Conductive polymer-containing liquid and method for producing the same, and conductive laminate and method for producing the same

Abstract

To provide a conductive polymer-containing liquid containing an additive which can be dissolved in an organic solvent and has an antioxidant function, to provide a method for producing the same, to provide a conductive laminate using the conductive polymer-containing liquid, and to provide a method for producing the same.SOLUTION: A conductive polymer-containing liquid comprising: a conductive composite comprising a π - conjugated conductive polymer and a polyanion; an additive comprising a compound having one or more phenolic hydroxyl groups and a (meth) acrylic group in a molecule; and at least one of water and an organic solvent.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a conductive polymer-containing liquid containing a π-conjugated conductive polymer and a method for producing the same, as well as a conductive laminate and a method for producing the same. [Background technology]

[0002] A π-conjugated conductive polymer having a π-conjugated main chain forms a conductive complex by doping with a polyanion having an anionic group, and becomes dispersible in water. A conductive polymer dispersion containing the conductive complex can be applied to a film substrate or the like to produce a conductive film or the like having a conductive layer.

[0003] A conductive layer containing a conductive complex may lose its conductivity over time when exposed to the atmosphere. To prevent this, a method of adding a water-soluble antioxidant to the conductive layer has been proposed (Patent Document 1). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2010-196022 Summary of the Invention [Problem to be solved by the invention]

[0005] However, when the conductive composite is dispersed in an organic solvent, even if a water-soluble antioxidant such as that disclosed in Patent Document 1 is added, it cannot be dissolved, resulting in the problem that a sufficient antioxidant function cannot be obtained.

[0006] The present invention provides a conductive polymer-containing liquid containing an additive having an antioxidant function that can be dissolved in an organic solvent, a method for producing the same, and a conductive laminate using the conductive polymer-containing liquid and a method for producing the same. [Means for solving the problem]

[0007] [1] A conductive polymer-containing liquid containing a conductive complex including a π-conjugated conductive polymer and a polyanion, an additive consisting of a compound having one or more phenolic hydroxyl groups and a (meth)acrylic group in the molecule, and at least one of water and an organic solvent. [2] The conductive polymer-containing liquid according to [1], wherein the additive is one or more compounds selected from Compound 1 represented by Formula (1) below. [3] The conductive polymer-containing liquid according to [1] or [2], which contains the organic solvent, and in which some anion groups of the polyanion have been modified by reaction with at least one of an amine compound, an epoxy compound, and a quaternary ammonium compound. [4] The conductive polymer-containing liquid according to [1] or [2], which contains the water and further contains a binder component, the binder component being a water-dispersible resin. [5] The conductive polymer-containing liquid according to any one of [1] to [3], which contains the organic solvent and further contains a binder component, the binder component being an acrylic compound or polyester. [6] The conductive polymer-containing liquid according to any one of [1] to [5], wherein the π-conjugated conductive polymer is poly(3,4-ethylenedioxythiophene) or the polyanion is polystyrene sulfonic acid. [7] A method for producing a conductive polymer-containing liquid, comprising adding a compound having one or more phenolic hydroxyl groups and a (meth)acrylic group in the molecule to a conductive polymer aqueous dispersion containing a conductive complex including a π-conjugated conductive polymer and a polyanion, and at least water among water and an organic solvent. [8] A method for producing a conductive polymer-containing liquid, comprising the step of mixing a conductive complex containing a π-conjugated conductive polymer and a polyanion, an organic solvent, and a compound having one or more phenolic hydroxyl groups and a (meth)acrylic group in the molecule to obtain a conductive polymer-containing liquid, wherein a portion of the anion groups of the polyanion constituting the conductive complex are modified by reaction with at least one of an amine compound, an epoxy compound, and a quaternary ammonium compound. [9] A method for producing a conductive laminate, comprising the steps of applying the conductive polymer-containing liquid according to any one of [1] to [6] to at least a part of the surface of a substrate and drying it to form a conductive layer.

[10] A conductive laminate comprising a substrate and a conductive layer formed on at least a portion of the surface of the substrate, the conductive layer comprising a cured product of the conductive polymer-containing liquid according to any one of [1] to [6]. [Effects of the Invention]

[0008] According to the conductive polymer-containing liquid of the present invention, a conductive layer having excellent resistance to exposure to the atmosphere can be easily formed. According to the method for producing a conductive polymer-containing liquid of the present invention, the above-mentioned conductive polymer-containing liquid can be easily produced. The conductive laminate of the present invention includes a conductive layer that is excellent in resistance to exposure to the atmosphere. According to the method for producing a conductive laminate of the present invention, the conductive laminate can be easily produced.

[0009] This invention is believed to contribute to SDG Goal 12, "Responsible Consumption and Production."

[0010] In this specification and claims, the lower and upper limits of numerical ranges indicated with "to" are included in the numerical range. DETAILED DESCRIPTION OF THE INVENTION

[0011] ≪Conductive polymer-containing liquid≫ A first aspect of the present invention is a conductive polymer-containing liquid containing a conductive complex including a π-conjugated conductive polymer and a polyanion, an additive consisting of a compound having one or more phenolic hydroxyl groups and a (meth)acrylic group in the molecule, and at least one of water and an organic solvent. In the conductive polymer-containing liquid of this embodiment, the conductive complex may be in a dispersed state or a dissolved state, and the terms "dispersed" and "dissolved" are not distinguished unless otherwise specified.

[0012] <π-conjugated conductive polymers> The π-conjugated conductive polymer is not particularly limited as long as it has the effects of the present invention and is an organic polymer whose main chain is composed of a π-conjugated system, and examples thereof include polypyrrole-based conductive polymers, polythiophene-based conductive polymers, polyacetylene-based conductive polymers, polyphenylene-based conductive polymers, polyphenylene vinylene-based conductive polymers, polyaniline-based conductive polymers, polyacene-based conductive polymers, polythiophene vinylene-based conductive polymers, and copolymers thereof. From the viewpoint of stability in air, polypyrrole-based conductive polymers, polythiophenes, and polyaniline-based conductive polymers are preferred, and from the viewpoint of transparency, polythiophene-based conductive polymers are more preferred.

[0013] Polythiophene-based conductive polymers include polythiophene, poly(3-methylthiophene), poly(3-ethylthiophene), poly(3-propylthiophene), poly(3-butylthiophene), poly(3-hexylthiophene), poly(3-heptylthiophene), poly(3-octylthiophene), poly(3-decylthiophene), poly(3-dodecylthiophene), poly(3-octadecylthiophene), poly(3-bromothiophene), poly(3-chlorothiophene), and poly(3-iodothiophene). thiophene), poly(3-cyanothiophene), poly(3-phenylthiophene), poly(3,4-dimethylthiophene), poly(3,4-dibutylthiophene), poly(3-hydroxythiophene), poly(3-methoxythiophene), poly(3-ethoxythiophene), poly(3-butoxythiophene), poly(3-hexyloxythiophene), poly(3-heptyloxythiophene), poly(3-octyloxythiophene), poly(3-decyloxythiophene), poly(3-dodecyloxythiophene) oxythiophene), poly(3-octadecyloxythiophene), poly(3,4-dihydroxythiophene), poly(3,4-dimethoxythiophene), poly(3,4-diethoxythiophene), poly(3,4-dipropoxythiophene), poly(3,4-dibutoxythiophene), poly(3,4-dihexyloxythiophene), poly(3,4-diheptyloxythiophene), poly(3,4-dioctyloxythiophene), poly(3,4-didecyloxythiophene), poly(3,4-di dodecyloxythiophene), poly(3,4-ethylenedioxythiophene), poly(3,4-propylenedioxythiophene), poly(3,4-butylenedioxythiophene), poly(3-methyl-4-methoxythiophene), poly(3-methyl-4-ethoxythiophene), poly(3-carboxythiophene), poly(3-methyl-4-carboxythiophene), poly(3-methyl-4-carboxyethylthiophene), and poly(3-methyl-4-carboxybutylthiophene). Examples of polypyrrole-based conductive polymers include polypyrrole, poly(N-methylpyrrole), poly(3-methylpyrrole), poly(3-ethylpyrrole), poly(3-n-propylpyrrole), poly(3-butylpyrrole), poly(3-octylpyrrole), poly(3-decylpyrrole), poly(3-dodecylpyrrole), poly(3,4-dimethylpyrrole), poly(3,4-dibutylpyrrole), poly(3-carboxypyrrole), poly(3-methyl-4-carboxypyrrole), poly(3-methyl-4-carboxyethylpyrrole), poly(3-methyl-4-carboxybutylpyrrole), poly(3-hydroxypyrrole), poly(3-methoxypyrrole), poly(3-ethoxypyrrole), poly(3-butoxypyrrole), poly(3-hexyloxypyrrole), and poly(3-methyl-4-hexyloxypyrrole). Examples of polyaniline-based conductive polymers include polyaniline, poly(2-methylaniline), poly(3-isobutylaniline), poly(2-anilinesulfonic acid), and poly(3-anilinesulfonic acid). Among the above-mentioned π-conjugated conductive polymers, poly(3,4-ethylenedioxythiophene) is particularly preferable in terms of conductivity, transparency, and heat resistance. The conductive polymer-containing liquid of this embodiment may contain one type of π-conjugated conductive polymer, or two or more types of polymers.

