but examples thereof include vinylpyrrolidone resin, acrylic resin, urethane resin, methyl methacrylate resin, styrene-butadiene resin, vinyl acetate resin, polyamide resin, phenol resin, epoxy resin, melamine resin, thermosetting polyimide, nitrocellulose or other cellulose resins, polyvinyl alcohol resin, etc. Curing methods include heat curing and UV curing.

[0036] The binder resin (C) is preferably at least one selected from the group consisting of vinylpyrrolidone resin, urethane resin, acrylic resin, and epoxy resin, in view of its excellent film-forming properties.

[0037] The content of the binder resin (C) is not particularly limited, but is preferably 1 to 1,500 parts by weight, more preferably 5 to 1,000 parts by weight, and even more preferably 10 to 500 parts by weight, relative to 1 part by weight of the polythiophene (A).

[0038] The organic solvent (D) is not particularly limited, and examples thereof include alcohol solvents (e.g., methanol, ethanol, normal propyl alcohol, isopropyl alcohol, normal butanol, isobutanol, tertiary butanol, ethylene glycol, etc.), aromatic hydrocarbon solvents (benzene, toluene, xylene, etc.), ketone solvents (acetone, methyl ethyl ketone, methyl propyl ketone, methyl isobutyl ketone, diacetone alcohol, etc.), ether solvents (methyl cellosolve, ethyl cellosolve, butyl cellosolve, 1,4-dioxane, etc.), glycol ester solvents (ethylene glycol monoethyl ether acetate, propylene glycol, Examples of suitable solvents include ethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, etc.), glycol ether solvents (methyl carbitol, ethyl carbitol, butyl carbitol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, etc.), halogenated solvents (chloroform, dichloromethane, 1,2-dichloroethane, chlorobenzene, etc.), amide solvents (N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, dimethylimidazolidinone, hexamethylphosphoric triamide, etc.), and sulfur-containing solvents (dimethyl sulfoxide, sulfolane, etc.).

[0039] These organic solvents (D) may be used alone or in combination of two or more kinds.

[0040] The organic solvent (D) is preferably one or more organic solvents selected from the group consisting of 1-butanol, methyl isobutyl ketone, methyl ethyl ketone, and propylene glycol monomethyl ether, in view of their excellent compatibility with the resin.

[0041] The content of the organic solvent (D) is not particularly limited, but is preferably 10 to 3,000 parts by weight relative to 1 part by weight of the polythiophene (A), more preferably 50 to 2,000 parts by weight relative to 1 part by weight of the polythiophene (A), and even more preferably 100 to 1,500 parts by weight relative to 1 part by weight of the polythiophene (A).

[0042] In the conductive polymer composition of this embodiment, the compositional ratios of the components (A), (B), (C), and (D) (the total of the components (A), (B), (C), and (D) is taken as 100% by weight) are not particularly limited, but are preferably, for example, 0.001 to 5% by weight of polythiophene (A), 0.001 to 4% by weight of amine compound (B), 0.005 to 25% by weight of binder resin (C), and 66 to 99.993% by weight of organic solvent (D).

[0043] The conductive polymer composition of the present embodiment is expected to be useful in applications such as antistatic, capacitors, touch sensors, organic thin-film solar cells, organic electroluminescence (EL), electrodes, etc. The conductive polymer composition of the present embodiment may contain additives such as known surfactants and binders depending on the application.

[0044] The surfactant is not particularly limited, but examples thereof include polymeric nonionic surfactants, amphoteric surfactants, fluorine-based surfactants, silicone-based surfactants, and acetylene glycol-based surfactants.

[0045] The amphoteric surfactant is not particularly limited, but examples thereof include betaine-type amphoteric surfactants, such as alkyl dimethyl betaine, lauryl dimethyl betaine, stearyl dimethyl betaine, and lauryl dihydroxyethyl betaine.

[0046] The fluorine-based surfactant is preferably one having a perfluoroalkyl group, and although there are no particular limitations, examples thereof include perfluoroalkanes, perfluoroalkylcarboxylic acids, perfluoroalkylsulfonic acids, and perfluoroalkylethylene oxide adducts.

[0047] 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 compound.

[0048] Fluorine-based surfactants and silicone-based surfactants are effective as leveling agents to improve the flatness of the coating film.

[0049] The conductive polymer composition of the present embodiment is not particularly limited and can be produced by mixing the components according to a general method. For example, it is preferable to produce it according to the following procedure.

[0050] Step 1: An aqueous solution of the polythiophene (A) is prepared according to a conventionally known production method.

[0051] Step 2: The alcohol solution of the amine compound (B) is added to the aqueous solution of the polythiophene (A), and the mixture is mixed and stirred to obtain a composition of the polythiophene (A) and the amine compound (B).