[0014] <Polyanion> A polyanion is a polymer having two or more monomer units with an anionic group in the molecule. The anionic group of this polyanion functions as a dopant for a π-conjugated conductive polymer, improving the conductivity of the π-conjugated conductive polymer. The anionic group of the polyanion is preferably a sulfo group or a carboxy group. Specific examples of such polyanions include polymers having sulfo groups, such as polystyrene sulfonic acid, polyvinyl sulfonic acid, polyallyl sulfonic acid, polyacrylic acid esters having sulfo groups, polymethacrylic acid esters having sulfo groups (for example, poly(4-sulfobutyl methacrylate, polysulfoethyl methacrylate, polymethacryloyloxybenzenesulfonic acid), poly(2-acrylamido-2-methylpropanesulfonic acid), and polyisoprene sulfonic acid; and polymers having carboxylic acid groups, such as polyvinyl carboxylic acid, polystyrene carboxylic acid, polyallyl carboxylic acid, polyacrylic acid, polymethacrylic acid, poly(2-acrylamido-2-methylpropanecarboxylic acid), and polyisoprene carboxylic acid. These may be homopolymers or copolymers of two or more types. Among these polyanions, polymers having sulfo groups are preferred, and polystyrene sulfonic acid is more preferred, as they can provide higher antistatic properties. The polyanions may be used alone or in combination of two or more. The mass-average molecular weight of the polyanion is preferably 20,000 to 1,000,000, more preferably 100,000 to 500,000. The mass-average molecular weight is the average molecular weight based on mass measured using gel permeation chromatography and calculated as pullulan.

[0015] The content of the polyanion in the conductive composite is preferably in the range of 1 part by mass to 1,000 parts by mass, more preferably 10 parts by mass to 700 parts by mass, and even more preferably 100 parts by mass to 500 parts by mass, per 100 parts by mass of the π-conjugated conductive polymer. If the content of the polyanion is equal to or greater than the lower limit, the doping effect on the π-conjugated conductive polymer tends to be stronger, resulting in higher conductivity. On the other hand, if the content of the polyanion is equal to or less than the upper limit, the π-conjugated conductive polymer can be sufficiently contained, thereby ensuring sufficient conductivity.

[0016] A conductive composite is formed by doping a π-conjugated conductive polymer with a polyanion. In the polyanion in the conductive composite, not all of the anionic groups are doped into the π-conjugated conductive polymer, and there are excess anionic groups that are not involved in the doping. Because these excess anionic groups are hydrophilic groups, the dispersibility of a conductive composite that is not modified with an anionic group is high in water but low in organic solvents. Of all the anionic groups in the polyanion, the excess anionic groups preferably account for 30 to 90 mol %, more preferably 45 to 75 mol %, of all the anionic groups in the polyanion.

[0017] The excess anionic groups of the polyanion that are not involved in the doping (hereinafter also referred to as "some anionic groups") may be modified by reaction with at least one of an epoxy compound, an amine compound, and a quaternary ammonium compound.

[0018] When some of the anion groups of the polyanion react with the epoxy compound, the following substituent (A) is formed. When a portion of the anionic groups of the polyanion reacts with an amine compound, the following substituent (B) is formed. When some of the anionic groups of the polyanion react with a quaternary ammonium compound, the following substituent (C) is formed.

[0019] (Substituent A) The substituent (A) is presumed to be a group represented by the following formula (A1) or a group represented by the following formula (A2).

[0020] [ka]

[0021] [In formula (A1), R 1 , R 2 , R 3 , and R 4 are each independently a hydrogen atom or an arbitrary substituent.

[0022] [ka]

[0023] [In formula (A2), m is an integer of 2 or more, and 5 , multiple R 6 , multiple R 7 , and multiple R 8 are each independently a hydrogen atom or an arbitrary substituent, and a plurality of R 5 may be the same or different, and multiple R 6 may be the same or different, and multiple R 7 may be the same or different, and multiple R 8 may be the same or different.]

[0024] In formulas (A1) and (A2), the bond at the left end represents that the substituent (A) is substituted with a proton of an anionic group. Examples of the anionic group having a substituted proton include an anionic group having an active proton bonded to an oxygen atom, such as "-SO3H."

[0025] In formula (A1), R 1 , R 2 , R 3 , and R 4 Examples of the optional substituent of R include an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent. 1 and R 3 may be bonded to form a ring which may have a substituent. For example, R 1 and R 3 and R are the hydrocarbon groups; 1 a divalent hydrocarbon group obtained by removing any one hydrogen atom from the monovalent hydrocarbon group of R 3 and a divalent hydrocarbon group obtained by removing any one hydrogen atom from the monovalent hydrocarbon group above, wherein the carbon atoms from which the hydrogen atom has been removed are bonded to form a ring. In formula (A2), R 5 , R 6 , R7 , and R 8 Examples of the optional substituent of R include an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent. 5 and R 7 may be bonded to form a ring which may have a substituent. Examples of ring formation are the same as those mentioned above. In this specification, the term "optionally substituted" includes both cases where a hydrogen atom (-H) is substituted with a monovalent group and cases where a methylene group (-CH2-) is substituted with a divalent group. Examples of monovalent groups as substituents include alkyl groups having 1 to 4 carbon atoms, alkenyl groups having 2 to 4 carbon atoms, halogen atoms (such as fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms), and trialkoxysilyl groups (such as trimethoxysilyl groups). Examples of the divalent group as a substituent include an oxygen atom (—O—), —C(═O)—, and —C(═O)—O—. m is an integer of 2 or more, preferably 2 to 100, more preferably 2 to 50, and even more preferably 2 to 25. When m is equal to or greater than the above lower limit, the hydrophobicity of the conductive composite is sufficiently high. When m is equal to or less than the above upper limit, it is possible to prevent the hydrophobicity from becoming too high or the conductivity from decreasing.

[0026] An epoxy compound (epoxy group-containing compound) is a compound having one or more epoxy groups in one molecule. From the viewpoint of preventing aggregation or gelation, the epoxy compound is preferably a compound having one epoxy group in one molecule. The epoxy compound that reacts with the polyanion may be one type or two or more types.

[0027] Examples of monofunctional epoxy compounds having one epoxy group per molecule include ethylene oxide, propylene oxide, 2,3-butylene oxide, isobutylene oxide, 1,2-butylene oxide, 1,2-epoxyhexane, 1,2-epoxyheptane, 1,2-epoxypentane, 1,2-epoxyoctane, 1,2-epoxydecane, 1,3-butadiene monoxide, 1,2-epoxytetradecane, glycidyl methyl ether, 1,2-epoxyoctadecane, 1,2-epoxyhexadecane, ...propylene oxide, propylene oxide, propylene oxide, propylene oxide, propylene oxide, propylene oxide, propylene oxide, propylene oxide, propylene oxide, propylene oxide, propylene oxide, propylene oxide, propylene oxide, propylene oxide, propylene oxide, propylene oxide, propylene oxide, propylene Glycidyl ether, glycidyl isopropyl ether, tert-butyl glycidyl ether, 1,2-epoxyeicosane, 2-(chloromethyl)-1,2-epoxypropane, glycidol, epichlorohydrin, epibromohydrin, butyl glycidyl ether, 1,2-epoxyhexane, 1,2-epoxy-9-decane, 2-(chloromethyl)-1,2-epoxybutane, 2-ethylhexyl glycidyl ether, 1,2-epoxy-1H,1H,2H,2H,3H,3H-trifluorobutane, allyl glycidyl ether, tetracyanoethylene oxide, glycidyl butyrate, 1,2-epoxycyclooctane, glycidyl methacrylate, 1,2-epoxycyclododecane, 1-methyl-1,2-epoxycyclohexane, 1,2-epoxycyclopentadecane, 1,2-epoxycyclopentane, 1,2-epoxycyclohexane, 1,2-epoxy-1H,1H,2H,2H,3H,3H-heptadecafluorobutane, 3,4-epoxytetrahydrofuran, glycidyl stearate, 3-glycidyloxypropyltrimethylsilane thoxysilane, epoxysuccinic acid, glycidyl phenyl ether, isophorone oxide, α-pinene oxide, 2,3-epoxynorbornene, benzyl glycidyl ether, diethoxy(3-glycidyloxypropyl)methylsilane, 3-[2-(perfluorohexyl)ethoxy]-1,2-epoxypropane, 1,1,1,3,5,5,5-heptamethyl-3-(3-glycidyloxypropyl)trisiloxane, 9,10-epoxy-1,5-cyclododecadiene, glycidyl 4-tert-butylbenzoate, 2,2-Bis(4-glycidyloxyphenyl)propane, 2-tert-butyl-2-[2-(4-chlorophenyl)]ethyloxirane, styrene oxide, glycidyl trityl ether, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-phenylpropylene oxide, cholesterol-5α,6α-epoxide, stilbene oxide, glycidyl p-toluenesulfonate, ethyl 3-methyl-3-phenylglycidate, N-propyl-N-(2,3-epoxypropyl)perfluoro-n- Examples include octylsulfonamide, (2S,3S)-1,2-epoxy-3-(tert-butoxycarbonylamino)-4-phenylbutane, (R)-glycidyl 3-nitrobenzenesulfonate, glycidyl 3-nitrobenzenesulfonate, parthenolide, N-glycidylphthalimide, endrin, dieldrin, 4-glycidyloxycarbazole, 7,7-dimethyloctanoate [oxiranylmethyl], 1,2-epoxy-4-vinylcyclohexane, and higher alcohol glycidyl ethers having 10 to 16 carbon atoms.

[0028] The higher alcohol glycidyl ether is preferably one or more higher alcohol glycidyl ethers having 10 to 16 carbon atoms, more preferably one or more higher alcohol glycidyl ethers having 12 to 14 carbon atoms, even more preferably at least one of a C12 (12 carbon atoms) higher alcohol glycidyl ether and a C13 (13 carbon atoms) higher alcohol glycidyl ether, and particularly preferably a mixed C12 and C13 higher alcohol glycidyl ether.

[0029] Examples of polyfunctional epoxy compounds having two or more epoxy groups in one molecule include 1,6-hexanediol diglycidyl ether, 1,7-octadiene diepoxide, neopentyl glycol diglycidyl ether, 4-butanediol diglycidyl ether, 1,2:3,4-diepoxybutane, 1,2-cyclohexanedicarboxylic acid diglycidyl, triglycidyl isocyanurate, neopentyl glycol diglycidyl ether, 1,2:3,4-diepoxybutane, polyethylene glycol diglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, and the like. Examples of suitable glycidyl ethers include glycerin diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, trimethylolpropane polyglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hexahydrophthalic acid diglycidyl ester, glycerin polyglycidyl ether, diglycerin polyglycidyl ether, polyglycerin polyglycidyl ether, sorbitol-based polyglycidyl ether, and ethylene oxide lauryl alcohol glycidyl ether.

[0030] The epoxy compound preferably has a molecular weight of 50 or more and 2,000 or less, since this improves dispersibility in organic solvents. Furthermore, the epoxy compound preferably has a carbon number of 4 or more and 120 or less, more preferably 7 or more and 100 or less, even more preferably 10 or more and 80 or less, and particularly preferably 15 or more and 50 or less, since this improves dispersibility in low-polarity hydrocarbon solvents and ester solvents.

[0031] (Substituent B) The substituent (B) is presumed to be a group represented by the following formula (B). -HN + R 11 R 12 R 13 (B) [In formula (B), R 11 ~R13 are each independently a hydrogen atom or a hydrocarbon group which may have a substituent, provided that R 11 ~R 13 At least one of them is a hydrocarbon group which may have a substituent.]

[0032] In the substituent (B), the bond at the left end represents the bond between the negative charge of the anionic group and the positive charge of the amine compound. Examples of anionic groups that can be negatively charged include "-SO3 - ", an anionic group in which an active proton can be bonded to an oxygen atom.

[0033] R in chemical formula (B) 11 ~R 13 is a hydrogen atom or a hydrocarbon group which may have a substituent. 11 ~R 13 is a substituent derived from an amine compound described below. Examples of the hydrocarbon group in chemical formula (B) include an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent. Examples of the aliphatic hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. Examples of the substituent on the aliphatic hydrocarbon group include a phenyl group and a hydroxyl group. Examples of the aromatic hydrocarbon group include a phenyl group and a naphthyl group. Examples of the substituent on the aromatic hydrocarbon group include an alkyl group having 1 to 5 carbon atoms and a hydroxyl group.

[0034] The amine compound is at least one selected from the group consisting of primary amines, secondary amines, and tertiary amines. The amine compound that reacts with the conductive composite may be one type or two or more types. Examples of primary amines include aniline, toluidine, benzylamine, and ethanolamine. Examples of secondary amines include diethanolamine, dimethylamine, diethylamine, dipropylamine, diphenylamine, dibenzylamine, and dinaphthylamine. Examples of tertiary amines include triethanolamine, trimethylamine, triethylamine, tripropylamine, tributylamine, trihexylamine, trioctylamine, triphenylamine, tribenzylamine, and trinaphthylamine. Among the amine compounds, tertiary amines are preferred, and at least one of trioctylamine and tributylamine is more preferred, as this allows for easy production of the conductive polymer-containing liquid of this embodiment.

[0035] In order to enhance dispersibility in organic solvents, the amine compound preferably has a substituent having 4 or more carbon atoms on the nitrogen atom, more preferably has a substituent having 6 or more carbon atoms, and even more preferably has a substituent having 8 or more carbon atoms on the nitrogen atom.

[0036] When the polyanion has a substituent (A) and a substituent (B), the mass ratio of [substituent (A)]:[substituent (B)] (hereinafter also referred to as the A / B ratio) is preferably 10:90 to 90:10, more preferably 20:80 to 80:20, and even more preferably 25:75 to 75:25. When the A / B ratio is within the above range, it is easy to achieve a balance between dispersibility and conductivity. The mass of the [substituent (A)] can be calculated by [(mass of reactant A obtained by reacting an epoxy compound with a conductive composite) - (mass of the conductive composite before reaction with an epoxy compound)]. The mass of the [anionic group bonded to a substituent (B)] can be calculated by [(mass of reactant B obtained by reacting the reactant A with an amine compound) - (mass of reactant A obtained by reacting an epoxy compound with a conductive composite)].

[0037] (Substituent C) The substituent (C) is presumed to be a group represented by the following formula (C).

[0038] -N+ R 11 R 12 R 13 R 14 (C) [In formula (C), R 11 ~R 14 are each independently a hydrocarbon group which may have a substituent.