[0052] Step 3: Water and alcohol are removed from the mixture of step 2 to obtain a solid that is a composition of the polythiophene (A) and the amine compound (B).

[0053] Step 4: The organic solvent (D) is added to the solid obtained in Step 3, the binder resin (C) is added, and if necessary, other additives are added, and the mixture is mixed and stirred to obtain the conductive polymer composition of the present embodiment.

[0054] The step 1 is not particularly limited, but may be, for example, a compound represented by the following general formula (3):

[0055] [ka]

[0056] [In the above general formula (3), R 1 , m, and n are R in the above general formulas (1) and (2). 1 , m, and n. M + represents a hydrogen ion or a metal ion. The reaction can be carried out by subjecting a compound represented by the formula (I) to oxidative polymerization by a conventionally known method, followed by acid treatment by a conventionally known method.

[0057] The metal ions are not particularly limited, but include transition metal ions, noble metal ions, non-ferrous metal ions, alkali metal ions (e.g., lithium ions, sodium ions, potassium ions, cesium ions, etc.), and alkaline earth metal ions (calcium ions, magnesium ions, etc.).

[0058] The aforementioned M +is preferably a hydrogen ion or an alkali metal ion, and more preferably a hydrogen ion, a sodium ion, or a potassium ion.

[0059] In regard to the steps 2 and 3, in order to obtain a conductive polymer composition having excellent conductivity, it is preferable to react a polythiophene (A) containing at least one structural unit selected from the group consisting of a structural unit represented by the general formula (1) and a structural unit represented by the general formula (2) with an amine compound (B) in water and / or an alcohol solvent, and then, if necessary, combine such operations as solvent washing, reprecipitation, centrifugal sedimentation, ultrafiltration, dialysis, and ion exchange resin treatment.

[0060] The alcohol solvent is not particularly limited, but examples thereof include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol, pentanol, isopentanol, hexanol, isohexanol, cyclohexanol, octanol, 2-ethylhexanol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, hexanediol, ethylene glycol monomethyl ether, and ethylene glycol monoethyl ether.

[0061] When mixing the conductive polymer composition of this embodiment (step 4 above), in addition to a general mixing and dissolving operation using a stirrer tip, a stirring blade, or the like, ultrasonic irradiation or homogenization treatment (for example, using a mechanical homogenizer, an ultrasonic homogenizer, a high-pressure homogenizer, or the like) may be performed.

[0062] The conductive polymer composition of the present embodiment can be applied to a support to produce a coating film, and then the coating film can be dried to produce a conductive polymer film (hereinafter, the support and the conductive polymer film will be collectively referred to as a "coated article").

[0063] The support is not particularly limited as long as it can be coated with the conductive polymer composition of this embodiment, and examples thereof include a polymer substrate or an inorganic substrate. The polymer substrate is not particularly limited, and examples thereof include a thermoplastic resin, a nonwoven fabric, and paper. Examples of thermoplastic resins include polyethylene, polypropylene, polyethylene terephthalate, polyacrylate, polycarbonate, and polyimide. Examples of nonwoven fabrics include natural fibers and synthetic fibers. Examples of paper include those containing general cellulose as a main component. Examples of inorganic substrates are not particularly limited, and examples thereof include glass, glass fiber, ceramics, aluminum oxide, and tantalum oxide.

[0064] The method for applying the conductive polymer composition is not particularly limited, but examples thereof include a casting method, a dipping method, a bar coating method, a dispenser method, a roll coating method, a gravure coating method, a flexographic printing method, a spray coating method, a spin coating method, and an inkjet method.

[0065] The drying temperature for the coating film is not particularly limited as long as it is a temperature at which a uniform conductive polymer film can be obtained and is equal to or lower than the heat resistance temperature of the substrate, but is in the range of room temperature (15 to 25°C) to 300°C, preferably in the range of room temperature to 250°C, and more preferably in the range of room temperature to 200°C.

[0066] The drying atmosphere may be air, an inert gas, a vacuum, or a reduced pressure, but from the viewpoint of preventing deterioration of the polymer film, an inert gas such as nitrogen or argon is preferred. [Example]

[0067] Examples are shown below, but the present invention is not limited to these examples. Analytical instruments and measurement methods used in the examples are listed below. [Surface resistivity measurement] Apparatus: Mitsubishi Chemical Loresta GP MCP-T600. [Film thickness measurement] Device: DEKTAK XT manufactured by BRUKER. [Measurement of the conductivity of conductive polymer compositions] 0.5 ml of the conductive polymer composition of the present invention containing polythiophene (A) was applied to a 25 mm square alkali-free glass plate, dried at room temperature overnight, and then heated at 150°C for 30 minutes to obtain a conductive polymer film. The film thickness and surface resistance were calculated using the following formula.

[0068] Conductivity [S / cm]=10 4 / (Surface resistivity [Ω / □]×film thickness [μm]).

[0069] Example 1 An aqueous solution containing 1 wt% of poly(3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-methyl-1-propanesulfonic acid) (hereinafter referred to as "PEDOT-MPS"; polythiophene (A) consisting of structural units represented by the following formula (1a) and structural units represented by the following formula (2a)) was synthesized in accordance with Synthesis Examples 1 and 2 of a known document (JP 2019-196443 A). The PEDOT-MPS had a weight-average molecular weight of 6,303 in terms of standard polystyrene as measured by gel permeation chromatography, and contained 44 ppm and 12 ppm (relative to the polymer) of iron ions and sodium ions, respectively.

[0070] [ka]

[0071] 7.4 g of a methanol solution containing 5 wt% di-n-octylamine as the amine compound (B) was added to 50.0 g of an aqueous solution containing 1 wt% of the PEDOT-MPS (polythiophene (A)) in a glass container while stirring, and the mixture was stirred at room temperature for 1 hour. The precipitate was separated into solid and liquid using a vacuum filter, and then vacuum dried to obtain 0.6 g of polythiophene P1 (solid). The conductivity of polythiophene P1 was 326 S / cm.

[0072] 0.2 g of the polythiophene P1 was dissolved in 9.8 g of 1-butanol as an organic solvent (D) to prepare 10 g of a 1-butanol solution containing 2.0 wt % of polythiophene P1.

[0073] As the binder resin (C), polyvinylpyrrolidone K30 (hereinafter referred to as PVP) was dissolved in 1-butanol to prepare 10 g of a 1-butanol solution containing 10 wt % of polyvinylpyrrolidone K30.

[0074] 0.10 g of a 2.0 wt % 1-butanol solution of polythiophene P1, 1.0 g of a 10 wt % 1-butanol solution of polyvinylpyrrolidone K30, 0.7 g of 1-butanol, and 0.20 g of ethylene glycol were weighed out and mixed thoroughly with stirring to obtain a conductive polymer composition.

[0075] The resulting conductive polymer composition contained 1.13 mg of polythiophene (A), 0.87 mg of amine compound (B), 100 mg of binder resin (C), and 1898 mg of organic solvent (D).

[0076] 0.7 g of this conductive polymer composition was cast onto a glass substrate that had been treated with UV and ozone, prebaked on a hot plate in a nitrogen atmosphere, and then baked at 200°C for 60 minutes to obtain a conductive polymer film. In the obtained conductive polymer film, the polythiophene (A) and binder resin (C) were uniformly dissolved together, and no non-uniform separation or dispersion was observed. The surface resistivity of the obtained conductive film is shown in Table 1.

[0077] Example 2. A conductive polymer composition and a conductive polymer film were obtained and evaluated in the same manner as in Example 1, except that 0.50 g of a 2.0 wt % 1-butanol solution of polythiophene P1 was used instead of 0.10 g of the 2.0 wt % 1-butanol solution of polythiophene P1, and 0.3 g of 1-butanol was used instead of 0.7 g of 1-butanol. The results are shown in Table 1. In the obtained conductive polymer film, polythiophene (A) and binder resin (C) were uniformly dissolved together, and no non-uniform separation or dispersion was observed.

[0078] The resulting conductive polymer composition contained 5.65 mg of polythiophene (A), 4.35 mg of amine compound (B), 100 mg of binder resin (C), and 1890 mg of organic solvent (D).

[0079] Example 3 A conductive polymer composition and a conductive polymer film were obtained and evaluated in accordance with the method of Example 1, except that 0.80 g of a 2.0 wt % 1-butanol solution of polythiophene P1 was used instead of 0.10 g of the 2.0 wt % 1-butanol solution of polythiophene P1, and 0.7 g of 1-butanol was used instead of adding 1-butanol. The results are shown in Table 1. In the obtained conductive polymer film, polythiophene (A) and binder resin (C) were uniformly dissolved together, and no non-uniform separation or dispersion was observed.

[0080] The resulting conductive polymer composition contained 9.04 mg of polythiophene (A), 6.96 mg of amine compound (B), 100 mg of binder resin (C), and 1884 mg of organic solvent (D).

[0081] Example 4. 0.7 g of polythiophene P2 was obtained by using di-2-ethylhexylamine instead of dioctylamine in Synthesis Example 1. 0.80 g of a 2.0 wt % 1-butanol solution of polythiophene P2, 1.0 g of a 10 wt % 1-butanol solution of polyvinylpyrrolidone K30, and 0.20 g of ethylene glycol were weighed out and thoroughly mixed with stirring to obtain a conductive polymer composition.