[0039] In the substituent (C), the bond at the left end is the negative charge of the anion group, for example, the negative charge of the sulfonic acid group "-SO3 - " represents the bond between the ammonium salt and the positive charge of the quaternary ammonium cation.

[0040] R in chemical formula (C) 11 ~R 14 is a hydrocarbon group which may have a substituent. R in chemical formula (C) 11 ~R 14 is a substituent derived from a quaternary ammonium compound. Examples of the hydrocarbon group in chemical formula (C) include an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent. Examples of the aliphatic hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. Examples of the substituent on the aliphatic hydrocarbon group include a phenyl group and a hydroxyl group. Examples of the aromatic hydrocarbon group include a phenyl group and a naphthyl group. Examples of the substituent on the aromatic hydrocarbon group include an alkyl group having 1 to 5 carbon atoms and a hydroxyl group.

[0041] In order to improve dispersibility in organic solvents and conductivity, the quaternary ammonium compound preferably has a substituent on the nitrogen atom having 3 or more carbon atoms, more preferably 5 or more carbon atoms, and even more preferably 7 or more carbon atoms. The upper limit of the number of carbon atoms in each substituent on the nitrogen atom is not particularly limited, and taking into consideration solubility in solvents and reactivity, it is, for example, preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less. In addition, the R 11 ~R 14 The total number of carbon atoms is preferably 8 to 44, more preferably 12 to 40, and even more preferably 16 to 36. The number of carbon atoms in each of the substituents on the nitrogen atom may be the same or different.

[0042] Specific examples of the quaternary ammonium compound include quaternary ammonium salts such as tetramethylammonium salt, tetraethylammonium salt, tetrapropylammonium salt, tetrabutylammonium salt, tetra-n-octylammonium salt, tetraphenylammonium salt, tetrabenzylammonium salt, and tetranaphthylammonium salt. Examples of counter anions of the ammonium cation include halogen ions such as bromide ion and chloride ion, and hydroxy ion.

[0043] When the conductive composite has a substituent (A) and a substituent (C), the mass ratio of [substituent (A)]:[substituent (C)] is preferably 10:90 to 90:10, more preferably 20:80 to 80:20, and even more preferably 25:75 to 75:25. Within this range, dispersibility and conductivity are easily balanced. The mass of [substituent (A)] can be calculated by [(mass of reaction product A obtained by reacting with an epoxy compound) - (mass of the conductive composite before reacting with the epoxy compound and the polyanion not forming the conductive composite)]. The mass of [substituent (C)] can be calculated by [(mass of reaction product C obtained by reacting the reaction product A with a quaternary ammonium compound) - (mass of the reaction product A)].

[0044] The content of the conductive complex relative to the total mass of the conductive polymer-containing liquid of this embodiment is, for example, preferably 0.01 mass % or more and 5 mass % or less, more preferably 0.05 mass % or more and 2 mass % or less, and even more preferably 0.1 mass % or more and 1 mass % or less. When the content is at least as large as the lower limit of the above range, the conductivity of the conductive layer formed by applying the conductive polymer-containing liquid can be further improved. When the content is equal to or less than the upper limit of the above range, the dispersibility of the conductive complex in the conductive polymer-containing liquid is improved, and a uniform conductive layer can be formed.

[0045] <Additives> The conductive polymer-containing liquid of this embodiment contains one or more additives made of a compound having one or more phenolic hydroxyl groups and a (meth)acrylic group in the molecule. The phenolic hydroxyl groups contribute to improving resistance to exposure to the atmosphere, and the (meth)acrylic groups contribute to solubility in organic solvents. Here, the term "(meth)acrylic group" refers to at least one of a methacrylic group and an acrylic group. From the viewpoint of improving solubility in organic solvents, the molecular weight of the additive is preferably 500 or less, more preferably 400 or less, and even more preferably 350 or less. The additive is preferably a compound represented by the following formula (1):

[0046] [ka]

[0047] In formula (1), R1, R2, and R3 each independently represent a hydrogen atom or an arbitrary substituent, provided that at least one of R1, R2, and R3 represents a hydroxyl group. R4 represents a hydrogen atom or a methyl group. Examples of the arbitrary substituent include a hydroxyl group and an alkyl group having 1 to 6 carbon atoms. In this specification, the compounds represented by formula (1) may be collectively referred to as "compound 1." Preferred specific examples of compound 1 include compound 1-a, compound 1-b, and compound 1-c represented by formula (1-a), formula (1-b), and formula (1-c).

[0048] [ka]

[0049] The content of the additive relative to the total mass of the conductive polymer-containing liquid of this embodiment is preferably 0.01 mass% or more and 3.00 mass% or less, more preferably 0.10 mass% or more and 2.00 mass% or less, and even more preferably 0.20 mass% or more and 1.50 mass% or less. When the content is at least as large as the lower limit of the above range, the resistance of the formed conductive layer to exposure to the atmosphere is further improved. When the content is equal to or less than the upper limit of the above range, it is possible to prevent a decrease in conductivity due to a decrease in the relative content of the conductive composite.

[0050] In the conductive polymer-containing liquid of this embodiment, the content of the additive relative to 100 parts by mass of the conductive composite is preferably 10 parts by mass or more and 1,000 parts by mass or less, more preferably 50 parts by mass or more and 750 parts by mass or less, and even more preferably 100 parts by mass or more and 500 parts by mass or less. When the content is at least as large as the lower limit of the above range, the resistance of the formed conductive layer to exposure to the atmosphere is further improved. When the content is equal to or less than the upper limit of the above range, it is possible to prevent a decrease in conductivity due to a decrease in the relative content of the conductive composite.

[0051] <Dispersion medium> The dispersion medium constituting the conductive polymer-containing liquid of this embodiment contains at least one of water and an organic solvent. In this specification, the term "dispersion" may be used without distinguishing between dispersion and dissolution, and the term "dispersion medium" may be used without distinguishing between a dispersion medium and a solvent.

[0052] The conductive composite contained in the conductive polymer-containing liquid is dispersible in water when not chemically modified as described above, and therefore, it is preferable to use an aqueous dispersion medium as the dispersion medium. On the other hand, when the conductive composite is chemically modified and hydrophobic as described above, it is preferable to use an organic solvent as the dispersion medium.

[0053] (organic solvent) The organic solvent may be a water-soluble organic solvent, a water-insoluble organic solvent, or a mixed solvent of a water-soluble organic solvent and a water-insoluble organic solvent. Here, a water-soluble organic solvent is an organic solvent that dissolves in an amount of 1 g or more in 100 g of water at 20° C., and a water-insoluble organic solvent is an organic solvent that dissolves in an amount of less than 1 g in 100 g of water at 20° C.

[0054] Examples of the water-soluble organic solvent include alcohol-based solvents, ether-based solvents, ketone-based solvents, nitrogen atom-containing solvents, and ester-based solvents. Examples of alcohol-based solvents include methanol, ethanol, 1-propanol, 2-propanol (isopropanol), 2-methyl-2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, allyl alcohol, ethylene glycol, propylene glycol, propylene glycol monomethyl ether, and ethylene glycol monomethyl ether. Examples of the ether solvent include diethyl ether, dimethyl ether, propylene glycol dialkyl ether, and diethylene glycol diethyl ether. Examples of ketone solvents include diethyl ketone, methyl propyl ketone, methyl butyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, methyl amyl ketone, diisopropyl ketone, methyl ethyl ketone, acetone, and diacetone alcohol. Examples of nitrogen atom-containing solvents include N-methylpyrrolidone, dimethylacetamide, and dimethylformamide. The water-soluble organic solvents may be used alone or in combination of two or more. The water-soluble organic solvent is preferably an alcohol-based solvent or a ketone-based solvent, as this improves the coating properties of the conductive polymer-containing liquid on the substrate.