[0082] 0.7 g of this conductive polymer composition was cast onto a glass substrate that had been treated with UV and ozone, prebaked on a hot plate in a nitrogen atmosphere, and then baked at 200°C for 60 minutes to obtain a conductive polymer film. In the obtained conductive polymer film, the polythiophene (A) and binder resin (C) were uniformly dissolved together, and no non-uniform separation or dispersion was observed. The surface resistivity of the obtained conductive film is shown in Table 1.

[0083] The resulting conductive polymer composition contained 1.16 mg of polythiophene (A), 0.84 mg of amine compound (B), 100 mg of binder resin (C), and 1898 mg of organic solvent (D).

[0084] Example 5. 0.6 g of polythiophene P3 was obtained by using trihexylamine instead of dioctylamine in Synthesis Example 1. 0.80 g of a 2.0 wt % 1-butanol solution of polythiophene P3, 1.0 g of a 10 wt % 1-butanol solution of polyvinylpyrrolidone K30, and 0.20 g of ethylene glycol were weighed out and thoroughly mixed with stirring to obtain a conductive polymer composition.

[0085] 0.7 g of this conductive polymer composition was cast onto a glass substrate that had been treated with UV and ozone, prebaked on a hot plate in a nitrogen atmosphere, and then baked at 200°C for 60 minutes to obtain a conductive polymer film. In the obtained conductive polymer film, the polythiophene (A) and binder resin (C) were uniformly dissolved together, and no non-uniform separation or dispersion was observed. The surface resistivity of the obtained conductive film is shown in Table 1.

[0086] The resulting conductive polymer composition contained 1.15 mg of polythiophene (A), 0.85 mg of amine compound (B), 100 mg of binder resin (C), and 1898 mg of organic solvent (D).

[0087] Comparative Example 1 A conductive polymer composition and a conductive polymer film were obtained and evaluated in the same manner as in Example 1, except that 0.8 g of 1-butanol was used instead of the 2.0 wt % 1-butanol solution of polythiophene P1. The results are shown in Table 1.

[0088] [Table 1] [Industrial Applicability]

[0089] The conductive polymer composition of this embodiment is a conductive composition using polythiophene, which is soluble in organic solvents and has high conductivity, and can form a good conductive polymer film and reduce the surface resistance of the coating film. Therefore, the conductive polymer composition can be used as an antistatic agent, a solid electrolyte for capacitors, an antistatic film, a solid electrolyte for solid electrolytic capacitors, and a separator for wound aluminum electrolytic capacitors. Other applications of the conductive polymer composition include organic thin-film solar cells, organic electroluminescence (EL), electrochromic elements, transparent electrodes, transparent conductive films, thermoelectric conversion materials, chemical sensors, actuators, electromagnetic wave shielding materials, conductive paints, and conductive inks.

Claims

1. A conductive polymer composition comprising: a polythiophene (A) containing at least one structural unit selected from the group consisting of a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2); one or more amine compounds (B) selected from the group consisting of diisooctylamine, triisooctylamine, di-n-hexylamine, tri-n-hexylamine, N-methyl-N,N-di-n-octylamine, N-methyl-N,N-diisooctylamine, N-methyl-N,N-di-n-hexylamine, and di-2-ethylhexylamine; a binder resin (C) made of a vinylpyrrolidone resin; and an organic solvent (D), wherein the polythiophene (A) and the binder resin (C) are uniformly and compatibly dissolved in each other. 【Chemical 1】 {In the above general formulas (1) and (2), R １ represents a hydrogen atom, a methyl group, an ethyl group, an alkyl group having 3 to 6 carbon atoms, or a fluorine atom; m represents an integer of 1 to 6, and n represents 0 or 1.}

2. The conductive polymer composition according to claim 1 , wherein m represents 2 or 3.

3. The conductive polymer composition of claim 1 , wherein n represents 1.

4. 2. The conductive polymer composition according to claim 1, wherein the content of the binder resin (C) is 1 to 1,500 parts by weight per 1 part by weight of the polythiophene (A).

5. 5. The conductive polymer composition according to claim 1, wherein the organic solvent (D) is an alcohol solvent, an aromatic hydrocarbon solvent, a ketone solvent, an ether solvent, a glycol ester solvent, a glycol ether solvent, a halogenated solvent, an amide solvent, a sulfur-containing solvent, or a mixture thereof.

6. 5. The conductive polymer composition according to claim 1, wherein the organic solvent (D) is one or more organic solvents selected from the group consisting of 1-butanol, methyl isobutyl ketone, methyl ethyl ketone, and propylene glycol monomethyl ether.

7. 2. The conductive polymer composition according to claim 1, wherein the content of said organic solvent (D) is 10 to 3,000 parts by weight per 1 part by weight of said polythiophene (A).

8. 8. A method for producing a conductive polymer film, comprising applying the conductive polymer composition according to claim 1 to a substrate and then drying the composition to obtain a conductive polymer film.

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