[0055] Examples of the non-water-soluble organic solvent include hydrocarbon solvents, etc. Examples of the hydrocarbon solvent include aliphatic hydrocarbon solvents and aromatic hydrocarbon solvents. Examples of the aliphatic hydrocarbon solvent include hexane, cyclohexane, pentane, heptane, octane, nonane, decane, and dodecane. Examples of aromatic hydrocarbon solvents include benzene, toluene, xylene, ethylbenzene, propylbenzene, and isopropylbenzene. The water-insoluble organic solvents may be used alone or in combination of two or more. Among the non-water-soluble organic solvents, aromatic hydrocarbon solvents are preferred, and toluene is more preferred, in terms of ease of producing the conductive polymer-containing liquid in this embodiment.

[0056] When the conductive composite of this embodiment is chemically modified as described above to have the substituent (A), the substituent (B), or the substituent (C) and to be hydrophobized, the content of the organic solvent relative to the total mass of the dispersion medium of the conductive polymer-containing liquid is preferably more than 50 mass%, more preferably 70 mass% to 100 mass%, and even more preferably 90 mass% to 100 mass%. When the content ratio of the organic solvent is within the above range, the hydrophobized conductive composite can be easily dispersed, and the conductive layer can be easily formed.

[0057] (aqueous dispersion medium) The aqueous dispersion medium is water or a mixture of water and a water-soluble organic solvent. Examples of the water-soluble organic solvent include alcohol-based solvents and ketone-based solvents. One type of water-soluble organic solvent may be used alone, or two or more types may be used in combination. The content of water relative to the total mass of the aqueous dispersion medium is 15% by mass or more, preferably 60% by mass or more, more preferably 80% by mass or more, and may be 100% by mass.

[0058] When the conductive composite of this embodiment does not have the above-mentioned chemical modification, it is desirable that the dispersion medium contain a large amount of water from the viewpoint of dispersing the conductive composite, but it is preferable that the dispersion medium contain a large amount of organic solvent, particularly alcohol-based solvent, from the viewpoint of increasing the solubility of Compound 1. From the viewpoint of achieving a balance between the dispersibility of the unmodified conductive composite and the solubility of Compound 1, the ratio of water:organic solvent (e.g., alcohol-based solvent) to the total mass of the dispersion medium of the conductive polymer-containing liquid of this embodiment is, in this order, preferably 10:90 to 50:50, more preferably 15:85 to 40:60, and may be 20:80 to 30:70 within this range.

[0059] <Binder components> The conductive polymer-containing liquid of this embodiment may contain a binder component. The binder component is a resin other than the π-conjugated conductive polymer and the polyanion or a precursor thereof, and is a thermoplastic resin or a curable monomer or oligomer that cures during the formation of the conductive layer. The thermoplastic resin becomes the binder resin as it is, and the curable monomer or oligomer becomes the resin formed by curing. The binder component may be used alone or in combination of two or more kinds.

[0060] Specific examples of binder resins derived from binder components include epoxy resins, acrylic resins (acrylic compounds), polyester resins, polyurethane resins, polyimide resins, polyether resins, melamine resins, and silicones.

[0061] The curable monomer or oligomer may be a thermosetting monomer or oligomer, or a photocurable monomer or oligomer, where the oligomer is a polymer having a mass average molecular weight of less than 10,000. Examples of the curable monomer include an acrylic monomer (acrylic compound), an epoxy monomer, and an organosiloxane. Examples of the curable oligomer include an acrylic oligomer (acrylic compound), an epoxy oligomer, and a silicone oligomer (curable silicone). When an acrylic monomer or an acrylic oligomer is used as the binder component, it can be easily cured by heating or irradiating with light.

[0062] When a curable monomer or oligomer is contained, it is preferable to further contain a curing catalyst. For example, when a thermosetting monomer or oligomer is contained, it is preferable to contain a thermal polymerization initiator that generates radicals upon heating, and when a photocurable monomer or oligomer is contained, it is preferable to contain a photopolymerization initiator that generates radicals upon light irradiation.

[0063] When a curable monomer or oligomer is contained as a binder component, the monomer or oligomer preferably has at least one functional group selected from the group consisting of an epoxy group and an oxetane group, in order to enhance the curability of the binder component. The epoxy resin is formed by curing the monomer or oligomer (prepolymer) having the epoxy group or the oxetane group.

[0064] When the dispersion medium of the conductive polymer-containing liquid is an aqueous dispersion medium, the binder resin contained therein is preferably a water-dispersible resin, more preferably a water-dispersible emulsion resin. The water-dispersible resin is an emulsion resin or a water-soluble resin.

[0065] Specific examples of water-dispersible emulsion resins include acrylic resins, polyester resins, polyurethane resins, polyimide resins, melamine resins, etc., which are emulsified with an emulsifier. Among these, polyester emulsions are preferred because they increase the strength of the coating film formed by applying the conductive polymer-containing liquid to the film substrate and improve the adhesion of the coating film to the film substrate.

[0066] Specific examples of the water-soluble resin include acrylic resin, polyester resin, polyurethane resin, polyimide resin, and melamine resin, which have an acid group such as a carboxy group or a sulfo group or a salt thereof. Here, the water-soluble resin is preferably one that dissolves in 100 g of distilled water at 25° C. in an amount of 1 g or more, preferably 5 g or more, and more preferably 10 g or more.

[0067] The acid group, such as a carboxy group or a sulfo group, contained in the water-dispersible resin may form a salt with a cation, such as a sodium ion or a potassium ion.

[0068] The content ratio of the binder component in the conductive polymer-containing liquid is preferably 100 parts by mass or more and 10,000 parts by mass or less, more preferably 200 parts by mass or more and 5,000 parts by mass or less, and even more preferably 300 parts by mass or more and 3,000 parts by mass or less, relative to 100 parts by mass of the conductive composite. When the content of the binder component is equal to or greater than the lower limit, the film strength of the formed conductive layer can be further improved. When the content of the binder component is equal to or less than the upper limit, a decrease in conductivity due to a decrease in the content of the conductive composite can be suppressed.

[0069] (Other additives) The conductive polymer-containing liquid may contain other known additives. The additives are not particularly limited as long as they can achieve the effects of the present invention, and examples thereof include surfactants, inorganic conductive agents, antifoaming agents, coupling agents, antioxidants, and ultraviolet absorbers. The surfactant may be a nonionic, anionic, or cationic surfactant, with the nonionic surfactant being preferred from the standpoint of storage stability. A polymer surfactant such as polyvinylpyrrolidone may also be added. Examples of inorganic conductive agents include metal ions, conductive carbon, etc. Metal ions can be generated by dissolving a metal salt in water. Examples of the antifoaming agent include silicone resin, polydimethylsiloxane, and silicone oil. The coupling agent may be a silane coupling agent having a vinyl group or an amino group. Examples of the ultraviolet absorber include benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, salicylate-based ultraviolet absorbers, cyanoacrylate-based ultraviolet absorbers, oxanilide-based ultraviolet absorbers, hindered amine-based ultraviolet absorbers, and benzoate-based ultraviolet absorbers. When the conductive polymer-containing liquid of this embodiment contains the additive, the content thereof is determined appropriately depending on the type of additive, and can be, for example, in the range of 0.001 parts by mass or more and 5 parts by mass or less per 100 parts by mass of the π-conjugated conductive polymer.

[0070] <Method 1 for producing conductive polymer-containing liquid> A second aspect of the present invention is a method for producing a conductive polymer-containing liquid, the method comprising adding a compound having one or more phenolic hydroxyl groups and a (meth)acrylic group in the molecule to a conductive polymer aqueous dispersion containing a conductive complex including a π-conjugated conductive polymer and a polyanion, and at least water among water and an organic solvent. The manufacturing method of this embodiment makes it possible to manufacture the conductive polymer-containing liquid of the first embodiment.

[0071] The conductive polymer aqueous dispersion can be prepared by a known method, for example, by polymerizing a monomer that forms a π-conjugated conductive polymer in a reaction solution containing a polyanion and an aqueous dispersion medium, to obtain a conductive polymer aqueous dispersion containing a conductive complex including the π-conjugated conductive polymer and a polyanion, and the aqueous dispersion medium.

[0072] The method for polymerizing the monomer is preferably polymerization by chemical oxidation. Chemical oxidation polymerization can be carried out using a known catalyst and oxidizing agent. Examples of the catalyst include transition metal compounds such as ferric chloride, ferric sulfate, ferric nitrate, and cupric chloride. Examples of the oxidizing agent include persulfates such as ammonium persulfate, sodium persulfate, and potassium persulfate.

[0073] A desired amount of the compound is added as an additive to a conductive polymer aqueous dispersion containing a conductive complex at a desired concentration, and a binder component and other additives are optionally blended to obtain a desired conductive polymer-containing liquid.

[0074] <<Method 2 for producing conductive polymer-containing liquid>> A third aspect of the present invention is a method for producing a conductive polymer-containing liquid, comprising the step of mixing a conductive complex containing a π-conjugated conductive polymer and a polyanion, an organic solvent, and a compound having one or more phenolic hydroxyl groups and a (meth)acrylic group in the molecule to obtain a conductive polymer-containing liquid, wherein a portion of the anion groups of the polyanion constituting the conductive complex have been modified by reaction with at least one of an amine compound, an epoxy compound, and a quaternary ammonium compound. The manufacturing method of this embodiment makes it possible to manufacture the conductive polymer-containing liquid of the first embodiment.

[0075] The conductive composite modified by the reaction can be prepared by a known method. For example, a modified conductive composite can be obtained by adding at least one of an amine compound, an epoxy compound, and a quaternary ammonium compound to an aqueous conductive polymer dispersion and allowing the mixture to react. For another example, the aqueous dispersion medium of the aqueous conductive polymer dispersion is removed by freeze-drying to obtain a freeze-dried conductive composite. An organic solvent and at least one of an amine compound, an epoxy compound, and a quaternary ammonium compound are then added to the freeze-dried conductive composite and allowed to react, thereby obtaining a modified conductive composite.

[0076] The desired conductive polymer-containing liquid can be obtained by blending the modified conductive composite, the organic solvent, the compound (additive), and optional components such as binder components and other additives in any ratio.

[0077] From the viewpoint of improving the dispersibility of the conductive composite in the obtained conductive polymer-containing liquid, it is preferable to carry out stirring using a dispersing machine with high shear force (such as a high-pressure homogenizer).

[0078] <Method for manufacturing conductive laminate> A fourth aspect of the present invention is a method for producing a conductive laminate, comprising the steps of applying the conductive polymer-containing liquid of the first aspect to at least a part of the surface of a substrate and drying the applied liquid to form a conductive layer.

[0079] Examples of a method for applying (coating) the conductive polymer-containing liquid to any surface of a substrate include a method using a coater such as a gravure coater, roll coater, curtain flow coater, spin coater, bar coater, reverse coater, kiss coater, fountain coater, rod coater, air doctor coater, knife coater, blade coater, cast coater, or screen coater; a method using a sprayer such as an air spray, airless spray, or rotor dampening; and an immersion method such as dipping.

[0080] The amount of the conductive polymer-containing liquid to be applied to the substrate is not particularly limited, but for example, it is 0.01 to 10.0 g / m as a non-volatile component. 2 The range is preferred.

[0081] The conductive layer can be formed by drying the coating film made of the conductive polymer-containing liquid applied onto the substrate to remove at least a portion of the dispersion medium and then curing the coating film. Methods for drying the coating film include heat drying, vacuum drying, etc. Heat drying can be performed using, for example, hot air heating or infrared heating. When heat drying is applied, the heating temperature is appropriately set depending on the dispersion medium used, but is usually within the range of 50°C to 200°C. Here, the heating temperature is the temperature set in the drying device. A suitable drying time within the above heating temperature range is preferably 0.5 minutes to 30 minutes, more preferably 1 minute to 15 minutes.

[0082] <Conductive laminate> A conductive laminate according to a fifth aspect of the present invention includes a substrate and a conductive layer formed on at least a portion of the surface of the substrate, the conductive layer including a cured product of the conductive polymer-containing liquid according to the first aspect. The conductive laminate according to this aspect may be produced by the production method according to the fourth aspect or by another method.

[0083] [Conductive layer] The conductive layer may be formed over the entire surface of the substrate or over only a portion of the surface. In a conductive film, it is preferable that a conductive layer of substantially uniform thickness is formed over substantially the entire surface of one or the other of the film substrate. When a conductive layer is formed over only a portion of the surface of the substrate, the conductive layer may be, for example, a fine conductive pattern such as a circuit or electrode, or may be simply a roughly divided area where a conductive layer is provided and an area where a conductive layer is not provided exist on the same surface.

[0084] The average thickness of the conductive layer is, for example, preferably 10 nm or more and 100 μm or less, more preferably 20 nm or more and 50 μm or less, and even more preferably 30 nm or more and 30 μm or less. When the average thickness of the conductive layer is equal to or greater than the lower limit, high conductivity can be exhibited, and when the average thickness is equal to or less than the upper limit, the adhesiveness of the conductive layer to the substrate is further improved.

[0085] [Base material] The substrate may be made of an insulating material or a conductive material. The shape of the substrate is not particularly limited, and examples thereof include a shape mainly having a flat surface, such as a film or a substrate. Examples of insulating materials include glass, synthetic resin, and ceramics. Examples of conductive materials include metals, conductive metal oxides, and carbon.

[0086] (Film substrate) When a film substrate is used as the substrate, the conductive laminate becomes a conductive film. Examples of the film substrate include plastic films made of synthetic resins, such as ethylene-methyl methacrylate copolymer resin, ethylene-vinyl acetate copolymer resin, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinyl alcohol, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyacrylate, polycarbonate, polyvinylidene fluoride, polyarylate, styrene-based elastomers, polyester-based elastomers, polyethersulfone, polyetherimide, polyetheretherketone, polyphenylene sulfide, polyimide, cellulose triacetate, and cellulose acetate propionate. From the viewpoint of improving the adhesion between the film substrate and the conductive layer, the synthetic resin for the film substrate is preferably a polyester resin, and among these, polyethylene terephthalate is preferred.

[0087] The synthetic resin for the film substrate may be amorphous or crystalline. The film substrate may be unstretched or stretched. The film substrate may be subjected to a surface treatment such as corona discharge treatment, plasma treatment, or flame treatment in order to further improve the adhesion of the conductive layer.

[0088] The average thickness of the film substrate is preferably 5 μm or more and 500 μm or less, and more preferably 20 μm or more and 200 μm or less. When the average thickness of the film substrate is equal to or more than the lower limit, the film is less likely to break, and when the average thickness is equal to or less than the upper limit, the film can have sufficient flexibility. The average thickness of the film substrate is determined by measuring the thickness at 10 randomly selected locations and averaging the measured values.

[0089] (glass substrate) Examples of the glass substrate include an alkali-free glass substrate, a soda-lime glass substrate, a borosilicate glass substrate, and a quartz glass substrate. If the substrate contains an alkali component, the conductivity of the conductive layer tends to decrease. Therefore, among the glass substrates, an alkali-free glass is preferred. Here, alkali-free glass refers to a glass composition having an alkali component content of 0.1% by mass or less relative to the total mass of the glass composition.

[0090] The average thickness of the glass substrate is preferably 100 μm or more and 3000 μm or less, and more preferably 100 μm or more and 1000 μm or less. When the average thickness of the glass substrate is equal to or more than the lower limit, the glass substrate is less likely to break, and when the average thickness is equal to or less than the upper limit, the conductive laminate can be made thinner. The average thickness of the glass substrate is determined by measuring the thickness at 10 randomly selected locations and averaging the measured values. [Example]

[0091] (Production Example 1) Production of polystyrene sulfonic acid 206 g of sodium styrenesulfonate was dissolved in 1000 ml of ion-exchanged water, and while stirring at 80°C, 1.14 g of an oxidizing agent solution of ammonium persulfate, which had been dissolved in 10 ml of water in advance, was added dropwise over 20 minutes, and the solution was stirred for 12 hours. To the resulting sodium polystyrene sulfonate-containing solution, 1000 ml of sulfuric acid diluted to 10% by mass was added, and 1000 ml of the solvent from the resulting polystyrene sulfonic acid-containing solution was removed by ultrafiltration. Next, 2000 ml of ion-exchanged water was added to the remaining solution, and approximately 2000 ml of the solvent was removed by ultrafiltration, and the polystyrene sulfonic acid was washed with water. This water washing procedure was repeated three times. Water in the resulting solution was removed under reduced pressure to obtain colorless solid polystyrene sulfonic acid.

[0092] (Production Example 2) Synthesis of a conductive polymer dispersion containing a π-conjugated conductive polymer and a polyanion 14.2 g of 3,4-ethylenedioxythiophene and a solution prepared by dissolving 36.7 g of polystyrene sulfonic acid in 2000 ml of ion-exchanged water were mixed at 20°C. The resulting mixed solution was kept at 20°C and, while stirring, an oxidation catalyst solution of 29.64 g of ammonium persulfate and 8.0 g of ferric sulfate dissolved in 200 ml of ion-exchanged water was slowly added, followed by stirring for 3 hours to allow the reaction to proceed. To the resulting reaction solution, 2000 ml of ion-exchanged water was added, and about 2000 ml of the solvent was removed by ultrafiltration. This procedure was repeated three times. Next, 200 ml of 10% diluted sulfuric acid and 2,000 ml of ion-exchanged water were added to the resulting solution, and approximately 2,000 ml of the solvent was removed by ultrafiltration. 2,000 ml of ion-exchanged water was added to the remaining liquid, and approximately 2,000 ml of the solvent was removed by ultrafiltration. This procedure was repeated three times. 2000 ml of ion-exchanged water was added to the resulting solution, and approximately 2000 ml of the solvent was removed by ultrafiltration. This procedure was repeated five times to obtain an aqueous dispersion of polystyrene sulfonate-doped poly(3,4-ethylenedioxythiophene) (PEDOT-PSS) with a concentration of 1.2% by mass.

[0093] (Production Example 3) 1000 g of the aqueous dispersion of PEDOT-PSS obtained in Production Example 2 was freeze-dried to obtain 12 g of a freeze-dried product of PEDOT-PSS (conductive composite).

[0094] (Production Example 4) 4.0 g of freeze-dried PEDOT-PSS and 3.5 g of trioctylamine were added to 1000 g of isopropanol and dispersed using a high-pressure homogenizer to obtain a conductive mixed solution containing PEDOT-PSS and amine (i.e., PEDOT-PSS in which the excess sulfonic acid groups not bonded to the PEDOT in PSS have been modified with trioctylamine).

[0095] (Production Example 5) To 100 g of the aqueous dispersion of PEDOT-PSS obtained in Production Example 2, 300 g of methanol and 25 g of an epoxy compound (Epolite M-1230, C12, C13 mixed higher alcohol glycidyl ether, manufactured by Kyoeisha Chemical Co., Ltd.) were added and heated with stirring at 60°C for 4 hours. During this time, the epoxy compound bonded to the excess sulfonic acid groups in the PEDOT-PSS that were not bonded to the PEDOT in the PSS, resulting in the disappearance of the excess sulfonic acid groups. As a result, the aqueous dispersibility of the PEDOT-PSS decreased, and a conductive composite containing the PEDOT-PSS and the epoxy compound that reacted and bonded to it was precipitated. This precipitate was collected by filtration, yielding 1.575 g of the conductive composite. Next, the above conductive complex was added to 315 g of methyl ethyl ketone and dispersed using a high-pressure homogenizer to obtain a conductive mixed solution containing a π-conjugated conductive polymer, a polyanion, and an epoxy compound (i.e., containing PEDOT-PSS modified by reaction with an epoxy compound).

[0096] (Production Example 6) 50 g of gallic acid was dissolved in 200 g of ethanol, and 2.4 g of triethylamine was added to the solution. 51.3 g of glycidyl methacrylate was then added dropwise and stirred at 80°C for 10 hours. After the reaction was completed, 300 g of butyl acetate and 500 g of water were added, and the lower layer was removed. The resulting butyl acetate solution was concentrated using an evaporator to obtain 100 g of compound 1-a.

[0097] (Production Example 7) 50 g of 3,4-dihydroxybenzoic acid was dissolved in 200 g of ethanol, and 2.4 g of triethylamine was added to the solution. 51.3 g of glycidyl methacrylate was then added dropwise and stirred at 80°C for 10 hours. After the reaction was completed, 300 g of butyl acetate and 500 g of water were added, and the lower layer was removed. The resulting butyl acetate solution was concentrated using an evaporator to obtain 100 g of compound 1-b.

[0098] (Production Example 8) 50 g of 4-hydroxybenzoic acid was dissolved in 200 g of ethanol, and 2.4 g of triethylamine was added to the solution. 51.3 g of glycidyl methacrylate was then added dropwise and stirred at 80°C for 10 hours. After the reaction was completed, 300 g of butyl acetate and 500 g of water were added, and the lower layer was removed. The resulting butyl acetate solution was concentrated using an evaporator to obtain 100 g of compound 1-c.

[0099] Example 1 A coating material consisting of a conductive polymer-containing liquid was obtained by adding 80 g of methanol, 10 g of water-dispersible polyester PLASCOAT RZ-105 (manufactured by GOO Chemical Industry Co., Ltd., an aqueous solution with a solids concentration of 25% by mass), and 0.25 g of the compound 1-a to 10 g of the aqueous dispersion of PEDOT-PSS obtained in Production Example 2. This coating material was applied to a PET film (manufactured by Toray Industries, Inc., Lumirror T60) using a #2 bar coater and dried at 120°C for 1 minute to obtain a conductive film with a conductive layer formed on the surface.

[0100] Example 2 A conductive film was obtained in the same manner as in Example 1, except that the amount of compound 1-a added was changed from 0.25 g to 0.5 g.

[0101] Example 3 A conductive film was obtained in the same manner as in Example 1, except that 0.25 g of the compound 1-a was changed to 0.25 g of the compound 1-b.

[0102] Example 4 A conductive film was obtained in the same manner as in Example 1, except that 0.25 g of the compound 1-a was changed to 0.5 g of the compound 1-b.

[0103] Example 5 A conductive film was obtained in the same manner as in Example 1, except that 0.25 g of the compound 1-a was changed to 0.25 g of the compound 1-c.

[0104] Example 6 A conductive film was obtained in the same manner as in Example 1, except that 0.25 g of the compound 1-a was changed to 0.5 g of the compound 1-c.

[0105] (Comparative Example 1) A conductive film was obtained in the same manner as in Example 1, except that the compound 1-a was not added.

[0106] (Comparative Example 2) A conductive film was obtained in the same manner as in Example 1, except that the compound 1-a was changed to gallic acid.

[0107] (Comparative Example 3) A conductive film was obtained in the same manner as in Example 2, except that the compound 1-a was changed to gallic acid.

[0108] <Evaluation> For each conductive film, the surface resistance (initial surface resistance) R0 was measured within one hour after production, and the surface resistance R1 was measured after leaving the film at a temperature of 85°C for 10 days. A resistivity meter (Hiresta, manufactured by Nitto Seiko Analytech Co., Ltd.) was used for the measurements, and the applied voltage was 10 V. The results of each measurement are shown in Table 1. In the table, 1.0E+10 means 1.0 x 10 10 The same applies to others.

[0109] [Table 1]

[0110] Example 7 To 81.25 g of the conductive mixed liquid obtained in Production Example 4, 3.75 g of urethane acrylate (Artresin UN-904M manufactured by Negami Chemical Industrial Co., Ltd., a methyl ethyl ketone solution with a solids concentration of 80% by mass), 15 g of diacetone alcohol, 0.075 g of Irgacure 127, and 0.6 g of the compound 1-a were added to prepare a coating material consisting of a conductive polymer-containing liquid. This coating material was applied to a PET film (Lumirror T60 manufactured by Toray Industries, Inc.) using a #16 bar coater, dried at 120°C for 1 minute, and irradiated with ultraviolet light at an energy of 400 mJ to obtain a conductive film with a conductive layer formed on the surface. The surface of the conductive layer of the obtained conductive film was wiped with steel wool #0000 at 1 kg / cm 2 After rubbing the surface 10 times with a load of 1000, the number of scratches was counted.

[0111] Example 8 A conductive film was obtained in the same manner as in Example 7, except that the amount of compound 1-a added was changed from 0.6 g to 1.2 g.

[0112] Example 9 A conductive film was obtained in the same manner as in Example 7, except that 0.6 g of the compound 1-a was changed to 0.6 g of the compound 1-b.

[0113] Example 10 A conductive film was obtained in the same manner as in Example 7, except that 0.6 g of the compound 1-a was changed to 1.2 g of the compound 1-b.

[0114] Example 11 A conductive film was obtained in the same manner as in Example 7, except that 0.6 g of the compound 1-a was changed to 0.6 g of the compound 1-c.

[0115] Example 12 A conductive film was obtained in the same manner as in Example 7, except that 0.6 g of the compound 1-a was changed to 1.2 g of the compound 1-c.

[0116] Comparative Example 4 A conductive film was prepared in the same manner as in Example 7, except that the compound 1-a was not added. obtained.

[0117] (Comparative Example 5) A conductive film was obtained in the same manner as in Example 7, except that the compound 1-a was changed to gallic acid.

[0118] (Comparative Example 6) A conductive film was obtained in the same manner as in Example 8, except that the compound 1-a was changed to gallic acid.

[0119] <Evaluation> For the conductive film of each example, the initial surface resistance R0 and the surface resistance R1 after standing at 85° C. for 10 days were measured in the same manner as in Example 1. The measurement results are shown in Table 2.

[0120] [Table 2]

[0121] Example 13 A coating material consisting of a conductive polymer-containing liquid was prepared by adding 15 g of polyester (Vylon 240, manufactured by Toyobo Co., Ltd., a methyl ethyl ketone solution with a solids concentration of 20% by mass) and 0.3 g of the compound 1-a to 85 g of the conductive mixed liquid obtained in Production Example 5. This coating material was applied to a PET film (Lumirror T60, manufactured by Toray Industries, Inc.) using a #2 bar coater and dried at 120°C for 1 minute to obtain a conductive film with a conductive layer formed on the surface.

[0122] Example 14 A conductive film was obtained in the same manner as in Example 13, except that the amount of compound 1-a added was changed from 0.3 g to 0.6 g.

[0123] Example 15 A conductive film was obtained in the same manner as in Example 13, except that 0.3 g of the compound 1-a was changed to 0.3 g of the compound 1-b.

[0124] Example 16 A conductive film was obtained in the same manner as in Example 13, except that 0.3 g of the compound 1-a was changed to 0.6 g of the compound 1-b.

[0125] Example 17 A conductive film was obtained in the same manner as in Example 13, except that 0.3 g of the compound 1-a was changed to 0.3 g of the compound 1-c.

[0126] Example 18 A conductive film was obtained in the same manner as in Example 13, except that 0.3 g of the compound 1-a was changed to 0.6 g of the compound 1-c.

[0127] (Comparative Example 7) A conductive film was obtained in the same manner as in Example 13, except that the compound 1-a was not added.

[0128] (Comparative Example 8) A conductive film was obtained in the same manner as in Example 13, except that the compound 1-a was changed to gallic acid.

[0129] (Comparative Example 9) A conductive film was obtained in the same manner as in Example 14, except that the compound 1-a was changed to gallic acid.

[0130] <Evaluation> For the conductive film of each example, the initial surface resistance R0 and the surface resistance R1 after standing at 85° C. for 10 days were measured in the same manner as in Example 1. The measurement results are shown in Table 3.

[0131] [Table 3]

[0132] <Result> The smaller the surface resistance value in each measurement result, the higher the conductivity. Also, the closer the surface resistance ratio (R1 / R0) is to 1.0, the more the deterioration of conductivity over time in the atmosphere is suppressed (higher resistance to atmospheric exposure). It is clear that the conductive layers formed using the conductive polymer-containing liquids of Examples 1 to 18 containing Compound 1 have the same initial conductivity as Comparative Examples 1 to 3 which do not contain Compound 1, but have higher resistance to exposure to the atmosphere.

[0133] Compounds 1-a, 1-b, and 1-c differ in the number of hydroxyl groups in the molecule. Of these, the conductive layer formed from the cured product of the conductive polymer-containing liquid to which compound 1-a was added exhibited particularly excellent conductivity.

[0134] The conductive polymer-containing liquids of Examples 1 to 6 were alcohol solvent-based paints containing a small amount of water, and were able to sufficiently dissolve Compound 1. In addition, they also had good compatibility with the polyester blended as a binder component.

[0135] The conductive polymer-containing liquids of Examples 7 to 12 were water-free alcohol solvent-based paints, and were able to sufficiently dissolve Compound 1. Furthermore, it is believed that when a urethane acrylate having a urethane bond and an acrylic group in the molecule and a photopolymerization initiator were blended as binder components and polymerized in the coating film, Compound 1 also copolymerized. As a result, the stability of Compound 1 in the coating film was improved, preventing volatilization and bleeding out, further improving resistance to atmospheric exposure. Furthermore, it was found that the abrasion resistance of the conductive layers of each Example was also improved.

[0136] The conductive polymer-containing liquids of Examples 13 to 18 were paints containing ketone-based solvents that did not contain water, and were able to sufficiently dissolve Compound 1. In addition, they also had good compatibility with the polyester blended as a binder component.

Claims

1. A conductive polymer-containing liquid comprising: a conductive complex containing a π-conjugated conductive polymer and a polyanion; an additive consisting of a compound having one or more phenolic hydroxyl groups and a (meth)acrylic group in the molecule; and at least one of water and an organic solvent.

2. The conductive polymer-containing liquid according to claim 1 , wherein the additive is one or more compounds selected from the group consisting of compounds 1 represented by formula (1): 【Chemistry 1】 [In the formula, R １ , R ２ , and R ３ each independently represents a hydrogen atom or an arbitrary substituent. １ , R ２ , and R ３ At least one of R represents a hydroxyl group. ４ represents a hydrogen atom or a methyl group.

3. 3. The conductive polymer-containing liquid according to claim 2, comprising the organic solvent, wherein a part of anion groups of the polyanion has been modified by reaction with at least one of an amine compound, an epoxy compound, and a quaternary ammonium compound.

4. The conductive polymer-containing liquid according to claim 2 , which contains the water and further contains a binder component, the binder component being a water-dispersible resin.

5. The conductive polymer-containing liquid according to claim 3 , comprising the organic solvent and further comprising a binder component, the binder component being an acrylic compound or a polyester.

6. 6. The conductive polymer-containing liquid according to claim 1, wherein the π-conjugated conductive polymer is poly(3,4-ethylenedioxythiophene), or the polyanion is polystyrene sulfonic acid.

7. A method for producing a conductive polymer-containing liquid, comprising adding a compound having one or more phenolic hydroxyl groups and a (meth)acrylic group in the molecule to a conductive polymer aqueous dispersion containing a conductive complex including a π-conjugated conductive polymer and a polyanion, and at least water among water and an organic solvent.

8. The method includes a step of mixing a conductive complex containing a π-conjugated conductive polymer and a polyanion, an organic solvent, and a compound having one or more phenolic hydroxyl groups and a (meth)acrylic group in the molecule to obtain a conductive polymer-containing liquid, a method for producing a conductive polymer-containing liquid, wherein a part of an anion group of the polyanion constituting the conductive complex is modified by a reaction with at least one of an amine compound, an epoxy compound, and a quaternary ammonium compound.

9. A method for producing a conductive laminate, comprising the steps of applying the conductive polymer-containing liquid according to claim 1 to at least a part of the surface of a substrate and drying the liquid to form a conductive layer.

10. A conductive laminate comprising a substrate and a conductive layer formed on at least a portion of the surface of the substrate, the conductive layer comprising a cured product of the conductive polymer-containing liquid according to claim 1.

Images